TW200406031A - Organic compositions - Google Patents

Abstract

The present invention provides a composition comprising: (a) dielectric material; and (b) porogen comprising at least two fused aromatic rings wherein each of the fused aromatic rings has at least one alkyl substituent thereon and a bond exists between at least two of the alkyl substituents on adjacent aromatic rings. Preferably, the dielectric material is a composition comprising (a) thermosetting component comprising (1) optionally monomer of Formula I as set forth below and (2) at least one oligomer or polymer of Formula II as set forth below where Q, G, h, i, j, and w are as set forth below and (b) porogen. Preferably, the porogen is selected from the group consisting of unfunctionalized polyacenaphthylene homopolymer, functionalized polyacenaphthylene homopolymer, polyacenaphthylene copolymer, polynorbornene, polycaprolactone, poly(2-vinylnaphthalene), vinyl anthracene, polystyrene, polystyrene derivatives, polysiloxane, polyester, polyether, polyacrylate, aliphatic polycarbonate, polysulfone, polylactide, and blends thereof. The present compositions are particularly useful as dielectric substrate material in microchips, multichip modules, laminated circuit boards, and printed wiring boards.

Description

200406031 玖 发明 Description of the invention (The description of the invention shall state: the technical field, prior art, content, implementation, and drawings of the invention are briefly explained) The rights of the application under review This case is under review 10/158513, the application date of 2002 Part of the serial case on May 30, 2015, the case requested the following examination of the rights of the temporary patent application jointly assigned: 60/294864, application date May 30, 2001; 60/350187, application date January 2002 15; 60/350557, application date January 22, 2002; 60/353011, January 30, 2002; 60/376219, April 29, 2002; and 60/378424, application date May 7, 2002 Date, all incorporated herein by reference. TECHNICAL FIELD The present invention relates to a semiconductor device, and more particularly, to a semiconductor device having an organic low dielectric constant material and a method for manufacturing the same. Prior art In order to improve the performance and speed of semiconductor devices, semiconductor device manufacturers sought to reduce the line width and pitch of interconnect devices, while minimizing transmission loss, and reducing the capacitive coupling of interconnect devices. One way to reduce power consumption and reduce capacitance is to lower the dielectric constant (also known as "k") of the insulating or dielectric material separating the interconnects. It is particularly desirable for insulating materials to have low dielectric constants. Low dielectric constants typically allow faster signal propagation, reduced capacitance and crosstalk between conductors, and reduced voltage required to drive integrated circuits. Since the air has a dielectric constant = 1.0, the main purpose is to reduce the dielectric constant of the insulating material to a theoretical limit = 1.0. The industry ’s known several methods to reduce the dielectric constant of the insulating material. These techniques include adding elements such as fluorine to the composition to reduce the dielectric constant of the host material. Other methods to reduce the value of k include 200406031 (2) Description of the Invention_Page :: Use of other dielectric materials. Another method is to introduce pores into the matrix. Therefore, with the increase of the line width of the interconnection device, it is also required to accompany the reduction of the dielectric constant of the insulating material, so as to achieve the improvement of the performance and speed required for future semiconductor devices. For example, a semiconductor element having an interconnect device with a line width of 0.13 or 0.10 micrometers or less desirably has a dielectric constant (k) < 3 for the insulating material. Silicon dioxide (SiO) and modified versions of silicon dioxide such as fluorinated silica or fluorinated silica glass (hereinafter referred to as FSG) are currently used. These oxides have a dielectric constant in the range of about 3.5 to 4.0 and are often used in semiconductor devices as a dielectric material. Although silicon dioxide and FSG have the mechanical and thermal stability required to withstand the thermal cycling and processing steps required in semiconductor device manufacturing, the industry still expects materials with lower dielectric constants. The methods used to deposit dielectric materials can be divided into two broad categories: spin-on deposition (hereinafter referred to as SOD) and chemical vapor deposition (hereinafter referred to as CVD). Efforts have been made to develop lower dielectric constant materials, including changing the chemical composition (organic, inorganic, organic / inorganic admixtures) or changing the dielectric matrix (porous, non-porous). Table 1 summarizes the development of certain materials with dielectric constants ranging from 2.0 to 3.5 (PE = plasma assisted; HDP = high-density plasma). However, the dielectric materials and substrates disclosed in the public documents shown in Table 1 do not have many desired combinations of physical and chemical properties, or even the combination of properties required for effective dielectric materials, such as mechanical stability, thermal stability, and glass. The transition temperature surface, modulus, or hardness is high, while still being solvent-mediated, spin-coated, or deposited on a substrate, wafer, or other surface. Therefore, it is expected to study other compounds or materials which can be used as dielectric materials and dielectric layers, even if these compounds or materials are in the form of their existence is not currently expected to be used as a dielectric material. ----------- Materials — Fluorinated Silicon Oxide — _ (Si〇F) __ Hydrogen Silsesquioxane (HSQ) Deposition Method PE-CVD ； HDP-CVD ~~ SOD " " " " Dielectric Constant (k) ~ 3.3-3.5 ^ ~~ 2.0-2.5 ~ —----____ References; 5? 370,9〇Γ × ~ 5,486,564; International Patent Bulletin w00 / 40637; ES · Moyer et al., "Ultra-low k-based resins based on silsesquioxane", the concept and needs of low dielectric constant < 0.15 micron interconnect materials: today and next millennium, American Chemical Society Sponsor—Page 128-146 (14-17 November 1999) Methylsilsesquioxane (MSQ) SOD 2.4-2.7 US Patent 6,143,855 Polyorganic SOD 2.5-2.6 US Patent 6,225,238 Gasification Non-Japanese ET Shi Mi (aC: F) HDP-CVD 2.3 U.S. Patent 5,900,290 Dong Bing 5 (BCB) SOD 2.4-2.7 U.S. Patent 5,225,586 Poly-Arylenyl (PΑE) SOD 2.4 U.S. Patent 5,986,045; 5,874,516 and 5,658,994 Parylene (Parylene) (N and F) CVD 2.4 U.S. Patent 5,268,202 SOD 2.6, U.S. Patents 5,965,679 and 6,288,188B1; and Waiterloos et al., "Porous Schilk (SiLK) The feasibility of the integration of bulk dielectric materials, "Proceedings of the International Conference on Interconnect Technology, 2001, pp. 253-254 (2001) Thermosetting phenylfluorene, cyclobutenes, polyarenes, thermosetting perfluoroethanes and monomers. --------- SOD 2.3 International Patent Publication WO 00/31183 Poly (Benji Junjin Forest), Organic Polysand Oxide SOD 2.3-3.0 US Patents 5,776,990; 5,895,263; 6,107,357 and 6,342,454; and the United States Patent Bulletin 2001/0040294 Organic Polysiloxane SOD Not Reported US Patent 6,271,273 Organic and Inorganic Materials SOD 2.0-2.5 US Patent 6,156,812 200406031 Invention Description Continued. .Vss * νζ, ^, *, 〆, organic and Inorganic material SOD 2.0-2.3 US patent 6,171,687 Organic material SOD not reported US patent 6,172,128 Organic SOD 2.12 US patent 6,214,746 Organic sesquioxane CVD, SOD < 3.9 WO 01/29052 Fluorosilicon Hemioxane CVD, SOD < 3.9 WO 01/29141 Unfortunately, the numerous organic SOD systems currently in development with a dielectric constant of 2.0 to 3.5 have certain disadvantages in terms of the aforementioned mechanical and thermal properties; therefore, the industry needs to develop Improved manufacturing methods and performance are available for dielectric films in this range of dielectric constants. In addition, the industry needs materials with low dielectric constant expansibility, in other words materials that can be reduced to even lower dielectric constants such as 2.7 to 2.5 to 2.2 to 2.0 and below.

Reichert and Mathias described compounds and monomers that contain Kanazawa U-bond molecules, which are mainly caged molecules, and the teachings can be used as diamond substitutes. [Polymer Preparation (American Chemical Society Polymer Chemistry Branch) 1993, Issue 34 (1) pages 495-6; Polymer Preparation (American Chemical Society Polymer Chemistry Branch), 1992 33 (2) Issue 144-5; Chemistry Materials, 1993, Issue 5 (1), pages 4-5; Macromolecules, 1994, Issue 27 (24), pages 7030-7034; Macromolecules, 1994, Issue 27 (24), pages 7015-7023; Polymer Preparation (Americanization) Society of Polymer Chemistry, 1995) Issue 741-742, 1995; 205th ACS National Conference, Conference Plan, 1993, 312; Macromolecule, 1994 (24) Issue 7024-9; Macromolecule, 1992 25 (9) Issue 2294-306; Macromolecule, 1991 24 (18) Issue 5232-3; Dr. Veronica R. Reichert Thesis, 55-06B 1994; ACS Seminar Series: Progressive Growth Polymerization of High Performance Materials Materials, 1996, Issue 624, pages 197-207; Macromolecules, 2000, Issue 33 (10), pages 3855-3859; Polymer Preparation (American Chemical Society, Polymer Chemistry Branch), 1999, 40 (2), Issues 620-621; Polymer Preparation (America 200406031 (5) Description of Invention Performance Page Society of Polymer Chemistry) 1999 40 (2) pages 577-78; macromolecules, 1997 30 (19) Issue 5970-5975; Journal of Polymer Science, Part A: Polymer Chemistry, 1997 35 (9) Issue 1743-1751; Polymer Preparation (American Chemical Society Polymer Chemistry Branch) 1996 37 (2) Issue 243 -244 pages; Polymer Preparation (American Chemical Society Polymer Chemistry Branch) 1996 37 (1) Issue 551-552; Polymer Science Journal, Part A: Polymer Chemistry, 1996 34 (3) Issue 397-402 Page: Polymer Preparation (American Chemical Society's Polymer Chemistry Branch), 1995, Issue 36 (2) pages 140-141; Polymer Preparation (American Chemical Society's Polymer Chemistry Branch), 1992, 33 (2) Issue 146-147; Journal of Applied Polymer Science, 1998, 68 (3): 475-482]. Reichert and Mathias' compounds and monomers based on Kanazawa Jane are preferably used to form polymers with adamantane molecules in the center of thermosetting materials. The compounds revealed by Reichert and Mathias in their research included only a design-selected compound based on adamantane. Structural formula A shows such a symmetrical para-isomer 1,3,5,7-[[4 '-(phenylethynyl) phenyl] adamantane:

Structural formula A In other words, Reichert and Mathias in their other 1J research work and joint research work are expected to cover a useful polymer that contains only an isomeric form of a monomer targeted primarily to adamantane. But when the adamantane is -12-200406031 (6) the invention said that the date and month page:

Wang < Monomer 4 Mono-isomeric Forms (Symmetric "All-para" Isomers) 1,3,5,7-Di [4-(phenylethylfluorenyl) phenyl] adamantane Formation and Treatment Major problems were encountered with polymers. According to Reichert's doctoral dissertation (see above) and macromolecular issue 27 (p. 7 015-7034) (see above), the symmetrical all-para-isomers 1, 3, 5, 7-- [4 '-( "Phenylethynyl) phenyl] adamantane" is found to be sufficiently soluble in aeroform to obtain a 4 NMR spectrum, but the time to obtain a 13C NMR spectrum of the solution is not consistent "indicates that the solubility of the all para-isomer is low. In this way, Reichert's symmetrical "all para" isomer 1,3,5,7-[[4, (phenylethyl block) phenyl] adamantane is insoluble in standard organic solvents and cannot be used for any requirements. ' Solubility or solvent-based processing applications such as flow coating, spin coating or dip coating. Patent application PCT / US01 / 22204 under joint transfer and in examination by the inventors, with filing date of October 17, 2001

The following applications are being investigated: US Application No. 09/545058, application dated April 7, 2000; US Application No. 09/618945, 'application dated July 19, 2000; US Application No. 09 / Application No. 897936, dated July 5, 2001: and US Application No. 09/902924, dated July 10, 2001; and International Publication No. WO 01/78110, dated October 18, 2001) 'The inventor found a composition comprising a mixture of isomerized thermosetting monomers or dimers, wherein the mixture comprises at least one monomer or dimer having a structural formula corresponding to R.1

R · 2 R \ R ， 4 yZ ^ // Ul / | hfl R.s R | -13-200406031 (7) Description of the invention continued:

Where Z is selected from the group consisting of caged compounds and silicon atoms; R, R'2, RS, R'4, R'5, and R'6 are respectively selected from the group consisting of aryl, branched aryl, and arylene ether; aryl At least one of the branched aryl group and the arylene ether has an ethynyl group; and R'7 is an aryl group or a substituted aryl group. The inventors have also disclosed methods for forming such thermosetting mixtures. These novel heterogeneous thermosetting monomers or binary mixtures are useful for microelectronic applications as dielectric materials and are soluble in a variety of solvents, such as cyclohexanone. These desirable properties make these isomer thermosetting monomer or binary mixtures ideal for forming thin films having a thickness of about 0.1 microns to about 1.0 microns. The issuer filed a patent application No. 60/384304 on the same day as the application, which requested a porous version of the aforementioned isomer.

The inventor's international patent publication WO 01/78110, published on October 18, 2001, teaches the introduction of nano-sized voids in the background, including physically mixing or chemically grafting thermally stable parts or thermally Steady part. The invention of the announcement is that nano-sized voids can be introduced into the dielectric material using caged structures such as adamantane or bis-adamantane to obtain a low dielectric constant material, and the low dielectric constant material is defined as having a dielectric constant less than 3.0. However, the announcement did not report any dielectric constant as an example. International Patent Publication WO 00/31183 teaches in Section B of its prior art that although porous thermoplastic materials are known to have acceptable dielectric constants, the pores tend to sag during subsequent high temperature processing. Therefore, International Patent Publication WO 01/78110 Announcement date October 18, 2001 The technical deviation of the teachings increased the porosity of the cage structure by introducing nano-sized voids. In addition, U.S. Patents 5,776,990; 5,895,263; 6,107,357; and 6,342,454 and U.S. Gazette -14-200406031 (8) #Explanation continued

2001/0040294 teaches that although the dielectric constant of 2.3-2.4 has been reached when the porosity is less than about 20%, the small area size that does not include the pore structure and / or the non-interconnection of the pore structure cannot further increase the pore content. Similarly, U.S. Patents 6,271,273; 6,156,812; 6,171,687 and 6,172,128 teach that the content of thermally unstable monomer units is limited to less than about 30% by volume. If the amount of thermally unstable monomers exceeds about 30 % Volume ratio, the resulting dielectric material has columnar or layered fields, rather than pores or voids, resulting in structural interconnects or depressions when removed, in other words structural interconnects when thermally decomposing thermally unstable monomer units Or framed. Although various methods are known in the industry to reduce the dielectric constant of materials, these methods have their disadvantages. Therefore, the semiconductor industry still needs a) to provide improved compositions and methods to reduce the dielectric constant of the dielectric layer; b) to provide dielectric materials with improved properties such as thermal stability, glass transition temperature (Tg), modulus, and hardness C) making thermosetting compounds and dielectric materials that can be solvent mediated and spin-coated onto wafers or layered materials; and d) providing materials with the extended properties shown.

The present invention provides excellent scalability, so manufacturers can use the composition of the present invention for many different generations of microchips. SUMMARY OF THE INVENTION In response to the needs of the industry and conducting research contrary to the general ideas of the industry, the inventors have developed a composition comprising: (a) a dielectric material; and (b) a pore former comprising at least two fused aromatic rings, Wherein each of the fused aromatic rings has at least one substituent substituted thereon, and at least one of the alkyl substituents existing on a neighboring aromatic ring is bonded. -15-200406031 (9) Invention description sheet '*, S, :: ,,,,,,,,,,,,,,,' ^ The inventor also found a composition comprising a cage structure having a dielectric constant of less than 2.7. The inventors have also discovered that a composition comprises:

(a) The thermosetting component contains: (1) at least one monomer of formula I, if required, Q α ·

Q

And (2) at least one oligomer or polymer of formula II

Here E is a cage compound; each Q is the same or different and is selected from hydrogen, aryl, branched aryl, and substituted aryl, wherein these substituents include hydrogen, halogen atom, alkyl, aryl , Substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxy, or carboxyl; Gw is aryl or Substituted -16-200406031 (10) Summary page of the invention, aryl group, where substituents include functional atoms and alkyl groups; h is 0 to 10; i is 0 to 10; j is 0 to 10; and w is 0 or 1; and (b) a porogen.

It should be understood that when w of the above formula II or the following formula IV, VI, VII, VIII or IX is 0, the two caged compounds are directly bonded. Each E has at least one Q attached thereto, preferably E does not carry more than one Q as hydrogen, and more preferably E does not carry Q as hydrogen. When Q is a substituted aryl group, it is more preferred that the aryl group is substituted with an alkenyl group or an alkynyl group. Preferred Q groups include (phenylethynyl) phenyl, hydrazone (phenylethlyl) benzyl, qinylethynyl (benzylethenyl) benzyl, and (winterylethynyl) phenylphenyl section. Preferred aryl groups include phenyl, biphenyl, and tritriphenyl. More preferably, the G group is phenyl. Preferably, w is 1. The invention also includes a method of using the foregoing composition. The steps in one method include: decomposition into a porogen; and gasification and decomposition of the porogen, thereby reducing the dielectric constant of the dielectric material. In another method, the method step includes decomposing into a porogen and pore former after gasification and decomposition, thereby forming pores in the dielectric material.

The inventors have also developed a composition comprising: (a) a compound having at least a bifunctional group, wherein the bifunctional groups may be the same or different, and at least one of the first functional group and the second functional group is selected A group consisting of a silicon-containing group, a nitrogen-containing group, a carbon bond to an oxygen-containing group, a hydroxyl group, and a carbon-containing double bond to a carbon-containing group; and (b) a pore former comprising at least two fused groups Aromatic rings, where each of the fused aromatic rings is based on at least one alkyl substitution, and at least one of the alkyl substituents present on a neighboring aromatic ring is bonded to one another. Embodiment -17- 200406031 (11) Summary page of the invention The inventor filed a patent application 10/158548 in the same application of the present application, which requested a composition of a thermosetting component and a porogen which is bonded to the thermosetting component. Dielectric materials:

Dielectric materials such as inorganic, organic, or mixed organic and inorganic materials are known to be used for the pore-forming agent described later. Examples include phenyl ethylated aromatic monomers or oligomers; fluorinated or unfluorinated poly (arylene ethers) such as commonly assigned U.S. Patent Nos. 5,986,045; 6,124,421; 6,291,628, and 6,303,733 Teaching; Bibenzocyclobutene and organosiloxanes are under review, for example, US patent application 10 / 078,919, teaching dated February 19, 2002.

As used herein, the terms "coupled structure", "caged molecule" and "caged compound" are intended to be used interchangeably to indicate a molecule that has at least eight atoms arranged in at least one bridge group covalently linked ring system. Two or more atoms. In other words, a caged structure, a caged molecule, or a caged compound contains a plurality of rings formed by covalently bonded atoms, where the structure, molecule, or compound bounds a volume, so that a point located inside the volume cannot pass through the ring And leave the volume. The bridging group and / or the ring system may contain one or more heteroatoms, and may contain an aromatic group, a partially cyclic or acyclic saturated hydrocarbon group, or a cyclic or acyclic unsaturated hydrocarbon group. It is further anticipated that the covered cage structure will include flillerenes and at least one crown of the bridge. For example, adamantane or bisadamantane is considered a caged structure, and fluorene or aromatic spiro compounds are not considered as a caged structure within this definition, because fluorene or aromatic spiro compounds do not have one or more Bridge base, therefore -18-200406031 (12) Description page of invention; not in the scope of the aforementioned cage compound. The caged compound is preferably adamantane and bisadamantane, and more preferably adamantane. The term "bridgehead carbon" is used here to indicate any caged carbon that is bonded to the other three carbons. So for example, diamond bridges have four bridge heads completed, while diamantane has eight bridge head carbons.

The preferred dielectric material is the patent application 60/347195, which is jointly assigned by the inventors, and is filed on January 8, 2002 and 60/384303. The application date is the same as this application, and the application date is January 3, 2003. The thermosetting composition disclosed and claimed by Japan and ΓΜ06878, which is incorporated herein by reference in its entirety. The present composition comprises at least one adamantane monomer of formula III

Q

And (b) at least one adamantane oligomer or polymer of formula IV

Q Q

Q

.Q

Q

Q

α

Q

Q α

Q α or ⑻ at least one bisadamantane monomer of formula V -19- 200406031 (13)

Q

Fen Ming said that the continuation sheet ft < S Ν »A, 丨 and (b) at least one oligomer or polymer of bisadamantane monomer of formula VI

Where Q, Gw, h, i, j, and w are as defined above. When h, i and j in the above formula IV are all zero, the adamantane binary system is shown in the following formula VII

Q

Q Here Q and Gw are defined as before. When w of formula VII is zero, the adamantane binary body is -20-200406031 (14) The invention achievement page: An example is shown in Table 2 below.

200406031

-22-200406031 (16) Outstanding achievement page

Η

When h is 1 and i and j are zero in the above formula IV, the adamantane triad shows the following formula VIII

Q

Ct a q

Q

Q Here Q and Gw are defined as before. When w of Formula VIII is preferably 1, a preferred triad is shown in Table 4 below, for example. Table 4

200406031 \) / —I Ming L hair 1 fi

ri ^ nm ·

Rii

. • .4r 200406031

-25-200406031 (19) Performance sheet:

-26- 200406031 (20) Description of the invention continued,

-27-200406031 (21) #Indicate performance page:

200406031

-29- 200406031 (23) Refer to the report page,, < »V- 'V " 〆 ,,, nine r

R

Preferably the present composition comprises at least one oligomer or polymer of formula VI above,

Here Q, G, h, i, j and w are as defined above. When h, i, and j in Equation VI are

At zero, the bisadamantane binary is shown in the following formula IX-Q Q

Here Q and Gw are defined as before. A preferred thermosetting component ⑻ includes: (1) adamantane monomer of formula XA

, Formula XB -30- 200406031 杳 Ming description page 丨 (24) Ri

XC

Ri

OR XD

Ri

And (2) an adamantane oligomer or polymer of formula XI

-31-200406031 (25) Emerging 龠 Result Sheet 'and preferred adamantane oligomer or polymer

Or (1) at least one bisadamantane monomer of formula XIIA

Ri -32- 200406031 (26)

, Type XIIC

Ri

Description of the invention

Or XIID

And (2) bisadamantane oligomer or polymer of formula XIII

200406031 (27) Silkworm month: clear pages, ,,, ♦, 々 · * ,, > ,, (V 'and preferably bisadamantane oligomer or polymer of the following formula

Ri of each of XI, XI, XIIA, XIIB, XIIC, and XHD are the same or different, and are selected from the group consisting of hydrogen, a letter, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, alkenyl , Alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxy, or carboxyl; and each Y of formula XA, XB, XC, XD, XI, XIIA, XIIB, XIIC, and XIID Are the same or different and are selected from the group consisting of hydrogen, alkyl, aryl, substituted aryl, or halo. Formulae II, IV, VI, XI, and XIII represent random or irregular structures in which any one of units h, i, and j may be repeated or may not be repeated several times before another unit is present. In this way, the order of the units of formulas II, IV, VI, XI, and XIII is random or irregular. In a specific embodiment, the preferred thermosetting composition comprises an adamantane monomer of the above formula XA, XB, XC and XD, and at least one adamantane oligomer or polymer of the above formula XI, where h, i and j are At least one is at least 1. Better-34- 200406031 (28) Fen Ming's performance sheet 丨 Thermosetting composition contains the bisadamantane monomer of the above formula XIIA, XIIB, XIIC or XIID, and at least one bisadamantane oligomer or polymer of the above formula XIII , Where at least one of h, i, and j is at least 1. Preferred thermosetting ingredients include adamantane monomers of the above formula XA, XB, XC or XD, and adamantane oligomers or polymers of the following formula XIV, where &, Y and w are as defined above and h is 0 or 1.

Preferred adamantane oligomers or polymers

The preferred thermosetting composition comprises a bisadamantane monomer of the above formula XIIA, XIIB, XIIC or XIID, and a bisadamantane oligomer or polymer of the following formula XV, where R 丨, Y and w are as defined above and h is 0 or 1. 200406031 (29) Invention description sheet

Preferably, the bisadamantane oligomer or polymer has the following formula

h The preferred thermosetting composition includes the adamantane monomer of the above formula XA, XB, XC or XD, and the adamantane binary of the following formula XVI, where R !, Y and w are defined as (30) 200406031

, jj νττΔ ^ χΙΐΒ ^ ^ 隹 The thermosetting component contains the above formula 邡 a binary gift, & virgin, ... more alkane monomer, and the bisadamantane of the following formula XVII

200406031 (31) Summary sheet of the invention: Bisdamantane binary

Higher carbon oligomers. Preferred thermosetting ingredients include adamantane monomers of the above formula XA, XB, XC or XD, and adamantane triplets of the following formula XVIII, where the ruler, Y and w are as defined above.

-38- 200406031 invention description sheet, (32)

The adamantane monomer and the bisadamantane triad of the following formula XIX.

-39- 200406031 (33) Fenming Broken Continued Preferred thermosetting ingredients include adamantane monomer of the above formula XA, XB, XC or XD, adamantane binary of the above formula XVI, and at least one adamantane of the above formula XI An oligomer or polymer, where at least one of h, i, and j is at least one. Preferred thermosetting ingredients include bisadamantane monomers of the above formula XIIA, XIIB, XIIC or XIID, bisadamantane binary bodies of the following formula XVII, and at least one bisadamantane oligomer or polymer of the above formula XIII, At least one of h, i, and j is at least 1.

Preferred thermosetting components include the adamantane monomer of the above formula XA, XB, XC or XD, the adamantane binary of the above formula XVI, the adamantane triple of the above formula XVIII, and at least one adamantane oligomer of the above formula XI or Polymer, where at least one of i and j is at least 1. Preferred thermosetting ingredients include bisadamantane monomers of the above formula XIIA, XIIB, XIIC or XIID, bisadamantetradane binary bodies of the above formula XVIII, bisadamantane triplets of the above formula, and at least one of the above formula XIII An adamantane oligomer or polymer, where at least one of i and j is at least one.

The thermosetting component comprises a monomer of the formula XA, which is a tetra-substituted adamantane, or a monomer of the formula XIIA, which is a tetra-substituted bis-adamantane. A preferred monomer is an adamantane monomer of formula XA. The adamantane main chain carries substituted aryl groups at positions 1, 3, 5 and 7. Compounds of formula XI are oligomers or polymers of monomers of formula XA adamantane which are linked through unsubstituted and / or substituted aryl units. A compound of formula XIII is an oligomer or polymer of a bisadamantane monomer of formula XII that is linked through unsubstituted and / or substituted aryl units. Usually h, i and j are integers from 0 to 10, preferably from 0 to 5 and more preferably from 0 to 2. The simplest adamantane oligomer is a binary body represented by the above formula XVI (in formula XI, h is 0, i is 0, and j is 0), in which two adamantane main chains are -40-200406031. (34) 杳 明 说明 Continued: Linked via an unsubstituted or substituted aryl unit. The simplest bisadamantane oligomer is a binary body represented by the above formula XVII (in formula XIII, h is 0, i is 0, and j is 0), in which two bisadamantane main chains pass through a Substituted or substituted aryl units are linked.

In another embodiment, it is preferred that the present thermosetting component comprises at least one adamantane oligomer or polymer of the above formula XI, where h is 0 to 10, i is 0 to 10, and j is 0 to 10. Preferably the present thermosetting composition comprises at least one bisadamantane oligomer or polymer of the above formula XIII, where h is 0 to 10, i is 0 to 10 and j is 0 to 10. Preferably, the present thermosetting component comprises at least one adamantane oligomer or polymer of the above formula XI, where h is 0 or 1, i is 0 and j is 0. The structure of this adamantane is shown by the above formula XIV. Preferably, the present thermosetting component comprises at least one bisadamantane oligomer or polymer of the above formula XIII, where h is 0 or 1, i is 0 and j is 0. Such a bisdamantane structural formula is shown by the above formula XV.

Preferably, the present thermosetting component comprises at least one adamantane oligomer or polymer of the above formula XI, where h is 0, i is 0, and j is 0. This adamantane binary system is shown by the above formula XVI. Preferably, the present thermosetting component comprises at least one bisadamantane oligomer or polymer of the above formula XIII, where h is 0, i is 0, and j is 0. Such a bisdamantane binary system is represented by the above formula XVII. Preferably, the present thermosetting component comprises at least one adamantane oligomer or polymer of the above formula XI, where h is 1, i is 0, and j is 0. This adamantane ternary system is represented by the above formula XVIII. -41-200406031 (35) Summary sheet of the invention; Preferably, the thermosetting component ⑻ contains at least one bisadamantane oligomer or polymer of the above formula XII, where h is 1, i is 0, and j is 0. Such a bisdamantane ternary system is shown by the above formula XIX. The preferred thermosetting composition comprises at least one adamantane oligomer or polymer mixture of the above formula XI, where h is 2, i is 0 and j is 0 (linear oligomer or polymer) and h is 0 and i is 1 And j is 0 (branched oligomer or polymer). Such a composition thus comprises a mixture of adamantane linear quaternary compounds represented by the following formula XX, where R !, Y and w are as defined above.

And the preferred linear adamantane quaternary

-42-200406031 (36)

And the preferred branched adamantane tetrad

SUM

A preferred thermosetting composition comprises at least one bisadamantane oligomer or polymer of the above formula XIII (where h is 2, i is 0, and j is 0. As a result, a linear oligomer or polymer is obtained; and h is 0, i is 1 and j are 0 results to obtain branched oligomers or polymers). Such a composition thus comprises a bisadamantane linear tetrad shown in the following formula XXII ..., where Ri, Y and w are defined as before -43-200406031 (37) assia.

u r \ u. • 44- 200406031 (38) issued

And the preferred branched bisdamantane tetrad

Preferred thermosetting components include the adamantane binary of formula XVI and the adamantane triple of formula XVIII. Preferred thermosetting ingredients include bisadamantane of the above formula XVII

-45-200406031 (39)

Fenming explanation: continued I binary and XIX bisadamantane ternary. A preferred thermosetting composition comprises the adamantane binary of formula XVI and at least one oligomer or polymer of adamantane of formula XI, where h is 0, i is at least 1 and j is 0. A preferred thermosetting composition comprises a bisadamantane binary of the above formula XVII and at least one bisadamantane oligomer or polymer of the above formula XIII, where h is 0, i is at least 1, j is 0, and w is 0 or 1 . In two specific embodiments, for the above formulae I and II, preferred Q groups include aryl groups and aryl groups substituted with alkenyl and alkynyl groups; more preferred Q groups include (phenylethyl) phenyl,贰 (phenylethynyl) phenyl, phenylethynyl (phenylethynyl) phenyl, and (phenylethynyl) phenylphenyl moieties. Preferred aryl groups include phenyl, biphenyl, and tritriphenyl. More preferably, the G group is phenyl. The respective Ri groups of the substituted ethynyl groups attached to the phenyl ring of the = C-adamantane or bis-adamantane ring are in the formula XA, XB, XC, XD, XI, XIIA, XIIB, XIIC, XIID, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII and XXIII are respectively the same or different. & is selected from the group consisting of hydrogen, halogen atom, alkyl, aryl, substituted aryl, heteroaryl, aryl acid, diaryl, alkynyl, alkoxy, light alkynyl, and aryl , Via alkenyl, alkynyl, via or alkynyl. Each R! May be unbranched or branched and unsubstituted or substituted, and the substituents may be unbranched or branched. Preferred alkynyl, fluorenyl, bulk, alkoxy, mesityl, hydroxyalkenyl, and hydroxyalkynyl groups contain about 2 to about 10 carbon atoms, and aryl, aryl ether, and hydroxyaryl groups The group contains about 6 to about 18 carbon atoms. If heart represents aryl, Ri is preferably phenyl. It is preferred that at least two I ^ C ^ C groups of the phenyl group are two different isomers. At least two different isomers 200406031 (40) Summary sheet of the invention_

Examples include meta-, para- and ortho-isomers. Preferably at least two different isomers are the meta- and para-isomers. The preferred monomer is 1,3,5,7-^ [374'-phenylethynyl] phenyl] adamantane (as shown in Figure 1D). There are five isomers: -, Right-, right-; (2) right-, right-, right-, between-; (3) right-, right-, between-, between-; ⑷ right-, between-, between-, between- And (5) inter-, inter-, inter-, inter-. XA, XB, XC, XD, XI, XIIA, XIIB, XIIC, XIID, XIII

Each γ of the phenyl ring in XIV, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, and XXIII is the same or different, and is selected from hydrogen, alkyl, aryl, substituted aromatic Radical or halogen atom. When Y is aryl, aryl includes, for example, phenyl or biphenyl. Y is preferably selected from hydrogen, phenyl and biphenyl, and more preferably hydrogen. Preferably, at least one phenyl group between the two bridgehead carbons of the adamantane or bisadamantane is present as at least two different isomers. The at least two different isomers include, for example, meta-, para-, and ortho- isomers. Preferably, the at least two isomers are meta- and para-isomers. The best binary 1,3 / 4- 贰 {Γ, 3 ', 5'-reference [374〃- (phenylethynyl) phenyl] adamantane-7'-yl} benzene (shown in Figure 1F) , Generate 14 kinds of isomers as follows. It is preferred that the phenyl group located between the two bridgehead carbons of the diamond is meta- and para-isomers. For each of the aforementioned two isomers, there are RiC = C-based isomers of seven phenyl groups as follows: (1) para-, para-, para-, para-, para-, para-; ⑺ right-, right-, right-, right-, right-, between-; (3) right-, right-, right-, right-, between-, between-; (4) right-, right-, right -, Inter-, inter-, inter-; (5) inter-, inter-, inter-, inter-, inter-, inter-; (6) inter-, inter-, inter, inter-, inter-, inter- -; And ⑺ between-, between-, between-, between-, between-, between-. In addition to the branched adamantane structure of the above formula XXI, it must be understood that when h is 0, i is 0, and j -47-200406031 (41) # 明 3 明 素 页: When 1, the above formula XI is further branched into the following formula XXIV As shown here, Ri, Y and w are defined as before. It should be understood that since further branching of the adamantane unit beside the structural formula of formula XXIV may occur, the branch may exceed the structural formula of formula XXIV.

The preferred adamantane structure has the formula

-48-200406031 (42) The monthly performance report page: In addition to the bisadamantane branch of the above formula XXIII, it must be understood that when h is 0, i is 0, and j is 1, the above formula XIII indicates that the further branch is as follows Formula XXV. It must be understood that the diamantane unit is further branched by the structural formula XXV, so the branch may appear to exceed the formula XXV.

The preferred bis-adamantane structure has the formula -49-200406031 (43)

Fenming's performance sheet: The content of thermosetting ingredients, monomers, oligomers or polymers is determined by gel permeation chromatography as described in section "Analytical test methods" below. The composition comprises an adamantane or bisadamantane monomer in an amount of about 30 to about 70 area%, more preferably about 40 to about 60 area%, and still more preferably about 45 to about 55 area%: oligomer or polymer The content is about 70 to about 30 area%, more preferably about 60 to about 40 area% and even more preferably about 55 to about 45 area%. Most preferably, the composition comprises a monomer (1) content of about 50 area% and an oligomer or polymer (2) content of about 50 area%. Usually, the ratio of the amount of the adamantane or bisadamantane monomer (1) to the oligomer or polymer (2) can be set in a desired manner, for example, in preparing the group -50-200406031 (44) according to the invention. By changing the molar ratio of the starting component during the compound, by adjusting the reaction conditions, and by changing the non-solvent to solvent ratio during the precipitation / separation step. A preferred method for preparing the thermosetting component VII includes the following steps. In step (A), adamantane or bisadamantane is reacted with a halobenzene compound of formula XXVI

Here Y is selected from the group consisting of hydrogen, alkyl, aryl, substituted aryl or halogen atoms, and Yl is a halogen atom to form a mixture using diamonds:!: When finished, the mixture contains at least one monomer of the above formula III And at least one oligomer or polymer of the above formula IV, where h is 0 to 10, i is 0 to 10, j is 0 to 10, w is 0 or 1, and Q is hydrogen or -QHsYiY, here Y! And Y is defined as before. Preferably the at least one oligomer or polymer has the formula

Or when bisadamantane is used, the mixture contains at least one of the above formula V-51-200406031 (45) # 明 敌 明 表 页 ”and at least one of the above formula VI oligomer or polymer, where h is 0 to 10, 1 is 0 to 10, j is 0 to 10, w is 0 or 1 and Q is hydrogen or -C6H3Y 丨 Y (here Y! And Y are as defined above) and preferably the at least one oligomer or polymer The following formula

Those skilled in the art must understand that the reactions can occur at bridgehead carbons of bisdamantane other than those indicated by the above formulas X and XVI.

In step (B), the mixture obtained in step (A) is reacted with terminal alkyne of the formula RiCsCH. Preferably, this method produces a composition of the above formula XA and XI or XIIA and XIII. In step (A), adamantane or bisadamantane is reacted with a halobenzene compound of formula XXVI. In addition to the halogen group y1 and the aforementioned group Y, the halobenzene compound also contains other substituents. The halobenzene compound is preferably selected from bromobenzene, dibromobenzene and iodobenzene. Bromobenzene and / or dibenzyl are preferred, and bromobenzene is even more preferred. The reaction of adamantane or bisadamantane with a halobenzene compound (step (A)) is preferably carried out via a Fleich-Claffford reaction in the presence of a Lewis acid catalyst. -52- 200406031 (46) Summary sheet of the invention, OK. Although all conventional Lewis acid catalysts can be used, it is preferred that the Lewis acid catalyst contains at least one member selected from the group consisting of aluminum (III) chloride (A1C13), aluminum (III) bromide (AlBr3), and Ion (III) ) (A1I3). I (III) chloride (A1C13) is the best. Although aluminum bromide (III) has a higher Lewis acidity, it is generally poorer to use because it has a low sublimation point of only 90 ° C, making it far more difficult on an industrial scale than, for example, aluminum (III) chloride. Take control.

In another preferred version, the Fleich-Clafford reaction is performed in the presence of a second catalyst component. The second catalyst component preferably contains at least one member selected from a third-stage haloalkane having 4 to 20 carbon atoms, a third-stage alkanol having 4 to 20 carbon atoms, a second and 4 to 20 carbon atoms Tertiary women's hydrocarbons and tertiary i alkylaryl compounds. In particular, the second catalyst component contains at least one selected from the group consisting of 2-bromo-2-methylpropane (third butyl bromide), 2-chloro-2-methylpropane (third butyl chloride), and 2-methyl- Compounds of 2-propanol (third butyl alcohol), isobutyl hydrazone, 2-bromopropane, and third butyl bromobenzene, and 2-bromo-2-methylpropane (third butyl bromide) is the best . In general, compounds whose alkyl group has 5 or more carbon atoms are less suitable, and solid components are precipitated from the reaction solution at the end of the reaction. The preferred Lewis acid catalyst is aluminum (III) chloride (A1C13), and the second catalyst component is 2-bromo-2-methylpropane (third butyl bromide) or third butyl bromobenzene. The preferred procedure for carrying out the Friuli-Crafort reaction is adamantane or bisdamantane, i-benzene compounds (such as bromobenzene), and Lewis acid catalysts (such as aluminum chloride) at 30 ° C to 50 ° C, preferably 35 ° C to 45 ° C, and especially 40 ° C for mixing and heating. At temperatures below 30 ° C, the reaction is not complete and, for example, a higher proportion of tri-substituted adamantane is formed. In principle, higher temperatures than those listed above can be used (Example -53-200406031 (47) Inventive beginning sulfonate f such as 60 ° C), but such a non-halogenated aromatic material which undesirably leads to the reaction mixture of step (A) (Eg benzene). The second component of the catalyst system, namely, third butyl bromide, is then usually added to the aforementioned reaction solution for 5 to 10 hours, and preferably 6 to 7 hours; after the addition is completed, the reaction mixture is mixed into the reaction temperature range for 5 to 10 hours and preferably 7 hours.

Unexpectedly, in addition to monomeric tetraphenylated compounds such as 1,3,5,7- (3 '/ 4'-bromophenyl) adamantane, oligomers or polymers also appeared in the step ( A) The resulting mixture. Unexpectedly, the weight ratio of the adamantane monomer of formula III to the adamantane oligomer or polymer of formula IV, or the weight of the bisadamantane monomer of formula V to the bisdamantane oligomer or polymer of formula VI The ratio can be controlled by the amount of adamantane or bis-adamantane, a benzene compound (such as bromobenzene), and a second catalyst component (such as third butyl bromide). In the reaction mixture of step (A), the molar ratio of the adamantane or bisadamantan p-toluene compound to the second catalyst component is preferably 1: (5-15) :( 2-10), or even 1: (8-12 ) :( 4-8).

In compounds of formula XA, XB, XC, XD, XI, XIIA, XIIB, XIIC, XIID, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV and XXV, halogen atoms are substituted Base Y, position is undefined. Better mixtures contain meta- and para-isomers, which, unlike full para-isomers, preferably produce improved solubility and good film properties. In the reaction mixture of step (A), in addition to monomers and oligomers or polymers, starting components and by-products (for example, non-perphenylated adamantane) may also occur. If necessary, the mixture obtained in step (A) is post-processed using a method known to those skilled in the art. For example, it is necessary to remove unreacted halophenyl compounds (such as bromobenzene) from the mixture and obtain a product with high proportions of formulas III, IV, V and -54- 200406031 (48) The invention claims: Ming continued;

Compound VI is available for further reactions. Any solvent or solvent mixture miscible with benzene compounds (such as bromobenzene), which is suitable for precipitating compounds of formula III, IV, V and VI, can be used to isolate such products. Preferably, for example, the mixture of step (A) is poured into a non-polar solvent or a solvent mixture by dropping, preferably an aliphatic hydrocarbon having 7 to 20 carbon atoms or a mixture thereof is used, and particularly at least one component is selected from the heptane fraction (Boiling point: 93-99 ° C), octane fraction (boiling point: 98-110 ° C), and alkane mixture. The market name is Spezial Benzin 80-110 ° C (boiling point: 80-110 ° C) (Petroleum ether) was obtained from Honeywell International. Specially used benzene clear 80-110 ° C (petroleum ether with boiling point 80-110 ° C) is the best. The weight of the organic mixture to the non-polar solvent is preferably about 1: 2 to about 1:20, more preferably about 1: 5 to about 1:13, and still more preferably about 1: 7 to about k11. In addition, a polar solvent or a solvent mixture (such as methanol or ethanol) may be used for the subsequent treatment of the mixture obtained in step (A), but it is not preferable because the product mixture is precipitated to form a rubbery composition. The inventors have found that if the mixture of step (A) is precipitated into some solvents, the peak ratio of the monomers obtained from the aforementioned step (A) to the peaks of its binary, ternary and oligomers in the reaction mixture is shifted violently. This discovery allows skilled artisans to advantageously adjust the processing conditions to achieve the target ratio of monomer to binary, ternary and oligomer. In order to reduce this ratio, it is preferable to use a solvent having a different solubility between the monomer and the oligomer or polymer. The preferred solvents that can achieve this type of monomer-to-binary and ternary ratio shift include special benzene 80-110 ° C (petroleum ether, boiling point 80-110 ° C), petroleum spirit (boiling point 90- 110 ° C) and heptane (boiling point 98 ° C). A better solvent is special benzene. In particular, in order to achieve from about 3: 1 monomers: binary + ternary + oligomer -55- 200406031 (49) invention delivery page;

Transfer to about 1: 1, and the mixture in step (A) is precipitated into special benzene, or in order to achieve the transfer from 3: 1 monomer: binary + triad + oligomer to about 1.7-2.0 丄 0 In step (A), the reaction mixture is precipitated into petroleum spirit and heptane. The inventors understand that the substantial change in the distribution of the spikes during precipitation can be attributed to the loss of monomers during precipitation filtration. Description: Loss of 2/3 in special benzene clear and 2 1/3 in petroleum benzine and heptane. Corresponding to 50% and 25-33% loss of monomer yield. In order to keep the monomer: binary + triad + oligomer ratio of 3: 1 constant, the reaction mixture in step (A) was precipitated into methanol, and no yield loss was observed here. This can be confirmed by measuring the yield loss of the filtrate and GPC analysis of the filtrate. Similar to the synthesis described by Ortiz, the Fleich-Clafford reaction performed according to a preferred version of step (A) of the present invention starts directly from King Kong Tiger, which is coupled to a halobenzene compound. Compared with previous synthetic methods, such as Reichert et al.'S method for synthesizing 1,3,5,7-bromo (3W-bromophenyl) adamantane, this method is particularly excellent because it does not require the first production of tetrabromoadamantane , Which can save the reaction steps. In addition, less undesirable benzene is formed.

It is known to those skilled in the art that in addition to the halogen atom group Yi of the compounds of the above formula III, IV, V and VI, in addition to the direct reaction of adamantane with a halophenyl compound (for example by means of the Fletcher Craft reaction), the halogen Yi Introduced by multi-stage synthesis, such as via adamantine-coupled phenyl compounds (that is, halogen-free Yi), followed by the group Yi, for example, the group Yi is introduced by addition (Y02 (such as Br2), However, this method is not good. In step (B) of the preferred method, the mixture obtained after step (A) (after treatment as necessary) is reacted with terminal alkyne of the formula RiOCH (where R! Is as defined above). -56-200406031 (50) Sun and moon program: In the formula R ^ OCH, & is the same as the adamantane product of the aforementioned formula XA, XB, XC, XD and the formula XIIA, XIIB, XIIC, XIID and XIII The group R! Of the adamantane product is so optimal to use ethynylbenzene (phenylethylidene) as the terminal block of the step reaction.

In the step (B), in order to couple the terminal alkyne to the halophenyl group located in the adamantane system, all the conventional methods suitable for this project can be used. ) "Metal-Catalyzed Crosslinking Reactions" 'Power-VCH 1998; and March, J. "Advanced Organic Chemistry", 4th ed., About Weili & Sons, 1992, pages 717/718. When Y of a phenyl group is attached to two bridged carbons of the coupled structure of formula XI or XIII above, Y can react with phenylacetylene to form a terminal terminal alkynyl group.

In a preferred version of the method according to the present invention, the reaction of the mixture obtained in step (A) (which is optionally post-processed) with terminal alkynes exists in the catalyst system used in the so-called Sonogashira coupling reaction. (Refer to Sonogashira; Tohda; Hagihara; Tetrahedron Letter, p. 4467, 1975). It is even more preferred to use a catalyst system which contains at least one free-triarylphosphine complex 'copper halide (eg, Cul) of formula [ArsPhPdX2 (where Ar = aryl and X = halogen) in each case. Such as dialkyl amine), triaryl scales and solubilizers. Such a preferred catalyst system according to the invention consists equally well of said components. The co-solvent preferably contains at least one selected from the group consisting of toluene, xylene, chlorobenzene, N, N-dimethylformamidine, and 1-methyl 4 pyrachidone (N-methylpyrrolidone (NMP)). ingredient. Contains the following ingredients: triphenylphosphine, palladium dichloride (ιι) (that is, [PhfLPdci2), triphenylphosphine (that is, [ph3P]), copper (I) iodide, triethylamine, and toluene. The co-solvent catalyst system is 07-200406031 (51) Can Ming said two achievements:

optimal.

The preferred reaction procedure for the mixture obtained from step (A) (and optionally post-processed) at the terminal alkyne is that the mixture is first mixed with a base (such as triethylamine) and a co-solvent (such as toluene). Stir for several minutes at room temperature. Then add palladium-triphenylphosphine complex (such as Pd (PPh3) 2Cl2), phenylphosphine (PPh3) and copper halide (such as copper (I) iodide), the mixture is at 5CTC to 90 ° C (more 80 ° C to 85 ° C). The terminal alkyne is then added within said temperature range within 1 to 20 hours (more preferably 3 hours). After the addition is complete, the mixture is heated at a temperature of 75 ° C to 85 ° C (more preferably 80 ° C) for at least 5 to 20 hours (more preferably 12 hours). Then, a solvent was added to the reaction solution, and distilled under reduced pressure. After filtration, the reaction solution is preferably cooled to a temperature of 20 ° C to 30 ° C (more preferably 25 ° C). Finally, the reaction mixture in step (B) is specifically for removing trace metals (such as palladium). The reaction mixture in step (B) is post-processed using methods known to those skilled in the art.

If the mixture of step (B) is precipitated into some solvents, the peak ratios of the monomers obtained in step (B) above to its dimers, trimers and oligomers are shifted in the reaction mixture. It is unexpectedly found that the reaction sequence directly starts from adamantane, and the oligomer or polymer content obtained in the reaction product of step (A) can pass through the adamantane, halobenzene compound, and the second catalyst component (that is, the third Butyl bromide). In a corresponding manner, the benzene content of the reaction mixture in step (A) is also successfully adjusted through this ratio. Since benzene is toxic for industrial scale synthesis, the adjustment of the benzene content is very important. The oligomer or polymer content allows the same secondary chemistry as the monomer (monomer is -58-200406031, for example) # 'Ming: description continued 丨 1, 3, 5, 7-, (374, bromophenyl) Jingang | Jane, that is, oligomer or polymer can be used as monomer for step (B) reaction with terminal alkyne). In a specific embodiment, a thermosetting component and a pore-forming agent are combined. The amount of the thermosetting component is about 50 to about 90% by weight, and the amount of the porogen is about 10 to about 50% by weight. The thermosetting component and the pore-forming agent may or may not react together. The adhesion promoter is preferably added subsequently. Preferably in another embodiment, the composition comprises a mixture of at least two different isomers of the formula XXVII

Η

Here Q is defined as before and includes porogens. Preferably the mixture contains at least two different isomers having formula XXVIII

, Formula XXIX

Or XXX 200406031

Here each γ is the same or different and is selected from hydrogen, alkyl, aryl, substituted aryl or halogen atom; and each R! Is the same or different and is selected from hydrogen, self atom, alkyl , Aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, fluorenyl, alkynyl, light or several base. Preferred mixtures contain at least two different isomers of the formula XXXI

Here each Q is defined as before. Preferred mixtures contain at least two different isomers of the formula XXXII

Formula XXXIII -60- 200406031 Fenming Instructions Continued '

(54) R

Η

Or formula XXXIV

Υ Here Υ and κ are as defined above. Adhesion accelerator: The term "adhesion accelerator" is used here to mean any component that, when added to a thermosetting component, is a component that improves the adhesion to the substrate when compared to a thermosetting component alone. The term "compound having at least a bifunctional group" is used herein to mean any compound having at least two functional groups which can interact or react or form a bond as follows. Bifunctional groups can react in numerous ways including addition reactions, affinity and electrophilic substitution or elimination reactions, group reactions, and the like. In addition, other reactions include the formation of non-covalent bonds such as Van der Waals bonds, electrostatic bonds, ion bonds, and hydrogen bonds. -61-200406031 (55) 杳 明 说明 Continued;

In a specific embodiment, an adhesion promoter and a pore-forming agent are combined. Based on a composition comprising an adhesion promoter, a pore-forming agent, and a thermosetting component, the amount of the adhesion promoter is about 3 to about 18% by weight, and the amount of the pore-forming agent is about 10 to about 50% by weight. The adhesion promoter and the pore-forming agent may react together or not. Preferably, the thermosetting ingredient is subsequently added in an amount of about 32 to about 87% by weight.

The inventors have found that adhesion promoters can advantageously improve the compatibility between pore formers and thermosetting ingredients. Although not intending to be bound by theory, the inventors believe that adhesion promoters can be used as emulsifiers, thus forming a homogeneous system. Adhesion promoters are disclosed in the patent applications 60/350187, which were jointly reviewed by the inventors, with application dates of January 15, 2002 and 10/160773, and applications dated May 30, 2002. Go here.

In the adhesion promoter, it is preferred that at least one of the first functional group and the second functional group is selected from a silicon-containing group, a nitrogen-containing group, a carbon bond to an oxygen-containing group, a hydroxyl group, and a carbon double bond to a carbon-containing group. base. Preferably, the silicon-containing group is selected from Si-H, Si-O, and Si-N; the nitrogen-containing group is selected from, for example, C-NH2 or other secondary and tertiary amines, imines, amidines, and amidines. Imines. The carbon-bonded to oxygen-containing system is selected from the group consisting of = CO, carbonyl (such as ketones and aldehydes), esters, -COOH, alkoxy groups containing 1 to 5 carbon atoms, ethers, glycidyl ethers, and rings Oxygen; hydroxy is phenol and carbon is double-bonded to a carbon-containing group selected from propenyl and vinyl. For semiconductor applications, preferred functional groups include silicon-containing groups; carbon bonds to oxygen-containing groups; hydroxyl groups; and vinyl groups. A preferred adhesion promoter with a silicon-based group is, for example, the formula XXXVI: Silane, where R2, R3, R4, and 115 each independently represent hydrogen -62- 200406031 (56) Phosphorus page:

, Hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkyl (here the substituent is amine or epoxy), saturated or unsaturated epoxy, unsaturated or saturated carboxylic acid or aryl ; At least two of R2, R3, R4, and R5 represent nitrogen, a hydroxyl group, a saturated or unsaturated alkoxy group, an unsaturated thiol group or an unsaturated double acid group; and k + l + m + n ^ 4. Examples include acetofluorite such as H20 CHSi (CH3) 2H and H2OCHSi (R6) 3, here CH3〇, C2H50, Ac〇, H2C = CH or H2C = C (CH3) 〇- or vinylphenyl Methylsilane; formula H2C = CHCHr Si (〇C2H5) 3 and H2C = CHCHrSi (H) (〇CH3) 2 acrylsilane; glycidyloxypropyl sulphate such as (3-glycidoxypropyl) Dimethoxysilane and (3-glycidyloxypropyl) trimethoxysilane; formula h2C = (CH3) COO (CH2) 3-Si (〇R7) 3 methacryloxypropyl stone Burning, here r7 is 元 'is preferably methyl or ethyl, aminopropyl crushed derivatives include

H2N (CH2) 3Si (OCH2CH3) 3, H2N (CH2) 3Si (0% or H2N (CH2) 3Q. The aforementioned silanes are commercially available from Gdest).

Preferred adhesion promoters with a carbon bond to an oxygen-containing group are, for example, condensed glyceryl ethers, including but not limited to 1, U-shen ((hydroxyphenyl) ethane tri-glycidyl ether), commercially available from Cui Quest (Ding Quest). Preferred adhesion promoters having a carbon bond to an oxygen-containing group are, for example, unsaturated carboxylic acid esters containing at least one carboxylic acid group. Examples include trifunctional methylpropionate, trifunctional propionate, trimethylolpropyl triacrylate, diisopentaerythritol pentaacrylate, and glycidyl methacrylate. Poverty is available on the market from Sartomer. A preferred adhesion promoter with a vinyl group is, for example, a vinyl cyclic pyridine oligomer or polymer, wherein the cyclic group is a pyridine aromatic or heteroaromatic -63-200406031 (57) group. Useful examples include, but are not limited to, 2-ethyridylpyridine and 4-vinylpyridine are commercially available from Reilly, ethynyl aromatic compounds, and vinyl heteroaromatic compounds, including but not limited to vinyl p Check 4. Vinyl Carba Jun, Ethyl Base Bites and Ethyl Base Bites. A preferred adhesion promoter with a silicon-based group is, for example, polymethanesilane, disclosed in commonly assigned and co-examined US Patent Application No. 09/471299, filed on December 23, 1999, the entire text of which is incorporated by reference Ways are incorporated here. Polymethylsilane has the formula XXXVII:

Si-R8 --- a p-Rio £ J: ... ol R11 a c 51 ^ 14) —R13 Η

RlS

Si —R17

I

R16, where r8, r14, and r17 each independently represent a substituted or unsubstituted alkylene, cycloalkylene, vinylidene, propylene, or aryl group; R9, R10, Rn, R12, R15, and R16 Each independently represents a hydrogen atom or an organic group containing an alkyl group, an alkylene group, a vinyl group, a cycloalkyl group, a propenyl group, or an aryl group, and may be linear or branched; R13 represents a silicone, a silyl group, a siloxy group, or an organic group And p, q, r, and s satisfy the condition [4 neighbors + q + r + s <100,000] and q and r and s may be zero together or independently. Organic groups contain up to 18 carbon atoms, but usually contain about 1 to about 10 carbon atoms. Useful alkyl groups include -CH2- and-(CH2) t-, where t> 1. Preferred polymethysilanes of the present invention include dihydroanion polymethysilanes, in which r8 is a substituted or unsubstituted alkylene or phenyl group, r9 is a hydrogen atom, and the polymethysilane chain has no side. Group; in other words q, r and s -64- 200406031 (58) sprouting said from the monthly page;, ', st; s; S ^, ί,', ', one,, * i / ν-^ ', 4' * ~ m are all zero. Another group of preferred polymethysilanes are those in which the R9, R1 (), Rn, R12, R15, and R16 groups of formula XXXVII are substituted or unsubstituted alkenyl groups containing 2 to 10 carbon atoms. Alkyl may be ethylene, allyl, propyl, butyl, or any other unsaturated organic backbone group containing up to 10 carbon atoms. The olefin is basically a dilute group, and includes an unsaturated fluorenyl group derived from or substituted by an alkyl group or an unsaturated organic polymer main chain. These preferred polymethysilanes include, for example, dihydroanions or polymethylsilyls substituted by polyhydroxides, such as polydihydroanions, methylsilyls, polypropylene hydrides, and methyldisilanes, and polypropylene. A random copolymer of methyl anion methylsilyl. In the more preferred polymethysilanes, the r9 group of the formula XXXVII is a hydrogen atom and r8 is a methylene group, and the bypass groups q, r, and s are zero. Other preferred polymethylsilyl compounds of the present invention are polymethylsilyl silanes of the formula XXXVII, in which R9 and R15 are hydrogen, R8 and R17 are methylene and R16 is fluorenyl and the by-passing groups q and r are zero. Polymethanesilane can be prepared by methods known in the prior art or provided by the manufacturer of the polymethanesilane composition. Among the best polymethysilanes, the R9 group of formula XXXVII is a hydrogen atom; Rg is -CH2-; q, r and s are zero and p is 5 to 25. The best polymethysilane is available from Starfire Systems. Specific examples of the best polymethylsilane: Polymethylsilane-weight average molecular weight (Mw) polydispersity peak molecular weight (Mp) 1 400-1,400 2-2.5 330-500 2 330 1.14 320 3 (with 10% propylene Group) 10,000-14,000 10.4-16 1160 4 (containing 75% propenyl group) 2,400 3.7 410 As can be known from formula XXXVII, the polymethylsilyl silane used in the present invention contains an oxidizing group in the form of a siloxy group at r &gt; 0. So when r> 0, R13 means organic -65-200406031 (59) Invention page:

Silicon, silyl, siloxy or organic. It is to be understood that the oxidized version (r &gt; 0) of polymethanesilane can be used very effectively and advantageously in the present invention. It is also obviously easy to know that, independently of p, q, and s, r may be zero. The only condition is that the groups p, q, r, and s of the polymethylsilazane of the formula XXXVII must meet the conditions [4 &lt; p + q + r + s &lt; 100,000], and q and r may be zero together or independently.

Polymethanesilane can be made from starting materials currently available from a number of manufacturers or using conventional polymerization methods. As for the synthesis examples of polymethysilane, the starting materials can be made from common organic silane compounds or polysilane as starting materials. The preparation method is to heat the mixture of polysilane and polyborosiloxane in an inert atmosphere to produce the corresponding polymer; or Polysilane and low molecular weight methylmercury mixture are heated in an inert atmosphere to produce the corresponding polymer; or via a mixture of polysilane and low molecular weight methylsilyl silane in an inert atmosphere and heated in the presence of a catalyst such as polyborodiphenylsiloxane, Accordingly, a corresponding polymer was produced. Polymethanesilane can also be synthesized by the Grignard reaction reported in U.S. Patent 5,153,295, which is incorporated herein by reference.

Preferred adhesion promoters with hydroxyl groups are, for example, phenol-formaldehyde resins or oligomers of the formula XXXVIII:-[R18C6H2 (〇H) (R19)] U-, where R18 is a substituted or unsubstituted alkylene Group, cycloalkylene, ethynyl, propionyl, or aryl; R19 is alkyl, alkylidene, ethylidene, cycloalkylene, propenyl, or aryl; and u = 3-100 . Useful alkyl groups include -CH2- and d- (CH2) v-, where v &gt; 1. Particularly useful phenol-formaldehyde resin oligomers have a molecular weight of 1500 and are commercially available from Schenectady International. The adhesion promoter is preferably added in a small amount, and an effective amount is about 0.5% to at most 20% by weight of the thermosetting composition, and at a weight ratio of up to about 5.0% -66- 200406031 (60) The number is usually better. By combining an adhesion promoter with a thermosetting component, and a heat source or high energy source, the resulting composition has properties throughout the polymer. Therefore, ensuring good affinity for any contact surface of the coating can also improve stripe control, viscosity, and film inspection. It was confirmed that the degree of streak control was improved. The composition also contains other ingredients such as additional adhesion foams, cleaners, flame retardants, pigments, plasticizers, and activators. Pore-forming agent: The term "pores" is used here to include voids in the material and any other indication of the space in the material occupied by the gas. Suitable for the same pure gas and its mixture. Air is predominantly nitrogen. Air is commonly distributed in the pores, but it is expected to cover nitrogen, helium, argon, carbon dioxide, or carbon monoxide. Spherical, but in addition or in addition may include a tube shape, a layered shape, an S-shaped gap of a disk shape, or a combination of the foregoing shapes, and is closed. The term "pore-forming agent" is used herein to denote a material that can be decomposed, decomposed, or otherwise decomposed by radiation, heat, chemical or moisture. Pore-forming agents include solids and liquids. The decomposed pore-forming agent can be removed, or can be gasified, or cross-linked or completely cross-linked matrix, and then the gap is completely hardened, so that the dielectric constant of the matrix is reduced, and sacrificial polymeric materials such as carbon dioxide can be used to remove Pore formers and grouping compounds receive excellent adhesion. The adhesion evenness. Mesh accelerators, inhibitors, interfacial cells, and any gas include pure gases mixed with oxygen, such as pores that are typically shaped, have materials that can be open or solvable, and decompose, depolymerize, or diffuse gas materials through the substrate to form pores组合。 The compound. Pore formation after super dissolution 200406031 (61) Description of the invention Continued Preferably used for thermally decomposable porogens, the porogen contains a material having a decomposition temperature lower than the glass transition temperature (Tg) of the dielectric material with which it is combined and higher than the hardening temperature of the dielectric material with which it is combined . The dielectric material and the porogen are thus different materials. Preferably, the pore former has a degradation or decomposition temperature of about 350 ° C or above. It is preferred that the porogen after vaporization or decomposition be vaporized at a temperature which is higher than the hardening temperature of the material with which the porogen is combined, and lower than the material Tg. It is preferred that the pore former after degradation or after decomposition is gasified at a temperature of about 280 ° C or above. Although International Patent Publication WO 00/31183 teaches that a pore former can be added to a heat-curable benzocyclobutadiene, a polyarylidene, or a thermosetting perfluoroacetamidine monomer, rhenium increases its porosity, thereby reducing the resin's Dielectric constant, but references teach that pore formers known to function well with a first matrix system may not function well with another matrix system. Pore formers useful in the present invention include at least two fused aromatic rings, wherein each of the fused aromatic rings has at least one alkyl substituent based thereon, and an alkyl substituent group bonded to an adjacent aromatic ring At least between the two. Preferably, the pore-forming agent includes an unfunctionalized polyfluorene homopolymer, a functionalized polyfluorene homopolymer, a polyfluorene copolymer described later, poly (2-ethylfluorenylnaphthalene), and vinyl anthracene and its fluorene组合。 The compound. Other useful pore formers include adamantane, bisdamantine, flillerene, and polyorbornene. Each of these pore formers may be blended with each other or with other pore former materials such as polycaprolactone, polystyrene and polyester. Useful adducts include unfunctionalized polyfluorene homopolymers and polycaprolactones. More preferred pore-forming agents are unfunctionalized polyfluorene homopolymers, functionalized polyfluorene homopolymers, polyfluorene copolymers, and polyorborneol. 200406031 (62) Description sheet of the invention: Useful polyfluorene homopolymers have a weight average molecular weight preferably in the range of about 300 to about 20,000; more preferably about 300 to about 10,000; and most preferably in the range of about 1,000 to about 7,000, It can also be prepared from fluorene polymerization using different initiators, such as 2,2'-azo hydrazone isobutyronitrile (AffiN); azodicarboxylic acid di-third butyl ester; azodicarboxylic acid diiso Propyl ester; Diethyl azodicarboxylate; Dimethyl azodicarboxylate; Diphenyl azodicarboxylate; 1, Γ-Azofluorene (cyclohexanecarbonitrile); Benzoyl peroxide (BPO); third butyl peroxide and diethyl boron trifluoride etherate. Polyfluorene homopolymers have functional end groups, such as double or reference bonds to the end of the chain; or use double or reference alcohols such as propanol, propynol, butynol, butenol, or hydroxyethyl Methylpropionate) quenches cationic polymerization. European Patent Publication No. 315453 teaches that silicon oxide and certain metal oxides can react with carbon to form volatile suboxides and gaseous carbon monoxide to form pores; and teaches that carbon sources include suitable organic polymers (including polyfluorene). However, this reference does not teach or suggest that polyfluorene is a useful non-metallic material or a porogen for reducing the dielectric constant of the substrate. Useful polyfluorene copolymers can be linear polymers, star polymers or highly branched polymers. The comonomer may have a large branched chain group, and the branched chain group will obtain a copolymer configuration similar to a polyfluorene homopolymer; or there may be a non-large branched chain group, the copolymer configuration obtained by the non-large branched chain group will be a non-similar polymer组态 Copolymer configuration of homopolymer. Comonomers with large branching groups include vinyl isovalerate, third butyl acrylate, styrene, α-methylstyrene, third butylstyrene, 2-vinylfluorene, 5-vinyl- 2-orbornene, vinylcyclohexane, vinylcyclopentane, 9-vinylanthracene, 4-vinylbiphenyl, -69- 200406031 (63) Description sheet of the invention: tetraphenylbutadiene, Stilbene, tert-butylstilbene, and indene; and preferably vinyl isovalerate. The blended polymethanesilane can be used as an additional comonomer or comonomer component with at least one of rhenium and the aforementioned comonomer. Useful blends include polymethylsilyl for example containing 10% or 75% propionyl. Comonomers with non-massive branching groups include ethyl acetate, methyl propionate, methyl methacrylate, and vinyl ether, and vinyl acetate is preferred. A preferred amount of comonomer is in the range of about 5 to about 50 mole% of the copolymer. These copolymers can be made by radical polymerization using initiators. Useful initiators preferably include 2,2'-azobisisobutyronitrile (AIBN); di-third butyl azodicarboxylate; diisopropyl azodicarboxylate; diethyl azodicarboxylate Esters; difluorenyl azodicarboxylate; diphenyl azodicarboxylate; 1, Γ-azohydrazone (cyclohexanecarbonitrile); benzamidine peroxide (BPO); and tert-butyl peroxide And more preferably AIBN. Copolymers can be prepared by cationic polymerization using initiators such as boron trifluoride diethyl etherate. Preferred copolymers have a molecular weight of about 500 to about 15,000. The thermal properties of fluorene copolymers and comonomers are set out in Table 5 below. In Table 5, Β means butyl acrylate; VP means ethylene isovalerate; VA means vinyl acetate; AIBN means 2,2'-azobisisobutyronitrile; BF3 means diethyl boron trifluoride etherate ; DBADC means di-tert-butyl azodicarboxylic acid; W1 means weight loss percentage from room temperature to 250 ° C; W2 means weight loss percentage after 250 minutes at 250 ° C; W3 means from 250 ° C to The weight loss percentage at 400 ° C; W4 represents the weight loss percentage at 400 ° C after 1 hour and W5 represents the total weight loss. 200406031 (64) P1 description page &lt; &lt; &lt; &lt; &lt; &lt; &lt; &lt; &gt; CO &gt; CD &gt; CO &gt; CO &gt; Co-monomer 3 5-2 5 00 &lt; 1 Os LT \ LO K) Copolymer AIBN AIBN BF3 BF3 ί _.....! BF3 BF3 BF3 I BF3 1 AIBN 1 AIBN AIBN AIBN AIBN AIBN BF3 AIBN AIBN AIBN AIBN Initiator K) C- Λ S one. U) to 5; LT \ LO comonomer ° / 〇N3 ΙΟ Lk)-Lk)-U)-j-H-^ μ-fc U)-initiator% xylene l · -9 xylene l · Xylene xylene 1 l · xylene l · l ·! Xylene l ·-€! THF ll · l · xylene l · xylene xylene 1___ solvent Lrt LT \ Ln g temperature CC) to to ro K) K ) \ &gt; 〇K) to to to to to to to to time (hours) 15.45 16.93 0.28 0.23 ί— U) 0.17 2.26 0.84 1 14.12 6.34 ί 14.7 1 4.15 5.32 16.22 11.93 10.01 13.41 14.63 1.631 1.346 0.01! 0.04 1 0.03 ο 0.06 o 0.32 0.26 0.69 0.37 0.66 0.41 0.58 2.96 s; 0.98 S W2 31.28 38.42 40.23 36.46 35.28 36.99 47.44 55.51 29.01 33.69 33.27 I 24.98 Bu 6.55 37.8 40.06 46.92 36.48 37.92 33.14 31.64 21.38 38.08 41.08 41.08 38.08 41.08 41.38 38.08 41.08 41.08 38.08 41.08 38.08 41.64 38.08 41.64 41.38 38.08 41.64 41.64 38.38 41.64 41.64 38.38 41.64 41.64 38.38 41.64 41.64 41.64 38.38 41.64 41.64 41.38 38.42 38.42 0.03 1 39.54 1 47.4 29.59 34.72 29.33 26.51 27.55 35.55 30.44 W4 80.00 78.13 79.50 78.90 77.72 78.33 78.69 95.73 81.31 76.67 88.20 76.90 1 82.12! 89.15 81.90 86.40 1 79.04 75.92 79.23 3109 3404 2270 2270 2 1786 2078 4037 4612 5342 2657 1598 5442 1502 3504 4638 4343 4797 3 6141 7193 3376 3692 3267 3549 2821 3229 6405 | 7782 9303 1 8621 2422 10007 2421 5489 7826 8103 10552 Mw 200406031 (65) Examples of known pore formers Linear polymers, star polymers, crosslinked polymer nanospheres, block copolymers, and highly branched polymers can be used for the novel thermosetting ingredients of formula I or II. Suitable linear polymers are polyethers such as poly (ethylene oxide) and poly (propylene oxide); polyacrylates such as poly (methyl methacrylate); aliphatic polycarbonates such as poly (propylene carbonate) Esters) and poly (ethylene carbonate); polyesters, polyfluorenes, polystyrene (including monomer units selected from halogenated styrene and hydroxyethyl substituted acetophenone); poly (α-methyl Phenylacetate); Polylactide; and other polymers based on vinyl. Useful polyester pore formers include polycaprolactone; poly (ethylene terephthalate); poly (oxyhexamethyleneoxy-1,4-phenylene); poly (oxyterephthalate) Oxy-1,4-phenylene); poly (oxyhexamethyleneoxy-1,6-hexamethylene); polycarbonates such as poly (hexamethylene carbonate) glycols having a molecular weight of about 500 To about 2500; and polyethers such as poly (bisphenol A-copolymer-epichlorohydrin) having a molecular weight of about 300 to about 6,500. Properly crosslinked insoluble nanospheres (prepared as nanoemulsions) are suitable to contain polystyrene or poly (methyl methacrylate). Suitable block copolymers are poly (styrene-copolymer-α-methylphenethylhydrazone), poly (styrene-ethylene oxide), poly (ether lactones), poly (ester carbonates), And poly (lactone lactide). Suitable highly branched polymers are highly branched polyesters such as highly branched poly (caprolactone) and polyethers such as polyethylene oxide and polypropylene oxide. Another useful pore former is ethylene glycol-poly (caprolactone). Useful polymer segments include polyvinylpyridines, hydrogenated polyvinylaromatics, polyacrylonitrile, polysiloxanes, polycaprolactams, polyurethanes, polydienes ( For example, polybutadienes and polyisoprenes), polyvinyl chlorides, polyacetals, and alkylene oxides based on amine groups. 200406031 (66) Invention description. Other useful thermoplastic materials include polyisoprenes, polytetrahydrocranes, and polyethylammoniums. The generation of pores:

The term "degradation" is used herein to indicate the breaking of covalent bonds. Such covalent bond breaks can occur in a variety of ways, including non-homogeneous breaks and homogeneous breaks. The covalent bond does not need to be completely broken, that is, not all cleavable bonds need to be broken. In addition, bonds may break faster than others. For example, the ester bond is generally less stable than the amidine bond, and therefore is cleaved at a faster rate. The breaking of the bond depends on the chemical composition of the degraded part, and may also result in the release of different fragments.

In the process of pore generation, the pore-forming agent used for thermal cracking applies thermal energy to the material containing the pore-forming agent, and the pore-forming agent is substantially degraded or decomposed into its original component or monomer. As used herein, "substantially degrading" means that at least 80% by weight of the pore former is degraded or decomposed. The preferred thermosetting ingredients for formulae I and II above have a Tg of about 400 ° C to about 450 ° C, so pore formers with a degradation or decomposition temperature of about 350 ° C or above are particularly useful for this thermosetting ingredient. For homopolymer or copolymer porogens, which are preferably polyfluorene-based, the inventors have discovered that by using analytical techniques such as thermal desorption mass spectrometry, the porogen can be degraded, decomposed, or depolymerized into its fluorene monomer. And comonomer starting ingredients. Thermal energy can also be applied to remove pore formers that have been substantially degraded or decomposed by gasification from the matrix of the thermosetting composition. Preferably, the thermal energy is used in the decomposition and gasification steps. As the amount of pore-forming agent that has been vaporized and degraded increases, the porosity of the resulting thermosetting component also increases. Used for the aforementioned thermosetting ingredients of the preferred formulas I and II, Tg is about 400 ° C to about 450 ° C, so the substantial degradation of this -73-200406031 (67)

Pore formers have a gasification temperature of about 280 ° C or above and are particularly suitable for this type of thermosetting composition. The hardening temperature, which is preferably used for cross-linking thermosetting components, can also be substantially degraded into a porogen, and the porogen is removed by gasification in a thermosetting matrix. Typical hardening temperatures and conditions will be described in the “Uses” section below.

The pores formed can be uniformly or randomly dispersed throughout the matrix. Preferably, the pores are uniformly dispersed throughout the matrix. In addition, other procedures or conditions can be used that at least partially remove the pore-forming agent without adversely affecting the thermosetting composition. It is preferred to substantially remove the porogen. Typical removal methods include, but are not limited to, exposure to radiation, such as, but not limited to, electromagnetic radiation such as ultraviolet, X-ray, laser, or infrared radiation; mechanical energy such as ultrasound or physical dust; or light emission of particles such as gamma rays, Alpha particles, neutron beams or electron beams. Purpose: The term "layer" is used here to mean films and coatings.

The term "low dielectric constant polymer" is used herein to mean an organic, organometallic, or inorganic polymer having a dielectric constant of about 3.0 or less. Low dielectric constant materials are typically manufactured in thin layers with a thickness of 100 to 25,000 Angstroms, but can also be used in the form of thick films, massive bodies, cylinders, spheres, and the like. The present composition consisting of a thermosetting component, an adhesion promoter, and a porogen can be used to reduce the dielectric constant of the material. Preferred dielectric materials have a dielectric constant k of less than or equal to about 3.0 and more preferably about 1.9 to 3.0. The dielectric material preferably has a glass transition temperature of at least about 350 ° C. This composition layer consisting of thermosetting ingredients, adhesion promoter and pore-forming agent -74- 200406031 Description of the Invention Continued pages, spin-coating, and flow-up The composition agent includes any, which can be similar to cyclic ketone acid amines Such as N-atoms; and the solubility of organic solvents can also be added. Multiple solutions. Other suitable dibutyl ether esters, 2-heptanone, propylene glycol methyl xylene, and the thickness of the type II layer are layers, and the layer thickness is a single integrated battery. Integrated electrical multilayer metal conductors or conductors (68) can be manufactured by solution technology, such as spray coating, roll coating, dip coating or casting; spin-coating is preferred for microelectronics. It is more soluble in solvents. Appropriate solution for the composition of the present invention is suitably pure or mixed with organic, organometallic or inorganic molecules and vaporized at a fixed temperature. Suitable solvents include aprotic solvents such as cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone; cyclic alkyl pyrrolidone, wherein the alkyl group contains about 1 to 4 carbon N-cyclohexylpyrrolidone and Its mixture. A variety of other are useful here, as long as these organic solvents can assist adhesion promotion, and at the same time effectively control the viscosity of the resulting solution as a coating liquid, such as stirring and / or heating can be used to assist the solvent including methyl ethyl methyl Ketones, methyl isobutyl ketones, cyclic dimethyl polysiloxanes, butyrolactone, γ-butyrolactone, ethyl 3-ethoxypropionate, polyethylene glycol [di] methyl ether, ether Acetate (PGMEA) and anisole; and hydrocarbon solvents such as toluene, benzene and xylene. A preferred solvent is cyclohexanone. Code 0.1 to about 15 microns. Dielectric intermediateness as a microelectronic device is usually less than 2 microns. This composition can be used in electrical devices, especially interlayer dielectric materials used as interconnect devices associated with circuit ("1C") wafers. Typical wafers have multiple layers of the composition and bulk layers on the surface. It also includes that the area of the composition is between the respective metal conductor areas on the same layer or the same height of the integrated circuit. When the polymer is applied to 1C, the composition solution is a conventional wet coating 200406031 (69) Summary sheet of the invention 丨

The method is applied to a semiconductor wafer by a spin coating method; in a special case, other well-known coating techniques such as spray coating, flow coating, or dip coating may also be used. For example, a cyclohexanone solution of the composition is spin-coated onto a substrate with a conductive element manufactured thereon, and then the coated substrate is subjected to heat treatment. The exemplary formulation of this composition is prepared by strictly following the clean operation scheme under ambient conditions, and dissolving this composition in cyclohexanone to prevent any trace metal contamination of any conventional device with a non-metallic pad. The resulting solution is preferably based on the total weight of the solution, and preferably contains about 70 to about 98 weight percent of a thermosetting component, about 2 to about 30 weight percent of an adhesion promoter, about 5 to about 25 weight percent of a pore former, and about 75 to about 95 weight percent solvent.

The purpose of the present invention will be described later. The application of the composition to form a layer on a surface or a flat or topographic surface of a substrate can be performed by any known device, preferably by a spin coater. The composition used herein has a controlled adhesion suitable for such a coater. Evaporation and removal of the solvent can be performed by any suitable means, such as simply air-drying and evaporation during spin coating, or exposure to the surrounding environment, or heating and evaporation to remove the solvent on a hot plate up to 350 ° C. The substrate may be provided with at least one layer of the preferred composition, which is composed of a thermosetting component, an adhesion promoter, and a pore former. The substrates contemplated herein include any desired substantially solid material. Particularly desirable substrate layers include films, glass, ceramics, plastics, metals, or coated metals or composite materials. In a preferred embodiment, the substrate includes chipped or gallium-coated die or wafer surfaces; the package surface appears, for example, on a leadframe surface of copper, silver, nickel, or gold; the copper surface appears, for example, on a circuit board or package Copper surface of solid interconnect; through-hole wall or stiffening -76- 200406031 (70) Summary sheet

Component surface ("copper" includes bare copper and its oxides); polymer-based packages or board dielectrics, such as appear on the surface of flexible packages, leads, or other metal alloy solder beads based on polyimide , Glass and polymers. Useful substrates include silicon, silicon nitride, silicon oxide, silicon oxycarbide, silicon dioxide, silicon carbide, silicon oxynitride, titanium nitride, hafnium nitride, tungsten nitride, aluminum, copper, buttons, organic silicon oxide Alkane, organosilicon glass and fluorinated silica glass. In other embodiments, the substrate includes materials commonly used in the package and circuit board industries, such as chip, copper, glass, and polymers. The composition can also be used in a microchip, a multi-chip module, a laminated circuit board or a printed wiring board as a dielectric substrate. Various conductive circuit patterns are provided on the surface of a circuit board composed of the composition. The circuit board includes various reinforcing members such as woven non-conductive fiber or glass cloth. Such circuit boards can be single-sided or double-sided.

Each layer made of the composition has low dielectric constant, high thermal stability, high mechanical strength, and excellent adhesion to the surface of an electronic substrate. Because the adhesion promoter is molecularly dispersed, these layers show excellent adhesion to all adhesion layers, which include the base substrate and the overlying cover or mask layer such as silicon oxide and silicon nitride cover layers. The use of these layers can eliminate the additional processing steps of at least one primer coating application form, and achieve film adhesion to the substrate and / or the top surface. After the composition is applied to a terrain substrate for electronics, the coated structure is subjected to baking and hardening heat treatment at a temperature range of about 50 ° C to at most about 450 ° C, and a polymer coating is applied. Since the lower temperature is not sufficient to complete the reaction described here, the hardening temperature is at least about 300 ° C. It is generally preferred that the hardening be performed at a temperature of about 375 ° C to about 425 ° C. Hardening can be performed in conventional hardening chambers such as -77-200406031 (71) #Specification sheet, circuit, hot plate, etc., usually in a hardening chamber under an inert (non-oxidizing) atmosphere (nitrogen). In addition to circuit or hot plate hardening, the composition can also be hardened by exposure to ultraviolet radiation, microwave radiation, or electron beam radiation, such as commonly assigned patent publications PCT / US96 / 08678 and US patent 6,042,994; 6,080,526; 6 , 177,143 and 6,235,353 teachings, each of which is incorporated herein by reference. Any non-oxidizing or reducing atmosphere (such as argon, helium, hydrogen, and nitrogen treatment gases) can be used to implement the low-k dielectric layer as long as the thermosetting component modified by the adhesion promoter can be effectively cured to achieve the low-k dielectric layer here. invention. Although not intended to be interpreted as a limitation, the treatment used to prepare the present low-dielectric constant composition was observed to obtain a homogeneous solution of a thermosetting component, an adhesion promoter, and a porogen. Preferred silane adhesion promoters can be advantageously used in low dielectric constant compositions to perform multiple functions. For example, the treatment of the composition can allow the better polymethylsilane adhesion promoter to interact with the unsaturated structure of the pore former and the thermosetting component. It is believed that the silane portion of the better polymethylsilylsilane interacts with the pore former and the thermosetting component. It is presumed that polymethysilane can be used as a surfactant or emulsifier to uniformly disperse the pore-forming agent in the thermosetting component of the low-dielectric composition. This is important for making a composition that can obtain a homogeneous film (or thin layer) with uniformly dispersed pores of extremely small size. The silane portion of polysilazane can also interact with the substrate surface, thus forming a chemically bonded adhesive interface for the main thermosetting monomer precursor. It has been proposed that silyl / silyl can be used in all compositions as a source of adhesion by chemically bonding to the interface surface to secure and secure any contact interface. The interaction between the components is described in -78- 200406031 (72) Continued description: The reaction with the silane part can occur during the preparation and during the processing before the formation of the layer. As indicated previously, the silane functional groups with pore-forming agents and thermosetting ingredients are dispersed throughout the composition, indicating that the porosity of the resulting layers is uniform. The dispersion of the silane functionality also obtains reactive groups, and the layer is excellently adhered to the lower substrate surface and the upper surface structure such as a capping layer or a masking layer. It is important to find here that the main structure of the polymethylsilazane adhesion promoter of the preferred formula XXXVII is polysilazane with silicon substituted with hydrogen anions. The characteristics of this polysilazane will be: (1) uniformly mixed with the pore-forming agent to form a homogeneous composition, (2) reactive with the thermosetting component; (3) uniformly mixed and dispersed into the pore-forming agent in thermosetting Ingredients, to obtain a homogeneous composition, as a result of which small pores are uniformly distributed in the final porous layer, and a polymethysilane modified thermosetting composition and a porous layer are produced, which have improved adhesion properties. As mentioned above, the adhesion promoter modified thermosetting component ⑻ coating can be used as an intermediate layer and can be covered by other coatings, such as other dielectric (silicon oxide) coatings, silicon oxide modified ceramic oxide layers, and silicon-containing coatings. Layer, silicon-carbon-containing coating, silicon-nitrogen-containing coating, silicon-nitrogen-carbon-containing coating, diamond-like carbon coating, titanium nitride coating, nitride button coating, tungsten nitride coating, aluminum coating , Copper coating, hafnium coating, organosiloxane coating, organosilicon glass coating, and fluorinated silica glass coating. Such multilayer coatings are taught in U.S. Patent No. 4,973,526, which is incorporated herein by reference. After full verification, the polymethysilane-modified thermosetting component prepared by this method is conveniently formed on the electronic or semiconductor substrate after manufacturing as an inter-line dielectric layer between adjacent conductor paths. It is preferred that this layer have a dielectric constant of less than 2.7, preferably less than 2.5, and more preferably 200406031 (73) Fenming explained that the performance page is 2.2 and the best is less than 2.0.

The film can be used for dual metal damascene (such as copper) processing and metal removal (such as aluminum or aluminum / tungsten) processing for integrated circuit manufacturing. The composition can be used as an etch stop layer, a hard mask, an air bridge, or a passive coating for developing a completed wafer. This composition can be used in desired full spin-coated stacked films, such as taught in Michael E. Thomas, "Spin-Coated Stacked Films for Low-keff Dielectric Devices," Solid State Technology (July 2001), which is incorporated herein by reference in its entirety. Office. Can be stacked with other layers and used in layers containing organosiloxanes, such as commonly assigned U.S. Patent 6,143,855 and pending U.S. application 10/078919, teaching date of Feb. 19, 2002; Hani HOSP⑧, a commercial product of Will International Corporation; such as the nanoporous silica which is taught in US Patent 6,372,666; Hanowell International Corporation ’s commercially available nano glass (NANOGLASS) ® E; commonly assigned to WO 01/29052 teaches silicone silsesquioxane; and fluorosilsesquioxane taught jointly by WO 01/29141, each case cited by reference

Ways are incorporated here. Analytical test method: Proton NMR: A sample of 2-5 mg of the material to be analyzed is placed in an NMR tube. Add about 0.7 ml of deuterated chloroform. The mixture was dissolved by manual shaking. The samples were then analyzed using Varian 400 MHz NMR. Gel Permeation Chromatography (GPC): Waters 2690 separation module is used for separation. This module has a Watt 996 diode array and a Watt 410 differential refractometer detector. Separation was performed on two PL gel 3 micron mixed E 300 X 7.5 mm columns with a flow rate of 1 mL / min in chloroform. About 1 mg / mL concentration solution was injected into a volume of 25 microliters in a repeat operation. Observed -80- 200406031 (74) Summary sheet: Good reproducibility. The columns were calibrated using relatively single dispersed polyphenylene terephthalate standards with molecular weights between 20,000 and 500. For the lower molecular weight standards, the nine types are individually divided and can be resolved by the analysis of the nine types of acetophenone oligomers corresponding to the butylacetophenone monomer. The logarithmic value of the peak molecular weight of the standard matches the third polynomial of the elution time. The widening of the instrument is based on the evaluation of the average elution ratio of toluene to the full width of the half-maximum peak. The absorption in Preparation Examples 1 and 2 below was at a maximum of about 284 nm. The chromatograms are similar in shape at wavelengths below about 300 nm. The results here correspond to 254 nm absorption. Spikes are identified by the molecular weight of polystyrene that can be eluted simultaneously. These values cannot be regarded as the measured molecular weights of the oligomers of Preparation Examples 1 and 2. Higher carbon oligomers, trimers, dimers, oligomers, and incomplete oligomers can be eluted sequentially over time. Each component is broader than that observed for a single dispersed species. This width is known from the full width (minutes) analysis of the half-maximum value of the spikes. Roughly consider widening the instrument and calculating the correction value of visibility_ [seeing sharp observation value of visibility detector] where width ^ is the peak elution time vs. toluene elution time than the observed toluene width after correction. The peak width is converted to a molecular weight width via a calibration curve, and the ratio to the peak molecular width is calculated. Because the molecular weight of styrene oligomer is proportional to the square of its size, the relative molecular weight width is converted to the relative oligomer size width by dividing _ by two. This procedure considers the molecular configuration differences between the two species.丨 3C NMR: The initial measurement value shows a maximum of 4 seconds, and the week is set accordingly. 200406031 (75) Summary page of the invention description; The time is to obtain a quantitative result. All samples were dissolved in CDC13 and 4000 scans were collected. The C, CH, CH2 and CH3 radicals are designated by DEPT. DEPT clearly identified CH2 at 41 I3pm, assigned three adjacent positions of the lost arm of adamantane, and clearly identified CH at 30 ppm as assigned to the unsubstituted position. The adamantane CH2 line near the attachment arm appears at 46-48 ppm. Similarly, the fourth carbon at 35 ppm and CH3 at 31.5 ppm can be assigned to the third butyl. The clusters of peaks between 120 and 123.5 in the aromatic zone are clearly unprotonated aromatics. Based on chemical shifts, the inventors designated these spikes as bromine aromatic carbons. A fourth aromatic in the range of 145-155 ppm is expected to be used for aromatic carbons attached to aliphatic groups, ie, in this case, adamantane. Some spectra have additional spikes at about 14, 23, 29, and 31.5 ppm. These spikes are assigned to heptane, which is used to wash samples. The relative amount of heptane varies substantially from sample to sample. Because heptane was unrealistic for final efficacy, the inventors did not quantify heptane. NMR conditions: • High-resolution 13C NMR spectra were obtained in Varian Unity Inova 400. • 13C frequency: 100.572 MHz. • Gated 4 uncoupling, modulation using WALTZ • Spectral width: 25 kHz • 13C π / 2 pulse -13 microseconds. • Cycle time: 20 seconds. • Data points: 100032, 2 seconds to get time. • Zero padding to 131072 points of FT • 1 Hz exponential smoothing. 200406031 (76) Description of the invention continued: 'Ye Caimu @ 才 斤-质: This analysis was performed on a Fmnigan / MAT TSQ7_ three-stage quadrupole mass spectrometer system with atmospheric pressure free ( API) interface unit, using HP series 1050 book with: the system as the chromatography entrance. Mass 1f ion current and variable single-wavelength UV light data were obtained on time-intensity chromatograms. Chromatography was performed on a 5-micron phenyl-hexyl column (250x4.6 mm) on a Fernominix Luna. The sample injection volume is usually 5 to 20 microliters of concentrated solution, including tetrahydrofuran and no tetrahydrofuran. A preferred preparation of a concentrated sample solution for analysis is to dissolve 10 microliters of injection in tetrahydrofuran at about 5 mg of solid product per milliliter. The mobile phase flowing through the column was L0 ml / min acetonitrile / water, initially at 70/30 for 1 minute, then the gradient program was planned to reach the acetonitrile at 10 minutes, and the concentration was maintained until the chirped bell. Krypton pressure chemical ionization (APCI) mass spectrometry is recorded separately in positive and negative free iL APCI paired end products (the molecular structure formula can provide more information and provide protonated pseudomolecular ions, including adducts with ethyl benzyl matrix). The% tritium discharge is 5 microamperes. The capillary line after heating is about 5 kV and the negative free kV is maintained at 200 ° C, and the gasifier unit is maintained at 400.. The system is set at 15 kV to convert the dynode and the volt electron multiplier. | Mass spectrometry soil 20,000, 丨 · 0 shift / scan 1 recorded, the negative free is about m / z 50 to 2000 amu and the positive pole is about m / z 150 am u. above. In the positive ion separation experiment, the scan in the low-quality-week / ^ ~ τ 'mode' mass range scans up to 2000 amu, and the high-quality μ week / plate-quan mode scans up to 4000 amu. (DSC): DSC measurement is performed using TA instrument-83-200406031, invention description page 2920 difference scanning card meter combined with controller and associated software. The temperature of standard DSC unit is 250. (: to 72 points range ( Inert atmosphere:% ml / min nitrogen ) For analysis. Liquid nitrogen is used as a source of cooling gas. An analytical balance using Mettler Toledo, with an accuracy of 0.0001 g, is carefully weighed in small (1 (M2 mg) samples to Automatic DSC aluminum sample tray (Part No. 999999-901). The sample is enclosed with a cover to cover the tray. The cover is perforated in the center to allow gas to escape. The sample is heated under nitrogen at a rate of 10 (rc / minute from 0 to 0). 450 ° C (Cycle 1), and then cooled to 以 at a rate of 100 ° C / min. Instantly heat from 0 ° C to 450 ° C at a rate of 100 C / min for a second cycle (repeated cycle ^). Crosslinking The temperature is determined by the first period. GTIfi analysis. FTIR spectra were obtained in transmission mode using a Nicolet Magna 550 FTIR spectrometer. The background spectrum of the substrate was obtained on an uncoated substrate. The substrate was used as the background to obtain Thin film spectrum. Analyze the change in peak position and intensity of the thin film spectrum. Dielectric constant: Coat an aluminum thin film on a hardened layer, then perform capacitance-voltage measurement at 1 MHz, and determine the k value based on the layer thickness to determine the dielectric constant . Li Han Teng Tang (Tg): The glass transition temperature of the film is determined by measuring the film stress as a function of temperature. The film stress measurement is performed on KLA 3220 Flexus. Before the film measurement, the uncoated The wafer is annealed at 500 ° C for 60 minutes to prevent any errors caused by the stress relaxation of the wafer itself. The wafer is then deposited with the test material and processed through all required method steps. Then the wafer is placed on a stress gauge. The stress gauge measures the bending of the wafer as a function of temperature. The instrument calculates the stress versus temperature line graph, but the wafer thickness is -84- 200406031 (78) Description Sheet: and the film thickness is known. The results are displayed as a line graph. To determine the Tg value, draw a horizontal tangent line (stress vs. temperature plot slope value = 0). The Tg value is where the curve crosses the horizontal tangent. Since the measurement process itself may affect Tg ', it must be reported that Ding g is measured after the first temperature cycle or the subsequent cycle using the highest temperature.

Isothermal f-field analysis is based on weight loss. • Total weight f loss is measured by TA Instruments 2950 Thermogravimetric Analyzer (TGA). TGA is used in conjunction with TA Instrument's thermal analysis controller and related software. Use a Platinum II thermocouple and standard furnace with a temperature range of 25 ° C to 1000 ° C and a heating rate of 0.1 ° c to 100 ° C / min. A small amount of sample (7 to 12 mg) was weighed on a TGA balance (resolution: ο ″ g; accuracy ··· to 0.1%) and heated on a platinum plate. The samples were heated under nitrogen at a sweep rate of 100 ml / min (60 liters / min to the furnace and 40 ml / min to the balance). The samples were equilibrated at 20 ° C for 20 minutes under nitrogen, then the temperature was increased to 200 ° C at a rate of 10 ° C / minute and maintained at 200 ° C for 10 minutes.

The temperature was then ramped up to 425 ° C at a rate of 10 ° C / minute and maintained at 425 ° C for 4 hours. Calculate weight loss at 425 ° C over 4 hours. Shrinkage: Film shrinkage is measured by measuring film thickness before and after treatment. Shrinkage is expressed as a percentage of the original film thickness. When the film thickness is reduced, the shrinkage is positive. The actual thickness measurement was performed optically using a J.A. Woollam M-88 spectroscopic ellipsometer. Use the Cauchy mode to calculate the best match of ψ and δ (ellipse metrology details can be found in-for example, "spectrospectral rounding metrology and reflection metrology", authors η · G · Thompkins and William A · McGahan, John Willy & Sons, a% years). Refractive index: The measurement of refractive index is the same as J A,-j J.A. Wu Jian M-88 spectroscopic spectrum ellipse -85-200406031 (79) Initial performance sheet: Round instrument and thickness measurement. Use the test mode to calculate the best matching ψ and δ. Unless otherwise noted, the refractive index is reported at a wavelength of 633 nanometers (for ellipsometry details refer to, for example, "Spectrum Ellipsometry and Reflectometry", authors HG Thompkins and William A. McGahan, John Willy & Sons, 1999 ). Modulus and hardness: Modulus and hardness are measured using a notch test with an instrument. MTS nanonotch XP (MTS Systems, Oak Ridge, Tennessee) was used for the measurements. In particular, the continuous stiffness measurement method is used, which can accurately and continuously determine the module and hardness, instead of measuring the individual values of the unloading curve. The system uses a fused silica calibration with a nominal modulus of 72 + -3.5 GPa. The modulus of the fused silica is obtained from an average of 500 to 1000 nanometer notch depth. The modulus and hardness of the film are based on the smallest value of the modulus versus the depth curve. Tape test: The tape test is performed in accordance with ASTM D3359-95. The grid is scribed on the dielectric layer as described later. The tape test was performed across the lattice marks in the following manner: (1) a piece of adhesive tape (preferably Scotch brand # 3m600-l / 2xl296) was placed on this layer and pressed down firmly to obtain good contact; and (2) ) Then, with an angle of 180 degrees with respect to the surface of the layer, quickly and evenly tear the tape apart. If the layer remains intact on the wafer, the sample is considered acceptable; if some or all of the film is torn off with the tape, it is considered unacceptable. • Buckle pull test: An epoxy-coated buckle is attached to the surface of a wafer containing the layer of the present invention. The ceramic cover plate is applied to the wafer cover side to prevent the substrate from bending and stress from being improperly concentrated on the edge of the buckle. Then borrow the test device and use the standard pull square .. procedure to pull the buckle perpendicular to the wafer surface. Ying -86-200406031 (80) Invented that the force was applied to the point of failure, and then the interface location was recorded. Solvent compatibility: Solvent compatibility is determined by measuring the film thickness, refractive index, FT1R spectrum, and dielectric constant before and after solvent treatment. No significant changes were observed for compatible solvents.

Average pore diameter: The sample is immersed in a 77 ° K liquid nitrogen bath of the sample tube, and measured in a Micromeretics ASAP 2000 automatic isothermal nitrogen adsorption apparatus, using UHP (ultra-high purity industrial gas) nitrogen measurement Nitrogen isotherms for porous samples. For sample preparation, materials are first deposited on a silicon wafer using standard processing conditions. Three wafers were prepared for each sample with a film thickness of about 6000 Angstroms. A powder sample was obtained by scraping the film off the wafer using a blade. The powder samples were pre-dried in a 180 ° C oven before weighing. Carefully pour the powder into a 10 mm ID sample tube, and then degas at 180 ° C at 0.01 Torr for more than 3 hours.

Unless analysis shows that it takes a long time, the nitrogen adsorption and desorption are automatically measured at 5 second equilibration intervals. The time required for isothermal measurement is directly proportional to sample mass, sample pore volume, measured data points, equilibrium interval, and P / Po tolerance (P is the actual sample pressure in the sample tube. P0 is the pressure around the outside of the instrument). The instrument measures the nitrogen isotherm and plots the nitrogen against P / Po. Using the linear segment of the BE Ding equation (to obtain an R2 match> 0.9999), using the BET theory, calculate the nominal BET surface-product from the P / Po area below the nitrogen absorption isotherm [Brunauer, Emmett, Teller method of solid surface multilayer gas absorption] Revealed by S. Day Runauer, PH Gmmett, E. Geller; Journal of the American Chemical Society, 60, 309-319 (1938)]. -87- 200406031 (81) Description of the invention The pore volume is calculated based on the nitrogen volume absorbed by the relative pressure P / Po value. Usually, P / Po is about 0.95. It is located in the flat area of the isotherm, where condensation is completed. It is assumed that the density of adsorbed nitrogen is equal to liquid nitrogen, and that in this P / Po, all pores are filled with condensed nitrogen.

The pore size distribution is based on the nitrogen isothermal theory (using the Kjeldahl equation) and the BJH pore size distribution (EP Barret, L.G. Zoyner, P.P. Halenda; 1951)) Calculated from the nitrogen isotherm absorption arm. The Kelvin equation is used here to suppress the vapor pressure curvature; and the Halsey equation states that the thickness of the adsorbed nitrogen single layer is relative to P / Po, and the volume of condensed nitrogen relative to P / Po is converted to a specific pore size range. Pore volume. The average cylinder bore diameter D is the cylinder diameter. The cylinder has the same nominal BET surface area Sa (square meters / gram) and the pore volume Vp (cubic centimeters / gram), so D (nanometer) = 4000 Vp / Sa. Pyrolysis Adsorption mass spectrometry: Thermal desorption mass spectrometry (TDMS) is used to analyze the desorption species and determine the thermal stability of materials when they are subjected to heat treatment.

TDMS measurement is performed in a high vacuum system. The system is equipped with a wafer heater and a mass spectrometer. The position of the mass spectrometer is close to the front of the wafer. The wafer is heated using a heating lamp, and the wafer is heated from the back side. Wafer temperature is measured by a thermocouple, which is in contact with the front side of the wafer. The heating lamp and thermocouple are connected to a programmable temperature controller that allows several temperature rises and falls and temperature maintenance cycles. The mass spectrometer was a Hiden analysis company HAL IV RC RGA 301. The mass spectrometer and temperature controller are connected to a computer. The computer reads and records the mass spectrometer and temperature signal versus time. For TDMS analysis, standard processing methods were used first, and the deposited material was thin-filmed on an 8-inch wafer. The wafer is then placed in a TDMS vacuum system. -88-200406031 (82) Invented the performance sheet. The system decompressed to a pressure of less than 7 torr by pump. Then use the temperature controller to start temperature rise and fall. Use a computer to record temperature and mass spectrometer signals. It is used for typical measurement of temperature rise and fall of about 10 ° C per minute, and a complete mass scan and temperature measurement are recorded every 20 seconds. After the measurement is completed, the mass spectrum at the specified time and the temperature at the specified time are analyzed. Example: Comparative Example A: The inventor measured the dielectric constant of the composition of Example 5 in the International Patent Publication WO 01/78110 of a similar inventor, and obtained a dielectric constant of 2.7. Comparative Example B: Although WO 00/31183 teaches that polybutadiene can be used as a pore-forming agent, the inventor tried to use polybutadiene as a pore-forming agent, and the inventor added polybutadiene to a similar U.S. application under review 60/350187 The application of the compositions of Invention Examples 4-7 dated January 15, 2002 shows that the refractive index of the composition is the same regardless of the molecular weight of polybutadiene, as shown in Table 6 below. Low dielectric constant materials. Table 6 Pore-forming agent% Pore-forming agent% Adhesion promoter% Solvent 1 Polybutadiene (Mw 1800) 35 6.7 Xylene 1.629 Polybutadiene (Mw 1000) with phenyl end group 35 6.7 Cyclohexanone 1.623 poly (indene-copolymer-coumarinone) (Mw 735) 35 6.7 cyclohexanone 1.602 poly (indene-copolymer-coumarinone) (Mw 735) 35 6.7 xylene 1.607 poly (indene-copolymerization) -Coumarinone) (Mw 1090) 35 6.7 Cyclohexanone 1.600 Poly (indene-copolymer-coumarinone) (Mw 1090) 35 6.7 Xylene 1.595 (83) 200406031 Preparation example: Μ 备 例 1-埶Preparation of solids (this dummy draft is used as "P1__l1 Step ⑻: 1, 3, 5, 7- (3V4'-bromophenyl) adamantane (shown in Figure 1A). L, 3 / 4- 贰 [1 ' , 3 ', 5, ginseng (3〃 / 4〃-bromophenyl) adamantane-7'yl] benzene (shown in Figure 1 (:) and at least 153- 贰 {374: [1〃53〃, 5〃 -Ginseng (3, 〃 / 4, 〃-bromophenyl) adamantyl 7,, yl] phenyl} -5,7- 贰 {3〃〃 / 4〃〃-bromophenyl} adamantane (shown in the figure) ic "&lt; &gt; Preparation of Kun compound (collectively referred to as" P1 step ⑻ product ").

The first container was loaded with adamantane (200 g), bromobenzene (1550 ml) and r — aluminum dioxide (50 g). The reaction mixture was heated to 40 ° C using a thermostatic water bath. Second bromine (1206 g) was added to the reaction mixture in a buffer over a period of 4-6 hours. The mixture was stirred at 40 ° C overnight. The second reaction vessel was filled with 1000 ml of aqueous hydrogen chloride (5% w / w). The contents of the first reaction vessel are slowly discharged into the inside of the second reaction vessel, while maintaining the reaction mixture by an external ice bath for about 25-35. (: The organic phase (dark brown phase) was separated and washed with water (1000 t liters). About 1700 ml of the organic phase remained. A third reaction vessel was charged with 20.4 liters of petroleum ether (mainly boiling point). 80 ° c-ii (Tc's well burned). The content of the second reaction vessel was added to the third reaction vessel over 1 hour. The resulting mixture was stirred for at least 1 hour. The precipitate was filtered off, and the filter cake was 300 milliliters each time. It was washed twice with the petroleum ether mentioned above. After washing, the filter and cake were dehydrated at 45 ° C overnight at Daiba. The product yield in step P1 was 407 grams of dry weight. This reaction is shown in Figures 1A to ic as follows. Figure 8 shows the monomers obtained. Figure 1B shows the general binary and higher carbon products obtained, and Figure 1c shows the specific binary and ternary bodies covered by the structural formula of Figure 1B. Includes LC-MS, NMR%, and Analytical techniques such as Gpc are used to identify the product. -90- 200406031 (84) Description of the invention LC-MS shows that the product is a hybrid mixture of a monomer and an oligomer star compound with a gold firing center. Identify The structural formula is shown in the table below (Ad = Adamantane; Ph = C6H5; Br = bromine; t-Bu = -C (CH3) 3 ): HPLC-MS analysis of IE1 step (a) product HPLC retention time, minutes M + peak estimated structure 12.8 598 AdPh3Br3 14 674 AdPh4Br3 14 676 AdPh3Br4 15.3 752 AdPh4Br4 15.8 830 AdPh4Br5 16 830 AdPh4Br5 16 810 AdPh3Br5 ( 16 828 AdPh5Br4 16.3 908 AdPh4Br6 16.5 908 AdPh4Br6 17.1 808 AdPh4Br4 (t-Bu) 17.3 886 AdPh4Br5 (t-Bu) 18.4 864 AdPh4Br4 (t-Bu) 2 Wide ~ 19 + 1040 Ad2Ph5Br5 1114 Ad2P5H2Br2Ph5Br 1194 Ad2Ph6Br6 1270 Ad2Ph7Br6 1272 Ad2Ph6Br7 1348 Αί ^ ΡΙίγΒΓγ 1426 AdzPhz / Brg wide ~ 21 + 1096 Ad2Ph5Br5 (t-Bu) 1172 Ad2Ph5Br6 (t-Bu) 1174 Ad2Ph5Br6 (t-Bu) -Bu) 1328 Ad2Ph6Br7 (t-Bu) 1404 Ad2Ph7Br7 (t-Bu) 1482 Ad2Ph7Br8 (t-Bu)

-91-200406031 (85) Summary sheet: NMR 13C analysis obtained the following peaks

13CNMR peak position, ppm structure 153.6, 151.8, 151.1, 148.3, 147.6 The fourth aromatic carbon is bonded to adamantane 136.0, 134.5, 134.2, 133.1, 131.6, 131.1, 130.2, 130.0, 129.6, 129.3, 128.5, 126.9, 123.8 Aromatic CH 123.1, 123.0, 122.9, 122.6, 121.4, 121.1, 120.3 Aromatic C-Br 47.7 Three tri-substituted adamantane c-h2 46.8 Four-substituted adamantane c-h2 41.0 Adjacent to unsubstituted diamond Position of c-h2 of adamantane 39.3, 39.0, 38.9, 38.4, 38.1 Fourth (aliphatic) carbon of adamantane 35.2 Fourth (aliphatic) carbon of third butyl 31.4 c-h3 of third butyl • 30 CH GPC structure analysis of tri-substituted adamantane-1,3,5,7-((374'-bromophenyl)) Kanazawa I (shown in Figure 3A) has a peak molecular weight of about 360; -1, 3 / 4-贰 [Γ, 37-gins (374〃-bromophenyl) adamantyl] benzene (shown in FIG. 3C) has a peak molecular weight of about 620; -1,3- 贰 {374'- [Γ, 3〃, 5〃 -Shen (3〃V4〃'-bromophenyl) adamantane-7〃-yl] phenyl} -5,7-7 {3〃〃 / 4〃〃-bromophenyl} adamantane (shown in Figure 3C ) Has a peak molecular weight of about 900 (shoulder). Step (b) ·· 1,3,5,7-[374 '-(phenylethynyl) phenyl] Kanaoka | Jane (shown in Figure ID); 1,3 / 4- 贰 {Γ, 3 ', 5'_see [3〃 / 4〃- (phenylethynyl) phenyl] adamantane-7'-yl} benzene (shown in Figure 1F); and at least 1,3- 贰 {374, [1 〃, 3 &quot;, 5 'reference [3〃V4'〃- (phenylethynyl) phenyl] adamantane-7〃-yl] phenyl} -5,7- 贰 [3〃〃 / 4〃〃- Preparation of a mixture of (phenylethynyl) phenyl] adamantane (shown in Figure 1F) (collectively referred to as "P1 step (b) product"). -92- 200406031 Fenming instructions ^ ~ (86) _-- 2 --—— The first reactor is placed under nitrogen 'The reactor is charged with toluene (500ml), triethylamine (4000ml) and as described above Preparation of the product from step P1 (1-g dry weight). The mixture was heated to 80 ° C, and 贰 ((triphenylphosphine) palladium dichloride) (ie [Ph3P] 2Pda2) (7.5 g) and triphenyl ether (ie [Ph3P]) (i5 g) were added After 10 minutes, broken copper (1) (7.5 g) was added. A solution of phenylacetylene (750g) was added to the first reactor over a period of 3 hours. The reaction mixture was stirred at 80 ° C for 2 hours to ensure that the reaction was complete. Toluene (4750 ml) was added, and the solvent was distilled off under reduced pressure and the highest pit temperature, and the reaction mixture was cooled to about 50 ° C. Triethylammonium bromide (about 160 ml) was removed by distillation. The filter cake was washed three times with 500 liters of toluene each time. The organic phase was washed with 1750 ml of hydrochloric acid (10 w / w%) and then with water (2000 ml). Water (1000 ml) was added to the organic phase after washing 'ethylenediaminetetraacetic acid (EDTA) (100 g) and dimethylethanol oxime (200 g). Add about 50 ml of ammonium hydroxide (25 w / w%) to obtain pH = 9. The reaction mixture was stirred for 1 hour. The organic phase was separated and washed with 100 ml of water. Using Ding Stark condensate flaps, perform dehydration until the escape of water stops. Add the filter agent dolomite (100 g) (trade name Tungsiel (Butnosii)). The mixture was heated to greasy for 30 minutes. The dolomite was filtered out using a Deng-made filter with a 6-gauge field hole, and the remainder was toluene (200 ml, ice: coke, on), and then washed first. Add silica (100 g). The reaction mixture was stirred for 30 minutes. To fine; ^ 丨 Special, two ,, take up the mouth. The cloth dagger is considered to filter out Shi Xi oxygen, and the rest is washed with toluene (200 ml). 250 η of real preparation, 2500 hair lice water (20 w / w%) and 12.5 g of N-ethyl t-cysteine Hv were added thereto. The phases were separated. The organic phase was washed with liter a I (10 / .w / w), and then washed with 10 ml of water each time. The toluene was removed by distillation under a reduced pressure of 120 bar. The internal temperature does not exceed about 70 ° -93-200406031 (87) ° C. Leaves a dark brown, viscous oil (1500-1700 ml). Isobutyl acetate (2500 ml) was added to the contents of the reactor while hot, resulting in a dark brown solution (4250 ml). The second reactor was charged with 17000 ml of petroleum ether (mainly isooctane with a boiling point of 80 ° C -110 ° C). The first reaction content was added to the second reactor over 1 hour and stirred overnight. The precipitate was filtered off and washed four times with 500 ml of the aforementioned petroleum ether each time. The product was dehydrated at 45 ° C under reduced pressure for 4 hours, and 80 ° C under reduced pressure for 5 hours. The yield of the product of step P1 (B) is 850-900 g. This reaction is shown in Figures 1D to 1F as follows. Figure 1D shows the resulting monomer. Figure 1E shows the general binary and high carbon products obtained, and Figure 1F shows the specific binary and ternary bodies covered by the structural formula of Figure 1F. Include LC-MS, NMR 4, NMR 13C, GPC, and FTIR analysis techniques to identify products. LC-MS analysis showed that the product was a complex mixture of monomer and oligomer star compounds with adamantane centers. The identified structural formula is shown in the table below (Ad = 金 金 丨 J alkane cage; T is tolyl-PhC three CC6H4-; t-Bu = -C (CH3) 3) · # M + spikes proposed structural formula la 664 AdT3H 2a 840 AdT4 3a 720 Ad (H) T3 (t-Bu) 4a, b 896 AdT4 (t-Bu) 5a, b 1326 Ad2T6 6a, b 1402 Ad2T6 (C6H4) 3 All the general structural formulas are observed with MWdbl00a.u. (Plus or minus PhC ^ C-based) analogs. b An analogue of the loss of the tolyl arm (-176 a.u.) was observed for these structural formulas. 4 NMR identified aromatic protons (6.9-8 ppm, 2.8 ± 0.2Η) and Jingang 1J alkane caged protons (1.7-2.7ppm, 1 ± 0.2Η). -94- 200406031 (88) Confirmation performance page :: &lt;·-;; &gt; &lt; :: 'ί :::: ϊ; ::: &gt; ::: 〇ΐ: ϋ .: ^ &gt;:-. · ::; ::; 13C NMR analysis obtained the following peak assignments:

13C NMR peak position, ppm structure 151.3, 151, 150, 149.9, 149.8, 149.3, 149.2 The fourth aromatic carbon is attached to the adamantane ring 132-131, 128.5, 125.3, 125, 2 CH aromatic carbon 129.6-129.1 Aromatic Group ring carbons 123.7-122.9, 121.8, 121.1, 120.9 The fourth aromatic carbon is attached to acetylene 93.6 The fourth acetylene carbon (on the disubstituted ring) 90.7, 90.3, 90.1, 89.7, 89.5, 89.4, 89.1, 88.8, 88.7 Tetraacetylene carbon 47.5, 46.7 c-h2 of tetra-substituted adamantane 47.1 c-h3 of tetra-substituted adamantane 41-c-h2 of tri-substituted adamantane 39.6 c-h3 of tri-substituted adamantane 39: 5, 39.2-39.0, 38.6 , 38.2, 35 Fourth carbon of tetra-substituted adamantine 32 c-h3 of third butyl ring of aromatic ring 30 CH GPC analysis results of tri-substituted adamantan: -1,3,5,7- 肆 [3V4'-phenyl Ethyl] phenyl] Kinoka Kan (shown in Figure 3D) has a peak molecular weight of about 744; -1,3 / 4- {Γ, 3 \ 5'-reference [3〃 / 4〃- (phenylethynyl ) Phenyl] adamantane-7'-yl} benzene (shown in Figure 3F) has a peak molecular weight of about 1300; -1,3- 贰 {374 '-[Γ, 3〃, 5〃-〃 [3〃' / 4'〃- (phenylethynyl) phenyl] adamantane-7〃-yl] phenyl} -5 7-fluorene (3 '/ 4'-(phenylethynyl) phenyl) adamantane (shown in Figure 3F) has a peak molecular weight of about 1680 (shoulder). From GPC, it is known that the ratio of monomers and small molecules to oligomeric compounds is 50 ± 5%. FTIR shows the following: Spikes, cm ^ (spike intensity) Structure 3050 (weak) Aromatic CH 2930 (weak) Adamantane's aliphatic CH 2200 (very weak) Acetylene 1600 (very strong) Aromatic C = C 1500 (strong) -95-200406031 (89) Description sheet 1450 (medium) 1350 (medium) Preparation Example 2-Preparation of thermosetting ingredients (herein referred to as "P2i") Step (a): 1, 3, 5, 7- (3 '/ 4'_bromophenyl) Jingang Jane (shown in Figure 1A);

1,3 / 4- 贰 [Γ, 3 ', 5'-ginseng (3〃 / 4〃-bromophenyl) adamantane-7, yl] benzene (shown in Figure 1 (:) and at least 1,3-贰 {374 '-[1〃, 3〃, 5〃-ginseng (3〃74〃'-bromophenyl) adamantane-7 &quot; -yl] phenyl} -5,7- 贰 {3〃〃 / 4 Preparation of a mixture of hydrazone-bromophenyl} adamantane (shown in Figure 1C) (collectively referred to as "P1 step hydrazone product"). The first reaction vessel was charged with 1,4-dibromobenzene (587.4 g) and Aluminum trichloride (27.7 g). The reaction mixture was heated to 90 ° C with a constant temperature water bath, and maintained at this temperature for 1 hour without stirring, and for 1 hour with stirring. The reaction mixture was cooled to 50 ° C. Adamantane (113.1 g) was added to the cold reaction mixture. Third butyl bromobenzene (7 96.3 g) was added to the reaction mixture over a period of 4 hours. The reaction mixture was stirred for another 12 hours.

The second reaction vessel was filled with hydrochloric acid (566 ml, 10% aqueous w / w). The contents of the first reaction vessel were discharged into the second reaction vessel at 50 ° C, while the reaction mixture was maintained at 25-35 ° C by an external ice bath. The reaction mass was a light brown suspension. The organic phase was a dark brown lower phase, and the organic phase was separated from the reaction mixture. The separated organic phase was washed with water (380 ml). Approximately 800 milliliters of organic phase remained after washing. The third reaction vessel was charged with heptane (5600 ml). The content of the second reaction vessel was added to the third reaction vessel with a buffer of 1 hour. The suspension was stirred for at least 4 hours and the precipitate was filtered off. The filter cake was washed twice with 300 ml of heptane each time. The yield of the product in step P2 was 526.9 grams (wet weight) and 470.1 grams (dry weight). -96- 200406031 (90) Description of the Invention Continued Includes LC-MS, NMR 13C and GPC analysis techniques to identify products. LC-MS showed that the product was a mixed mixture of monomer and oligomer star compounds with an adamantane center. The identified structural formulas are shown in the table below (Ad = Kanaoka 1J; Ph-C6H5; Br = bromine; t-Bu = -C (CH3) 3): HPLC-MS analysis of the product in step (a) of IE2, HPLC retention time, Minute M + peak estimated structure 12.8 598 AdPh3Br3 14 674 AdPh4Br3 14 676 AdPh3Br4 15.3 752 AdPh4Br4 15.8 830 AdPh4Br5 16 830 AdPh4Br5 * 16 810 AdPh3Br5 (t-Bu) 16 828 AdPh5Br4 16.3 908 AdPh4Br4 16.4Ph4Br1 886 AdPh4Br5 (t-Bu) 18.4 864 AdPh4Br4 (t-Bu) 2 Wide ~ 19 + 1040 Ad2Ph5Br5 1114 Ad2Ph7Br4 1116 Ad2Ph6Br5 1118 Ad2Ph5Br6 1192 1194 Ad2Ph6Br6 1270 Ad2Ph7Br6 1272 Ad2P2P2 + Ph6Br2 Ad2Ph6Br5 (t-Bu) 1174 Ad2Ph5Br6 (t-Bu) 1250 Ad2Ph6Br6 (t-Bu) 1326 Ac ^ PhyBr ^ t-Bu) 1328 Ad2Ph6Br7 (t-Bu) 1404 Ad2Ph7Br7 (t-Bu) 1482 Ad2Ph7Br8 (t-Bu)

-97- 200406031 (91) Description of the invention Continued NMR 13C analysis obtained the following peaks

13CNMR peak position, ppm structure 153.6, 151.8, 151.1, 148.3, 147.6 The fourth aromatic carbon is bonded to the diamond calcination 136.0, 134.5, 134.2, 133.1, 131.6, 131.1, 130.2, 130.0, 129.6, 129.3, 128.5, 126.9, 123.8 Aromatic CH 123.1, 123.0, 122.9, 122.6, 121.4, 121.1, 120.3 Aromatic C-Br 47.7 Three tri-substituted adamantane c-h2 46.8 Four-substituted adamantane c-h2 41.0 Adjacent to the unsubstituted gold. C-h2 of adamantane in the adamantane position 39.3, 39.0, 38.9, 38.4, 38.1 4th (aliphatic) charcoal 35.2 3rd butyl fourth (aliphatic) carbon 31.4 3rd butyl c- h3 30 CH GPC analysis structure of tri-substituted adamantane: -1,3,5,7-((374'-bromophenyl)) Kanazawa J (shown in Figure 3A) has a peak molecular weight of about 360; -1,3 / 4- 贰 [Γ, 3 \ 5'-ginseng (3〃 / 4〃-bromophenyl) adamantane-7 / -yl] benzene (shown in Figure 3C) has a peak molecular weight of about 570; -1,3- 贰{374'- [Γ, 3〃, 5〃-ginseng (3〃74〃'_ bromophenyl) adamantane-7〃-yl] phenyl} -5,7- 贰 {3〃〃 / 4〃〃 -Bromophenyl} adamantane (shown in Figure 3C) has a peak molecular weight of about 86 0 (shoulder). Step 骡 (b) ·· 1,3,5,7-[374 '-(phenylethynyl) phenyl] adamantane (shown in Figure ID); 1,3 / 4- 贰 {1Ά57- 参 [ 3〃 / 4〃- (phenylethynyl) phenyl] adamantane-7'-yl} benzene (shown in Figure 1F); and at least 1,3- 贰 {374f-[Γ, 3〃, 5〃- Reference [3〃V4'〃- (phenylethynyl) phenyl] adamantane-7〃-yl] phenyl} -5,7- 贰 [3〃〃 / 4〃〃-(phenylethynyl) benzene Preparation of a mixture of ammonium] damantane (shown in Figure 1F) (collectively referred to as "P2 step (b) product"). The first reactor was placed under nitrogen, and the reactor was charged with toluene (6 98 ml), 200406031 (92) Guiming Instructions continued on triethylamine (1860 ml) and the P2 step ⑻ product (465 g) prepared as before Dry weight). The mixture was heated to 80 ° C. Palladium-triphenylphosphine complex (ie [Ph (PPh3) 2Cl2] (4.2 g)) was added to the reaction mixture. After 10 minutes, triphenylphosphine (ie PPh3) (8.4 g) was added to the reaction mixture After waiting another 10 minutes, copper (I) iodide (4.2 g) was added to the reaction mixture.

A solution of phenylacetylene (348.8 g) was added to the reaction mixture over a period of 3 hours. The reaction mixture was stirred at 80 ° C for 12 hours to ensure the reaction was complete. Toluene (2209 ml) was added to the reaction mixture and then distilled off under reduced pressure and at the highest pit temperature. The reaction mixture was cooled to about 50 ° C 'and triethylammonium bromide was distilled off. The filter cake was washed twice with 250 ml toluene each time. The organic phase was washed with hydrochloric acid (10 w / w%) (500 ml) and water (500 ml).

Water (500 ml), EDTA (18.6 g) and dimethylethanol oxime (3.7 g) were added to the organic phase. Add ammonium hydroxide (25 w / w%) (about 93 ml) to maintain pH = 9. The reaction mixture was stirred for 1 hour. The organic phase is separated from insoluble and palladium complex-containing emulsions. The separated organic phase was washed with water (500 ml). Using a Ding Stark condensate flap, the washed organic phase was dehydrated by azeotropic distillation until water evolution ceased. Filtering agent dolomite (Thomsell) (50 g) was added and the reaction mixture was heated to 100 ° C for 30 minutes. The dolomite was removed by filtration through a cloth filter with fine pores, and the organic matter was washed with toluene (200 ml). Dream oxygen (50 g) was added and the reaction mixture was stirred for 30 minutes. The silica was filtered through a pore cloth filter, and the organic matter was washed with toluene (200 ml). Aqueous ammonia (20 w / w%) (250 ml) and N-acetamidocysteine (12.5 g) were added. The phases were separated. The organic phase was washed with hydrochloric acid (10% w / w :) (500 ml). The organic matter was washed twice with 500 ml of water each time. At about -99- 200406031 (93) it was confirmed that toluene was distilled off under reduced pressure of ~ r κ 120 mbar. The reactor temperature does not exceed 70 ° C. Leaves a dark brown sticky oil (about 500-700 ml). Add isobutyl acetate (1162 ml) to the reaction flask while hot. A dark brown solution (about 1780 ml) was produced.

The second reactor was charged with heptane (7120 ml). The contents of the first reaction vessel were added to the second reaction vessel over a period of 1 hour. Shen Dian stir at least: Mix for 3 hours and filter to remove. The product was washed 4 times with 250 ml heptane each time. The product was dehydrated at 80 ° C under a reduced pressure of 40 mbar. The yield of the product of step P2 (b) is 700 g or 419 g dry. Including LC-MS, NMR W, NMR 13C, GPC, and FTIR analysis techniques are used to identify the product. LC-MS analysis showed that the product was a complex mixture of monomer and oligomer star compounds with adamantane centers. The identified structural formulas are shown in the table below (Ad = 金 OKij alkane cage; Butyl is tolyl-PhC three CC6H4-; t-Bu = -C (CH3) 3): # M + 尖峰 1 Proposed structural formula la 664 AdT3H 2a 840 AdT4 3a 720 Ad (H) T3 (t-Bu) 4a'b 896 AdT4 (t-Bu) 5a, b 1326 Ad2T6 6a, D 1402 Ad2T6 (C6H4)

3 For all general structural formulas, analogs with MW ± 100a.u. (Plus or minus PhOC-group) were observed. b An analogue of the loss of the tolyl arm (-176 a.u.) was observed for these structural formulas. 4 NMR identified aromatic protons (6.9-8 ppm, 2.8 ± 0.2Η) and Jingang Jane caged protons (1.7-2.7ppm, 1 ± 0.2Η). 13C NMR analysis obtained the following peak assignments: 13C NMR peak position, ppm structure 151.3, 151, 150, 149.9, 149.8, 149.3, 149.2 The fourth aromatic carbon is attached to the adamantane ring -100- 200406031 (94) 132-131, 128.5, 125.3, 125.2 129.6-129.1 123.7-122.9, 121.8, 121.1, 120.9 93.6 90.7, 90.3, 90.1, 89.7, 89.5, 89.4, 89.1, 88.8: 88.7 47.5, 46.7 47.1 41 39.6 ¥ 'Instruction sheet: Aromatic Carbon fourth aromatic ring carbon group carbon attached to acetylene carbon (disubstituted ring) fourth acetylene carbon

1 G-adamantane C-H7 jT-adamantane c-h3 Adamantane c-h2 , 35 ~ 32

GPC analysis results:

1,3,5,7-[[3V4,-(phenylethylblock) phenyl] adamantane (shown in Tuqin) has a peak molecular weight of about 763; -1,3 / 4- 贰 {l ', 3 ', Y-ginseng [3W-(phenylethynyl) phenyl] adamantane_7, _yl} benzene (shown in Figure 3F) has a peak molecular weight of about 133〇;

-u-llusion tear-π &quot; "-ref [3 &quot; V4, 〃_ (phenylethyl block) phenyl] adamantine 7〃-yl] phenyl} -5,7- 贰 （3〃 &quot; / 4〃〃- (phenylethynyl) phenyl) adamantane (shown in FIG. 3F) has a peak dose of about 1S20 (shoulder). The ratio of monomers and small molecules to oligomeric compounds is 5 by GPC. 〇 ± 5%。 FTIR shows the following: Spikes, cm, spikes strong ~ Structure 3050 (weak) ^ Γ \ ^ ί Γ \ f ?? \ — — _ Fangxiang family 2930 (weak) 2200 (very weak) 1 / Γ AA f J.-C \ &quot; ----- --- rm an ^ U-rl B ---- 1600 (extremely strong) 1500 i strong,-_ aromatic 〇 = 〇x \ j \ jj 1450 (medium) '______ 1350 (nakaji) Preparation example 3

-101- 200406031 (95) Solvent for 1,3,5,7- [3 ', 4'-(phenylethynyl) phenyl] adamantane (shown in Figure 1D) for 1,3 / 4- 贰{Γ, 3 \ 5, reference [3〃 / 4〃- (phenylethynyl) phenyl] adamantane-7'-yl} benzene (shown in Figure 1F), and at least 1,3- 贰 {374f- [l〃, 3〃, 5〃-ginseng [3,4…-(phenylethynyl) phenyl] Kanaoka Jane-7 &quot; -yl] phenyl} -5,7-3 [3 ”74, ( The effect of the ratio of phenylethynyl) phenyl] adamantane (shown in Figure 1F).

850 ml of the product from step P1 was divided into four equal portions and precipitated in petroleum ether, petroleum spirit, heptane and methanol. Each precipitate was dissolved in 2520 ml of solvent, vacuum filtered (Burnner funnel diameter 185 mm), washed twice with 150 ml of solvent on the filter, and then dehydrated in a vacuum oven at about 20 ° C for 2 hours, and dehydrated at 40 ° C Dehydrate to constant weight overnight and at 70-80 ° C. Precipitation in hydrocarbons resulted in a very dispersed light serge-colored powder that could be dried without any problems. Precipitated into methanol to obtain a heavy brown granular solid (particle size of about 1 mm), which forms tar when dried at 20 ° C. This product is further dehydrated.

The reaction mixture was analyzed by GPC during the reaction and before precipitation. The whole filtrate and the final solid were analyzed by GPC. The results are shown in Table 7. In Table 7, PPT indicates precipitation, and the monomer is 1,3,5,7- (374, bromophenyl) adamantane (shown in Figure 1A); the binary is 1,3 / 4- 贰 [Γ, 3 ', 5, ginseng (3〃 / 4〃-bromophenyl) adamantane-7, yl] benzene (shown in Figure 1C); and the triad is 1,3-K {3V4'-[1〃, 3〃, 5〃-ginseng (3〃74'〃-bromophenyl) adamantane-7〃-yl] phenyl} -5,7- 贰 {3〃〃 / 4〃〃-bromophenyl} adamantane (Shown in Figure 1C). Table 7 Peak ratio before precipitation [monomer ratio (binary + ternary)] Shen; Dian solvent peak ratio after precipitation [monomer ratio (binary + ternary)] 75.0: 25.0 Petroleum acid 52.5: 47.4 75.0: 25.0 Petroleum 1 64.0: 36.0 -102-200406031

The value ratio is approximately 3: 1. Most of the products lost in the hydrocarbon precipitation filtrate (&gt; 90%) are monomers, and the loss in washing the filtrate is negligible. There was no product in the methanol precipitation filtrate. Increased ratio of monomer to (binary + ternary) after precipitation (1: 1- ^ 3: 1) ^ monomer consumption of filtrate is reduced (56-0%) sequence: petroleum ether, petroleum spirit, heptane And methanol. Preparation Example 4-Preparation of Thermosetting Ingredients Preparation Example 1, Product Mix of 1,3 / 4- 贰 {Γ, 3 ', 5' · Ref [374〃- (phenylethynyl) phenyl] adamantane-7'- Benzene (shown in Figure 1F) was separated using preparative liquid chromatography (PLC). PLC is similar to the aforementioned HPLC method, but uses larger columns to separate larger amounts of the mixture (from several grams to several hundred grams of the mixture). Preparation Example 5-Preparation of Thermosetting Ingredients Preparation Example 1 Product mixture of 1,3- 贰 {374'- [Γ, 3〃, 5〃-ginseng [3'〃 / 4〃 '-(phenylethynyl) phenyl ] Adamantane-7〃-yl] phenyl} -5,7- 贰 [3〃74〃〃- (phenylethynyl) phenyl] adamantane (shown in Figure 1F) uses preparative liquid chromatography (PLC) separation. Preparation Example 6-Preparation of a thermosetting component An oligomer or polymer of a bisadamantane monomer of the formula XIIA, XIIB, XIIC or XIID and a bisadamantane monomer of the formulae XIII, XV, XXII and XXV was prepared by the following method. As shown in Figure 2, bisadamantane is converted to brominated bisadamantane using a bromine and Lewis acid catalyst. The brominated bisdamantane product is then reacted with bromobenzene in the presence of a Lewis acid catalyst to form brominated bisdamantane. Then brominated bisdamantane is used in the so-called Sonojashula coupling reaction -103-200406031 (97) issued 'Ming Weiming Continued: The catalyst system to be used is reacted with terminal alkyne. The product of each step is as described in the patent application PCT / US01 / 22204 under examination by the inventor, and the application date is October 17, 2001. Preparation Example 7-Preparation of Thermosetting Ingredient ⑷

Oligomers or polymers of bisadamantane monomers of formula XIIA, XIIB, XIIC or XIID and bisadamantane monomers of formula XIII, XVI, XXII and XXV are prepared by the following method. As shown in FIGS. 1A to 1F, the bis-adamantane system was converted to a bis-adamant brominated benzoylation composition using a similar synthetic procedure described in Preparation Examples 1 and 2. In FIGS. 1A to 1C, a bisdamantane-based compound and a halophenyl compound are reacted in the presence of a Lewis acid catalyst described in Preparation Examples 1 and 2 and / or in the presence of a second catalyst component described in Preparation Example 2. The reaction mixture is subjected to post-treatment to obtain a mixture of monomers, binary, ternary and high-carbon oligomers. In Figs. 1D to 1F, a brominated bisdamantane mixture is then reacted with terminal alkynes in the presence of a catalyst to produce the depleted bisdamantane composition of the present invention. Invention Example 1-Preparation of a pore former comprising a copolymer of rhenium and vinyl isovalerate: A pore former comprising a copolymer of rhenium and ethyl isovalerate was prepared as follows. In a 250 ml flask equipped with a magnetic stirrer, add 20 grams of technical grade rhenium (75% purity-equivalent to 0.986 mol pure erbium), 3.1579 g (0.0246 mol) of ethyl ethyl isovalerate, 0.5673 g (2.464 mmol) Mol) Di-tert-butyl azodicarboxylate and 95 ml of xylenes. The mixture was stirred at room temperature for 10 minutes until a homogeneous solution was obtained. The reaction solution was then degassed under reduced pressure for 5 minutes and purged with nitrogen. This process was repeated three times. The reaction mixture was then heated to 140 ° C under nitrogen for a period of 6 hours. The solution was cooled to room temperature and added dropwise to 237 -104- 200406031 (98). The mixture was stirred at room temperature for another 20 minutes. The resulting precipitate was collected by filtration and vacuum dehydrated. The properties of the obtained copolymer are listed in copolymer 18 in Table 5 above. Other porogens containing copolymers of acetoisovalerate were prepared in a similar manner, but the percentage of comonomer used, type and percentage of initiator used, and reaction time and temperature were changed, as listed in Table 5 above. . Inventive Example 2-Preparation of a pore-forming agent comprising a copolymer of tert-butyl acrylate: 丨 A pore-forming agent comprising a copolymer of terbium and tert-butyl propionate was prepared as follows. In a 250 ml flask equipped with a magnetic stirrer, add 20 grams of technical grade rhenium (75% purity-equivalent to 0.0986 mol pure rhenium), 2.5263 g (0.01971 mol) of third butyl acrylate, 0.3884 g (2.365 mmol) Ear) 2,2'-Azo-isobutyronitrile and 92 ml of dibenzobenzene. The mixture was stirred at room temperature for 10 minutes until a homogeneous solution was obtained. The reaction solution was then degassed under reduced pressure for 5 minutes and purged with nitrogen. This process was repeated three times. The reaction mixture was then heated to 70 ° C under nitrogen for a period of 24 hours. The solution was cooled to room temperature and added dropwise to 230 ml of ethanol. The mixture was stirred at room temperature for another 20 minutes. The resulting precipitate was collected by filtration and dehydrated in vacuo. The properties of the obtained copolymer are listed in Copolymer 2 in Table 5 above. Other porogens containing copolymers of osmium and tert-butyl propionate were prepared in a similar manner, but the percentage of comonomer used, type and percentage of initiator used, and reaction time and temperature were changed, as listed in the table above. 5. Invention Example 3-Pore-forming Agent Containing Copolymer of Acetyl Vinyl Acetate

A porogen comprising a copolymer of rhenium and vinyl acetate was prepared as follows. In a 250 ml flask equipped with a magnetic stirrer, add 20 grams of technical grade osmium (75% purity-equivalent to 0.986 mol pure osmium), 1.6969 g (0.01971 mol) of ethyl acetate, 0.3884 g (2.365 mmol) Ear) 2,2 ^ Azoisobutyronitrile and 88 ml of xylenes. The mixture was stirred at room temperature for 10 minutes until a homogeneous solution was obtained. The reaction solution was then degassed under reduced pressure for 5 minutes and purged with nitrogen. This process is repeated three times. The reaction mixture was then heated to 70 ° C under nitrogen for a period of 24 hours. The solution was cooled to room temperature and added dropwise to 220 ml of ethanol. The mixture was stirred at room temperature for another 20 minutes. The resulting precipitate was collected by filtration and vacuum dehydrated. The properties of the obtained copolymer are listed in copolymer 18 in Table 5 above. A similar pore-forming agent comprising a copolymer of fluorene and vinyl acetate was prepared in a similar manner but changing the percentage of comonomers used; the properties of the resulting copolymers are listed in Copolymer 19 in Table 5 above. Invention Example 4-Preparation of Pore Forming Agent Containing Poly-Homopolymer:

The rhenium polymer is prepared as follows. A 250 ml flask equipped with a magnetic stirrer was charged with 30 g of technical grade rhenium (75% purity-equivalent to 0.148 mol pure rhenium), 0.3404 g of di-tert-butyl azodicarboxylate (1.478 mmol), and 121 ml of xylenes. The mixture was stirred at room temperature for 10 minutes until a homogeneous solution was obtained. The reaction solution was then degassed under reduced pressure for 5 minutes and purged with nitrogen. This process is repeated three times. The reaction mixture was then heated to 140 ° C under nitrogen for 6 hours. The solution was cooled to room temperature and added dropwise to 303 ml of ethanol. Mixture_ Stir for another 20 minutes at room temperature. The resulting precipitate was collected by filtration and vacuum dehydrated. The properties of the obtained homopolymer are listed in homopolymer 1 in Table 8 below, where DBADC stands for di-tert-butyl azodicarboxylic acid and PDI stands for polydispersity -106- 200406031 (100) property index (Mw / Mn) . Other porogens containing polyfluorene homopolymers are prepared in a similar manner, but the types and percentages of the initiators used, as well as the reaction time and temperature are shown in Table 8, where AIBN stands for 2,2'-azopyrazine Nitrile 0 Table 8 Homopolymer initiator type Initiator% Solvent temperature (° C) Time (hours) Mη Mw PDI 1 DBADC 1% xylene 140 6 3260 14469 4.44 2 DBADC 2% xylene 140 6 2712 11299 4.17 3 DBADC 3% xylene 140 6 3764 14221 3.78 4 DBADC 4% xylene 140 6 3283 8411 2.56 5 DBADC 6% xylene 140 6 2541 7559 2.97 6. DBADC 8% xylene 140 6 2260 6826 3.02 7 DBADC 12% xylene 140 6 2049 5805 2.83 8 DBADC 16% xylene 140 6 2082 5309 2.55 9 DBADC 20% xylene 140 6 1772 4619 2.61 10 DBADC 30% xylene 140 6 1761 3664 2.08 11 AIBN 2% xylene 70 24 3404 7193 2.11 12 AIBN 2% xylene 70 24 3109 6141 1.98 13 AIBN 2% xylene 70 24 3500 7295 2.08 14 AIBN 2% xylene 70 24 3689 6165 1.67

Inventive Example 5-Preparation of a composition comprising a polyfluorene homopolymer, a thermosetting component and a polymethylsilane, and Inventive Example 6-Preparation of a composition comprising a polyfluorene homopolymer and a thermosetting fluorene component for use in the invention Example 5: A commercially available polyfluorene homopolymer (25 g) was used as a pore-forming agent, and polymethysilane (CH2SiH2) q, where q is 20-30 (1.57 g) (supplied by Spark Systems) as an adhesion promoter And xylene (334 grams) was weighed into a plastic bottle. Add the stir bar to the bottle. Seal the bottle tightly and start stirring. The solution was stirred at room temperature for 24 hours. The solution was poured into a pre-weighed two-necked flask with a stir bar, which contained a thermosetting component (22.43 g) similar to that of Preparation Example 1 or 2 described above. The bottle was washed with xylene (approximately 111 grams), and the resulting xylene solution was added to a two-necked flask with -107- 200406031 (101) until the total weight of the reaction mixture reached 500 grams. The condenser was opened and the water source was turned on. The system is flushed from the top of the condenser (inlet) to the side neck (d (strong air flow)) for 30 minutes. The nitrogen inlet-air outlet at the top of the condenser, the side neck is closed with a plug. Continue. The flask is lowered to the oil bath (pre Heat to 145 ° C and cover the entire reaction flask with constant J. Stir bar in the reaction flask to boil and allow it to reflux for 15.5 hours. Then stop heating oil bath and allow the flask to cool to room temperature. Use and start with cyclohexane Ketones are solvent exchanged. Most of the xylenes are removed to the end by a rotary evaporator. The remaining reaction mixture weighs about 60 to 90 grams. However: Add to a flask. Remove most of the viscous liquid again by a rotary evaporator. The remaining reaction mixture is heavy. Repeat about 60 to two more times to ensure that all xylenes are exchanged into liquid and diluted with cyclohexanone to a 20% solids solution. Dissolve less than 20 pounds and slowly pass through the 0.1 micron Teflon filter step. The final composition is 20% Solid, with 6.7% weight, 50% by weight polyfluorene homopolymer, the difference is thermosetting. As for Invention Example 6, the invention is repeated to implement P adhesion promoter, so the composition is 50% by weight. Polyfluorene is a thermosetting component. . hair Exemplary Example 7-10-Preparation of Composition Containing Polyurethane Homopolymer and Thermosetting Silane Continued: .The flask is clamped to the water port 1) Use the nitrogen gas inlet to replace with weak nitrogen Flow I was stirred) and the reaction mixture was stirred. The flask was removed from the stir bar by a magnetic rod, and a viscous liquid was obtained. 500 g of cyclohexanone was added to xylene until 90 g was obtained. This treatment is cyclohexanone. The solution was then filtered per square inch. Repeat the previous volume ratio polymethylsilane component. | 5, but without the addition of a cohesive polymer, as well as the difference component and polyformamidine-108-200406031 (102) Summary of the Invention For the seventh embodiment of the invention, the fifth embodiment of the invention is repeated, but the polymethysilane (CH2SiH2) q , Where q is 20-30 (supplied by Spark Systems) and the amount is 2.68 grams. The final composition was 20% solids, containing 12 weight percent polyfluorene silane, 50 weight percent polyfluorene homopolymer, and the balance was a thermosetting component. As for the inventive examples 8 to 10, the inventive example 7 was repeated, but the weight percentage change of the polyfluorene homopolymer is shown in Table 9 below. Table 9 Weight percentage of polyfluorene homopolymer in inventive examples 1 8 — &quot; 1 9 20 1.. 10 1101 Inventive examples 11-17—compositions containing polyfluorene homopolymer, thermosetting ingredients and polymethylsilane The preparation was repeated for Inventive Example 5 except that polymethanesilane (CH2SiH2) q, where q is 20-30 (supplied by Spark Systems) and the amount was 1.92 g. The amount of polyfluorene homopolymer was changed as shown in Table 10 below. Table 10 I Weight percentage of polymer homopolymers in invention examples 11 28 12 26.8 13 27.2 14 26.5 15 25.4 16 38.3 17 30.1 Invention examples 18-21-Combinations of polymer homopolymers, thermosetting ingredients, and polymethylsilane Inventive Example 7 was repeated, but the amount of polyfluorene homopolymer was 25% by weight, and the type of polyfluorene homopolymer used is shown in Table 11 below. 200406031 (103) Illustrated performance page Table 11 Invention Examples Polyfluorene Homopolymer 18 Table 4 Homopolymer 1 19 Table 4 Homopolymer 2 20 Table 4 Homopolymer 3 21 Table 5 Homopolymer 4 Invention Implementation Example 22-23-Preparation of admixture containing poly-a homopolymer, thermosetting ingredients, and cresol

As for Inventive Example 22, a 65 ml plastic bottle equipped with a magnetic stirrer was filled with a thermosetting component (4.17 g) similar to the preparation example 1 or 2 above, and o-cresol novolac resin (0.125 g) was filled as a stick Accelerator, polyfluorene (1.074 g) as a pore former, and cyclohexanone (24.46 g). The mixture was stirred at room temperature for 2 hours, and the resulting homogeneous solution was filtered through a 0.1 micron Teflon filter. As for Inventive Example 23, Inventive Example 22 was repeated, but 6 weight percent of o-cresol novolac resin was used. Inventive Examples 24-30—Preparation of Compositions Containing Polyurethane Copolymer, Thermosetting Ingredients and Polymethane Silane As for Inventive Example 24, polyfluorene copolymer (4.48 g; copolymer of Table 2) as a pore former, Polymethysilane (CH2SiH2) q, where q is 20-30 (0.48g), is added as an adhesion promoter and xylenes (59.4g) to a plastic bottle equipped with a magnetic stirrer. The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 100 ml three-necked flask. A thermosetting component (4.00 g) similar to the aforementioned Preparation Example 1 or 2 was added, and 19.8 g of xylene was added. The solution was flushed with nitrogen for 5 minutes and heated at 145 ° C for 15.5 hours. Most of the xylene was then removed by a rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture weighed about 10 to 12 grams. Then 100 grams of cyclohexanone was added to the flask. Then use a rotary evaporator to remove most of -110-200406031 (104)

Partition the solvent to obtain a viscous liquid. The remaining reaction mixture weighed about 10 to 12 grams. This process was repeated two more times to ensure that all xylenes had been exchanged for cyclohexanone. The solution was then diluted with cyclohexanone to obtain 18 ° /. Solid concentration solution. The solution was slowly filtered through a 0.1 micron Teflon filter at a pressure of less than 20 psi. Repeat the previous steps. The final composition is 18% solids with 12% by weight polymethysilane and 50% by weight polyfluorene copolymer. The balance is thermosetting. As for the inventive examples 25 to 30, the inventive example 24 was repeated, but the porogen used was as shown in Table 12 below. Table 12 Examples of the invention Table 2 Copolymers 24 7 25 11 26 9 27 6 28 4 29 3 30 1

Inventive Examples 31-32-Preparation of Compositions Containing Polycaprolactone, Thermosetting Ingredients and Polymethanesilane As for Inventive Example 31, the solvent used was xylene. Polycaprolactone (4.48 g) was used as a pore-forming agent, polymethysilane (CH2SiH2) q, where q is 20-30 (0.48 g) as an adhesion promoter and xylenes (59.4 g) were added to the assembly with Inside the plastic bottle of the stir bar. The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 250 ml three-necked flask. A thermosetting ingredient (4.00 g) similar to the aforementioned Preparation Example 1 or 2 was added, and an additional amount of 19.8 g of xylene was added. The solution was flushed with nitrogen for 5 minutes and heated at 145 ° C for 15.5 hours. The solution was slowly filtered through a 0.1 micron Teflon filter at a pressure of less than 20 psi. Repeat -111-200406031 (105) Fenming i :: # Continued :: Previous steps. The final composition was 10% solids, with 12% by weight polymethylsilane, 50% by weight polycaprolactone, and the balance was a thermosetting component. As for Inventive Example 32, the solvent used was cyclohexanone. Polycaprolactone

(4.48 g) As a pore-forming agent, polymethysilane (CH2SiH2) q, where q is 20-30 (0.48 g) and xylenes (59.4 g) were added to a plastic bottle equipped with a magnetic stirrer. The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 250 ml three-necked flask. Adding a thermosetting component (4.00 g) similar to the aforementioned Preparation Example 1 or 2,

And an additional amount of 19.8 grams of xylene was added. The solution was flushed with nitrogen for 5 minutes and heated at 145 ° C for 15.5 hours. Most of the xylene was then removed by a rotary evaporator to obtain a viscous liquid. The remaining reaction mixture weighed about 10 to 12 grams. Then 100 grams of cyclohexanone was added to the flask. Most of the solvent was removed again by a rotary evaporator until a thick liquid was obtained. The remaining reaction mixture weighed about 10 to 12 grams. This treatment was repeated two more times to ensure that all xylenes were exchanged for cyclohexanone. The solution was then diluted with cyclohexanone to obtain an 18% solids concentration solution. The solution was slowly filtered through a 0.1 micron Teflon filter at a pressure of less than 20 psi. Repeat the previous steps. The final composition was 18% solids with 12% by weight polymethysilane and 50% by weight polycaprolactone and the balance was a thermosetting component. Inventive Examples 33-35—Preparation of a composition comprising a polycaprolactone, a thermosetting component and an admixture of o-cresol novolac resin The thermosetting ingredient (4.00 g) similar to the aforementioned Preparation Example 1 or 2 Varnish resin (0.12 g; molecular weight 1760; supplied by Schneider International) as adhesion promoter, polycaprolactone (2.53 g) as pore former, and 37.66 g of cyclohexanone added to plastic equipped with magnetic stirrer Inside the bottle. The solution was at -112-200406031 (106) Silkworm Ming Zhu: Achievement Page: Stir at room temperature for 2 hours. The solution was slowly filtered through a 0.1 micron Teflon filter at a pressure of less than 20 psi. Repeat the previous steps. The final composition was 15% solids with 3% by weight o-cresol novolac resin relative to the thermosetting component, 35% by weight polycaprolactone relative to the total solids, and the balance was the thermosetting component. Repeat as shown in Table 13 below. Table 13 Inventive Examples Weight percentage of o-cresol novolac resin 33 3.4 34 6.9. 35 12.2 Inventive Examples 36-37 — Admixtures containing polyfluorene homopolymer, polycaprolactone, thermosetting ingredients, and polymethylsilane Preparation of the composition As for Inventive Example 36, the solvent used was xylene. Polycaprolactone (4.48 g) and a commercially available polyfluorene homopolymer (0.7906 g) are used as a pore former admixture, polymethylsilazane (CH2SiH2) q, where q is 20-30 (0.48 g) ( (Supplied by Xinghuo System Co., Ltd.) as an adhesion promoter and dibenzobenzene (64.74 g) is added to a plastic bottle equipped with a magnetic stir bar. The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 250 ml three-necked flask. A thermosetting component (4.00 g) similar to the aforementioned Preparation Example 1 or 2 was added, and an additional amount of xylene (21.58 g) was added. The solution was flushed with nitrogen for 5 minutes and heated at 145 ° C for 15.5 hours. The solution was slowly filtered through a 0.1 micron Teflon filter at a pressure of less than 20 psi. Repeat the previous steps. The final composition was 16.5% solids with 12 weight percent polymethysilane in relation to the thermosetting component, 15 weight percent polyfluorene with respect to the weight of the thermosetting component, and the difference was the thermosetting component. As for Inventive Example 37, the solvent used was cyclohexanone. Polycaprolactone 200406031 (107) Sounding performance page: S, Λ · ^ &lt; Α V '^ * &quot; * *' one (4.48 g), and commercially available poly pet homopolymer (0.79) 6 g) As a pore former admixture, polymethylsilazane (CftSiFUq, here ^ is 20-30 (0.48 g) (supplied by Xinghuo Systems) as an adhesion promoter and xylenes (6 4.74 G) was added to a plastic bottle equipped with a magnetic stir bar. The falling liquid was stirred at room temperature for 24 hours. Then the solution was transferred to a 250 ml three-necked flask. A thermosetting component (4.00 g) similar to the aforementioned Preparation Example 1 or 2 was added. And an additional amount of 21.58 grams of xylene. The solution was flushed with nitrogen for 5 minutes' and heated at 145 C for 15.5 hours. Then most of the xylene was removed by a rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture weighed about 10 to 12 grams. Then added 〇Q grams of cyclohexanone to the flask. Remove the Da Shao solvent by rotating the hairpin again until a viscous liquid is obtained. The remaining reaction mixture weighs about 10 to 12 grams. This process is repeated twice more to ensure that all the toluene is toluene. The parent was changed to cyclohexanone. Then the solution was diluted with cyclohexanone to obtain 1 8% solids solution. The solution was slowly filtered through a 0.1 micron Teflon filter at less than 20 psi. Repeat the previous steps. Example 38-41-Inclusion and Polycaprolactone, 埶 呵 佳 成 义~ Base polymethylated stone eve_ Preparation of the composition of the exchange of Yuan As for Inventive Examples 38 and 40, Inventive Example 37 was repeated, but the amount of polymethylsilyl silane was changed as shown in Table 14. As for the inventive examples 39 and 41, Inventive Example 36 was repeated, but the amount of polyfluorene silane was changed as shown in Table 14. In Table 14, PAN represents a polyfluorene homopolymer, PCL represents polycaprolactone, and PCS represents polymethylsilane. Table 14 P 发明 q Through Example 38% PAN in pore former admixture% PCL in pore former admixture% PCS Solvents || 15 50 6.7 Cyclohexanone 39 15 50 ~ 6J Xylene-114- 200406031 Invention Performance Sheet '(108) 40 15 50 3 Cyclohexanone 41 15 50 3 Xylene Invention Example 42-Preparation of Film of Invention Example 5 Invention Example 5 The composition was applied using typical coating conditions known to those skilled in the art To the substrate. As a result, the obtained spin coating composition was subjected to nitrogen (&lt; 50 ppm oxygen) at the following temperature. To dry:. 125 ° C, 250 ° C and 300 ° C oven curing conditions

At N2 (26 liters / minute) at 400 ° C for 60 minutes, the temperature was increased from 250 ° C at 5 ° K per minute. The hardening temperature is in the range of 350 ° C to 450 ° C. In the composition, the pore-forming agent is decomposed, and the pore-forming agent after the decomposition is vaporized, thereby forming pores in the composition. As a result, each layer obtained was analyzed according to the aforementioned analytical test method, and the properties of the obtained layer are reported in Table 15 below. Table 15 Parameter Invention Example 42 Hardened prescription 400 ° C / 2 hours Film thickness 0.3-1.2 microns Refractive index η (after baking) 1.6600 Refractive index η (after curing) 1.3600 Thickness (after baking, nanometer) 2885.00 Thickness ( Nanometer after hardening) 2874.00% shrinkage (toasting to hardening) -0.30 Dielectric constant (around) 1.93 Dielectric constant (outgassing) 1.901 Modulus (Gpa) 2 · 26 ± 0 · 59 (1.2 microns) Hardness (Gpa) 0.16 ± 0.05 (1.2 microns) Glass transition temperature (° C)> 410 (first cycle) Average peak pore diameter 20 nm Average pore diameter 4.1 nm Pore volume (cubic centimeters / gram) 0.557 Good film quality tape The test passed a stability of 4.5% at 425 ° C. Inventive Example 43-Preparation of Inventive Example 6 Film -115-200406031 (109) Fen Ming Note Sheet: The composition of Inventive Example 6 is known to those skilled in the art Typical coating conditions were applied to the substrate using the baking and hardening conditions of Inventive Example 42. In the composition, the pore-forming agent is decomposed, and the pore-forming agent after the decomposition is vaporized, thereby forming pores in the composition. The layer formed as a result was analyzed according to the aforementioned analysis test method, and the properties obtained from the analysis are reported in Table 16 below. Table 16 Parameters! Invention Example 43 Refractive index η (after roasting) 1.6600 Refractive index η (after curing) 1.4150 Νζ 2.00 Thickness (after baking, nanometer) 2740.74 One thickness (after curing, nanometer) 2450.00 Shrinkage% (Toast to harden) -10.61 Film quality is fuzzy (indicating phase separation)

The results of the inventive example 43 show that the adhesive effect of the inventive example 42 exists. Inventive Examples 44-47-Preparation of Inventive Examples 7-10

The compositions of Inventive Examples 7-10 were applied to substrates using typical coating conditions known to those skilled in the art and baking and hardening conditions of Inventive Example 42. In the composition, the pore former is decomposed, and the pore former after the decomposition is vaporized, thereby forming pores in the composition. The layer formed as a result was analyzed according to the aforementioned analytical test method, and the properties obtained from the analysis are reported in Table 17 below. Scanning electron microscope (SEM) results are shown in FIGS. 4 and 5. Fig. 4 shows a cross section of the film, and Fig. 5 shows the surface of the film. With the increase of the porogen content, small pores can be observed or visible on the film surface, as shown by SEM. As the amount of pore-forming agent decreases, the surface shows lower porosity. In addition, with the increase of the porogen content, the average pore diameter increases, as shown in the cross-sectional SEM -116- 200406031 (110). Figure 6 is a TDMS mapping showing that the porogen begins to decompose at about 380 ° C. Table 17 Parameters Invention Example 44 Invention Example 45 Invention Example 46 Invention Example 47 Pore-forming agent content 50% 35% 20% 10% Adhesion promoter 12% 12% 12% 12% Hardening prescription 400 ° C / 1 hour 400 ° C / 1 hour 400 ° C / 1 hour 400 ° C / 1 hour Film thickness 0.3-1.2 microns 0.3-1.2 microns 0.3-1.2 microns 0.3-1.2 microns Refractive index (RI) n (after hardening) 1.39 1.50 1.56 1.59 (RI) (RI) 1.93 2.25 2.44 2.54 Shrinkage% (toasting to hardening) 11.7 10.5 6.4 4.1 Dielectric constant (around) 2.07 2.30 2.54 2.75 Dielectric constant (outgassing) 2.03 2.24 2.46 2.66 Modulus (Gpa) 2.40 ± 0.121 (1.2 microns) 3.60 ± 0 · 118 (1.2 microns) 4 · 80 ± 0 · 152 (1.2 microns) 5.13 soil 0.192 (1.2 microns) Hardness (Gpa) 0.12 ± 0.018 (1.2 microns) 0.24 ± 0.043 (1.2 microns ) 0.33 ± 0.025 (1.2 microns) 0.32 ± 0.037 (1.2 microns) Average peak pore diameter 12.0 nm 9.0 nm 5.0 nm 3.0 nm Average pore diameter 5.1 nm 4.0 nm 2.8 nm 2.7 nm Pore volume (cubic Cm / g) 0.669 0.511 0.315 0.233 Partially estimated microporosity and porosity (%) 41 34 24 19 Surface area (m2 / g) 521 511 450 341 Adhesive tape test Pass dry / wet pass dry / wet pass dry / wet pass dry / wet at 425 ° C The stability is 5.45% 5.07% 4.30% 4.07% The results show that the dielectric constant decreases with the increase of the amount of pore-forming agent. Inventive Examples 48-54-Production of Falling Film of Inventive Examples 11-17 and Comparative Example C

The compositions of Inventive Examples 11-17 were applied to substrates using typical coating conditions known to those skilled in the art and baking and hardening conditions of Inventive Example 42. Comparative Example C was prepared in a similar manner to U.S. Application 60 / 350,187, under review by the inventors, and the Invention Example of January 15, 2002, and therefore did not contain a pore former. In the composition, the pore-forming agent is decomposed, and the pore-forming agent after the decomposition is vaporized, thereby forming pores in the composition. Results The formed layer was analyzed according to the aforementioned analytical test method, and the properties obtained from the analysis are reported in Table 18 below. Table 1 8 [7 苍 明 实 # Examples or Comparative Examples Refractive index (after baking) Refractive index (after curing) Thickness (Angstroms) (After baking) Thickness (Angstroms) (After curing) Shrinkage% (Toasting After hardening) Dielectric constant k (around) Dielectric constant k (degassing) △ k% 48 1.661 1.529 8518.23 8067.62 -5.29 2.48 2.18 -12.10 49 1.657 1.532 8057.8 7541.79 -6.40 2.51 2.42 -3.59 50 1.661 1.499 7225.37 7093.32- 1.83 2.54 2.44 -3.94 51 1.658 1.521 8659.18 8510.56 -1.72 2.51 2.43 -3.19 52 1.657 1.510 8025.79 7952.16 -0.92 2.53 2.43 -3.95 53 1.659 1.500 8633.55 7815.56 -9.47 2.42 2.33 -3.72 54 1.661 1.504 8899.51 8605.25 -3.31 2.42 2.32 1.677 1.617 3152.00 3252.00 3.17 2.69 2.62 -2.60

Invention Example Surface Area (m2 / g) Pore Volume (cubic Dongm / g) Average Cylinder Pore Diameter (nm) Estimated BJH Spike Pore Diameter (nm) 48 559.00 0.427 3.10 10.00 49 568.00 0.410 2.90 10.00 50 564.00 0.436 3.10 10.00 51 443.00 0.306 2.80 8.00 52 543.00 0.425 3.10 10.00 53 612.00 0.491 3.20 8.00 54 574.00 0.461 3.20 8.00 Inventive Examples 55-58-Production of Inventive Examples 18-21 and Comparative Examples D. Inventive Examples 18-21 The composition was applied to a substrate using Code-118-(112) 200406031 known to those skilled in the art, continued: M1 Continued: Type coating conditions and baking and hardening conditions of Invention Example 42 were applied to the substrate. Comparative Example D was prepared in a similar manner to U.S. Application No. 60 / 350,187, which is under review by the inventors, and the invention examples of January 15, 2002, and therefore did not contain a porogen. Decomposition of the pore-forming agent in the composition ′ The pore-forming agent after decomposition is vaporized, thereby forming pores in the composition. Results The formed layer was analyzed according to the aforementioned analytical test method. The properties obtained from the analysis are reported in Table 19 below, where Rj represents the refractive index. Table 19 Inventive Examples or Comparative Examples Refractive Index (After Baking) Refractive Index (After Baking) (RI) (RI) [«(5) 1 (After Baking) Thickness (Angstroms) (After Baking) Shrinkage% ( After baking and hardening) 55 1.655 1.548 2.395 6800.55 6916.90 1.71 56 1.657 1.543 2.381 6814.10 6885.99 1.06 ~~ 57 1.657 1.549 2.400 6792.82 6871.42 1.16 58 1.655 1.567 2.456 7520.50 7394.75 D 1.677 1.617 2.615 3152.00 3252.00 3ΛΊ ~ Inventive Example | M / g) Pore answer product Γ cubic centimeter / g) Pore diameter of average cylinder (nanometer) Estimated BJH peak pore diameter (nanometer) 57 56 476__ 464 0.31 2.60 16.00 one &quot; ^ 5307 2.60 14.00 one one 5 ^ 97 2.50 20.00 57 468 58 _ 429__ ^ 0275 — 2.60 20.00 Inventive Example 59-6 Lithium Thin-Film m The composition of Inventive Examples 24-30 uses typical coating conditions known to those skilled in the art and uses Inventive Example 42 To dry and harden conditions. The pore-forming agent after the decomposition of the pore-forming agent in the composition is vaporized, thereby forming pores in the composition. The layer formed as a result was analyzed according to the aforementioned analytical test method, and the properties obtained from the analysis are reported in Table 20 below. The results show that the combination of a cage and a vinyl isovalerate copolymer porogen 200406031 (113) Reference: The bottle and sun moon secretion have a dielectric constant, which is higher than that of rhenium and triglyceride. The composition has a low dielectric constant.

Am Inventive Example Starting Composition: Inventive Example Refractive index (after hardening) Shrinkage% (after baking and hardening) Refractive index 2 Dielectric constant k (around) Dielectric constant k (outgassing) △ k% Surface area (M2 / g) Pore volume (cm3 / g) Average cylinder pore diameter (nm) Estimated BJH peak pore diameter (nm) 59 26 1.45 16.36 2.10 2.13 2.09 1.88 594 0.651 4.4 11.0 60 27 1.41 11.26 1.99 2.1 2.06 1.90 622 0.698 4.5 14.0 61 28 1.41 8.28 1.99 2.11 Γ? 07 1.90 600 0.697 4.6 12.0 62 29 1.41 9.15 2.00 2.09 2.05 1.91 614 0.696 4.5 11.0 63 30 `` 1.40 5.7 1.95 2.06 2.02 1.94 577 0.738 5.1 16.0 64 '31 1.54 25.16 2.36 2.48 2.42 2.42 581 0.389 2.7 No peaks 65 32 1.48 17.11 2.18 2.33 2.28 2.15 612 0.504 3.3 7.0 66 33 1.44 12.96 2.07 2.19 2.14 2.28 649 0.631 3.9 9.0 Invention implementation examples Explain Example 3ι ^^ &gt; preparation

The compositions of Inventive Examples 31-32 were applied to substrates using typical coating conditions known to those skilled in the art and baking and hardening conditions of Inventive Example 42. In the composition, the pore-forming agent is decomposed, and the pore-forming agent after the decomposition is gasified ', thereby forming pores in the composition. The layer formed as a result was analyzed according to the aforementioned analytical test method, and the properties obtained from the analysis are reported in Table 21 below, where NM means not measured and magic index means refractive index. Repeat the description, but change the amount of pore former. In Table 22, the results show that pore formers that do not have some thermal stability can be selected to obtain certain desired dielectric constants. In Table 22, RI indicates a refractive index. -

I% »/» ^ 21 Invention Examples or Comparative Examples Refractive index (after baking) Refractive index (after curing) (Ri) (Ri) Thickness (Angstrom) (After baking) Thickness (Angstrom) (After curing) Shrinkage% (after drying and hardening) 67 CO 1.581 1.570 2.466 10819 6275.94 -41.99 Oo NM --J LlMZlJ 2.468 NM NM NM -120- (114) 200406031 Example of the invention ) Average cylinder pore diameter (nanometer) Estimated BJH peak pore diameter (nanometer) 67 462 0.25 2.2 Very small 4 nm 68 99 ^^ 0.089 3.6 NM Table 22% porogen Mw (after hardening) (RI) (RI)% thickness change dielectric constant k (outgassing) 0 ^ Τ6Ϊ3 2.60 4 2.65 — 27 3000 ^ ΠΤ543 2.41 -12 2.49 27 1250 ^ --L568 2.46 -16-27 530-^ L594 2.54 -19 2.58 35 3000 Τ495 2.28 -17 2.44 35 1250 ^ ΠΓ556 2.42 -22 240 50 3000 ΪΑ65 2.15 -31 2.27 ^ 50 1250 ^ T497 2.24 -33 2.24 ~ Inventive Examples From 7] and a slightly lower rate of the film g. The compositions of Examples 33-35 use typical coating conditions known to those skilled in the art and use of the invention Example 42 Curing conditions of dry roast and administered to the substrate. Comparative Example E was prepared according to the US application 60 / 350,187 in the examination of the inventors, and applied for Invention Examples 4-7 of January 15, 2002, and thus does not contain the original hole sword. In the composition, the pore-forming agent is decomposed, and the pore-forming agent after the decomposition is vaporized, thereby forming pores in the composition. The resulting layer was analyzed according to the aforementioned analytical test method. Layer properties are reported in Table 23 below.

Am

Nature Invention Example 69 Invention Example 70 Invention Example 71 Tb conversion 1.542 1.540 1.528 ~ L623 ^ '(hardened 16.5 〇C 〇 ~ 20.4 12.3 —r \ c Λ _ 2.58 2.48 ~ ΐπΤ ^ —gas) 1 ^ 2 · 54 i Λ I _ 2.54 2.43 2.70 ^ · △ k% 1.42 1.51 2.09 ι.ΤΓ ^ Mean pore diameter (nano) 15 1 15 33 ΓΓ J

[4i -121. 200406031 Fayu I. Continuation page, (115) Pore volume (cubic centimeter. 323 364 • 392.257 m / g) Implementation. Surname 72 · 77 — Invention Example 38-4L ^^ Ju The amine of column F> The composition of Invention Examples 38-41 was applied to the substrate using typical coating conditions known to those skilled in the art and baking and hardening conditions of Invention Example 42. Comparative Example F was prepared in a similar manner to U.S. Application 60 / 350,187 'under review by the same inventors, and was invented on January 15, 2002 in a similar manner, and thus did not contain this pore former. In the composition, the pore-forming agent is decomposed 'and the pore-forming agent is vaporized, thereby forming pores in the composition. The layer formed as a result was analyzed in accordance with the aforementioned analytical test method, and the properties obtained from the analysis are reported in Table 24 below. Here, NM indicates that the refractive index is not measured and that it indicates the refractive index. Inventive Examples or Comparative Examples Refractive index (after baking) Refractive index 1 (after curing) ⑽⑽ Thickness (Angstrom) (After drying) Thickness (Angstrom) (After curing) ------- Shrinkage% ( After baking and hardening) 1 Dielectric constant | k (peripheral) Dielectric constant k (outgassing)-72 '1.592 1.549 2.400 10000.36 5980.85 -40.19 2.75 1 2.61 no-73 NM 1.545 2.387 NM NM • NM NM 2.62 • j .uy 1 c —74 1.595 1.565 2.450 7815.35 4632.49 -40.73 2.78 2.66 &quot; J. 10 -4.32 ^ QQ —75 1.601 1.561 2.435 2927.49 1757.16 -39.98 ^ 2.76 2.65-76 1.603 1.524 2.322 2781.52 1798.23 -35.35 2.53 2.45 ^ 1 c '' 7 1.603 1.523 2.320 2752.07 1787.38 -35.05 2.60 ~ Ιό9 ~~ 2.51 162 ~ 0.10 -3.46 1.60 a--F 1.677 1.617-3152.00 3252.00 ------ ^ Tbjh peak pores | diameter (nm) / ΐ 5 nm [20 Invention ^ Example surface area i (m2 / g) | Pore volume (cm3 / g) Average cylinder pore diameter (nm) _ 72 507 0.2683 2.1 _ 73 483 0.23 1.9 ~ _ 74 486 0.238 ~~ Ιο ~~ · _ 75 482 0.251 ---- 2.1 _ 76 570 0.394 ~-_ 77 550 0.371 2.7 ~ 18 "J, 8 Nai ^^ • 122- 200406031 (116) Posted in September, explaining that the performance page was separated from Preparation Example 1, 3 / 4- 贰 {Γ, 3 ', 5 乂 ref [3〃 / 4〃- (phenylethynyl) phenyl] adamantane-7'-yl} benzene (shown in FIG. 1F) combines an adhesion promoter and a pore former, and then dissolves in a solvent, spin-coated on a broken wafer, and then Bake and harden into thin films for microchips or microchip modules. Invention Example 79 1,3- 贰 {3V4'- [Γ, 3〃, 5〃-〃 [3〃V4〃 '-(phenylethynyl) phenyl] adamantane-7〃 -Yl] phenyl} -5,7- 贰 [3〃〃 / 4〃〃- (phenylethynyl) phenyl] adamantane (shown in Figure 1F) combines adhesion promoter and pore former, and then dissolves in Solvents are spin-coated on silicon wafers, then baked and hardened into thin films for microchips or microchip modules. Brief Description of the Drawings Figures 1A to 1F show how to make a composition based on diamond gangue which can be used as the thermosetting component of the composition. Fig. 2 shows a method for producing a bisdamantane-based composition which can be used as a thermosetting component of the present composition. Figures 3A to 3F show another method of manufacturing a bismuth-based composition which can be used as the thermosetting component of the present composition. FIG. 4 shows a scanning electron micrograph of a cross section of a thin film of Example 44-47 of the invention. FIG. 5 shows a scanning electron micrograph of the surface of the thin film of the inventive example 44-47. Figure 6 shows a thermal desorption mass spectrometry plot of Inventive Examples 46-49.

Claims (1)

200406031 Patent application scope 1. A composition comprising: ⑻ a dielectric material; and (b) a pore former comprising at least two fused aromatic rings, each of which has at least one alkyl substitution The previous bond exists between the alkyl substituents on the adjacent aromatic ring. 2. The composition according to item 1 of the patent application range, wherein the pores are formed from unfunctionalized polyfluorene homopolymer, functionalized polyfluorene, polyfluorene copolymer, poly (2-ethylenylfluorene) And a group consisting of adducts of vinyl anthracene. 3. For example, the composition of claim 2 in the scope of patent application, wherein the polyfluorene copolymer made of pore-forming fluorene and monomer is selected from the group consisting of isoenyl ester, third butyl propionate, styrene, α-methylphenethyltributylstyrene, 2-vinyl tea, 5-vinyl-2-ortho-vinylcyclohexane, vinylcyclopentane, 9-ethenylanthracene, biphenyl, Tetraphenylbutadiene, stilbene, tert-butylfluorene, indene, and propenyl-substituted polymethylsilazane, ethyl ester, methyl acrylate, methyl methylpropionate, and ethyl ethyl ether group. 4. The composition according to item 2 of the patent application, wherein the pores are formed from unfunctionalized polyfluorene homopolymer, functionalized polyfluorene, polyfluorene copolymer, and unfunctionalized polyfluorene. Groups of adducts of polylactones. The above, and at least two selected homopolymers and their other agents are selected from the group consisting of ethylene valerate, dipene and 4-vinyl diphenylacetate, and polyhexamone 200406031. Patent application scope Continued 5. The composition according to any one of claims 2 or 3, wherein the dielectric material is an organic material. 6. The composition as claimed in claim 5 wherein the dielectric material is a phenylethynylated aromatic monomer or oligomer. 7. The composition as claimed in claim 5 wherein the organic dielectric material is a cage compound, preferably adamantane. 8. A spin-coating precursor comprising a composition as claimed in item 5 of the patent application. 9. A thermosetting matrix prepared from a spin-on precursor as described in item 8 of the patent application. 10. —Layer, containing a thermoset matrix as described in item 9 of the patent application. 11. The layer in the scope of patent application item 10, wherein the thermosetting base system is hardened. 12. A method for using a composition such as the item 5 in the scope of patent application. 13. The method according to item 12 of the scope of patent application, comprising the following steps: decomposing the pore-forming agent; and vaporizing the decomposed pore-forming agent, so that the dielectric constant of the dielectric material decreases. 14. The method of claim 12 includes the following steps: decomposing the pore-forming agent; and vaporizing the decomposed pore-forming agent so that pores are formed in the dielectric material. 15. The method according to item 13 of the patent application, wherein the step of decomposing into a porogen comprises hardening by furnace, hot plate, electron beam, microwave or ultraviolet radiation. 200406031 Patent Application Achievement Page 16. The method according to item 14 of the patent application, wherein the step of decomposing into a porogen includes hardening by furnace, hot plate, electron beam, microwave or ultraviolet radiation. 17. A composition comprising a cage structure having a dielectric constant less than 2.7. 18. The composition of claim 17 in which the caged structure is diamond-fired. 19. A spin coating precursor comprising a composition as set forth in claim 18 of the scope of patent application. 20. A thermosetting substrate prepared from a spin coating precursor as described in item 19 of the patent application. 21. —Layer, which contains a thermosetting matrix as described in item 20 of the patent application. 22. The layer as claimed in claim 21, wherein the thermosetting-based system is hardened. 23. A composition comprising: (a) a thermosetting component comprising: (1) at least one monomer of formula I Q Q 'as required Q Q and (2) at least one oligomer or polymer of formula II h Here E is a cage compound; each Q is the same or different and is selected from hydrogen, aryl, branched aryl and substituted aryl, wherein these substituents include hydrogen, i atom, alkyl, aryl Group, substituted aryl, heteroaryl, aryl ether, fluorenyl, decyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxy or carboxyl; Gw is aryl Or substituted aryl, where substituents include dent atoms and alkyl groups; h is 0 to 10; i is 0 to 10; j is 0 to 10; and w is 0 or 1; (b) porogen. 24. The composition as claimed in claim 23, wherein the porogen comprises a material having a decomposition temperature lower than the glass transition temperature of the thermosetting ingredient ⑻ and higher than the hardening temperature of the thermosetting ingredient ⑻. 25. The composition as claimed in claim 24, wherein the porogen comprises at least two fused aromatic rings, wherein each of the fused aromatic rings has at least one alkyl substitution based thereon, and a bond exists Between at least two of the alkyl substituents on adjacent aromatic rings. 200406031 Patent Application Continued Page 26. For the composition of Patent Application No. 24, wherein the pore-forming agent is selected from unfunctionalized polyfluorene homopolymer, functionalized polyfluorene homopolymer, and polyfluorene Copolymer, polyorbornene, polycaprolactone, poly (2-vinylfluorene), vinyl E, polystyrene, polystyrene derivative, polysiloxane, polyester, polyether, polyacrylic acid A group of esters, aliphatic polycarbonates, polyfluorenes, polylactides and their adducts. 27. The composition of claim 26, wherein the pore-forming agent is a polyfluorene copolymer made of rhenium and a monomer, and the single system is selected from vinyl isovalerate, third butyl acrylate, Acetophenone, α-methylstyrene, tertiary butylstyrene, 2-vinylfluorene, 5-vinyl-2-orbornyl, acetomethylcyclohexane, vinylcyclopentane, 9- Acetylanthracene, 4-vinylbiphenyl, tetraphenylsuccinic acid, diphenylethylidene, tert-butyldiphenylethylfluorene, indene, polymethylsilylsilane, vinyl acetate, substituted with propenyl Purpose, a group consisting of methyl acrylate, methyl methacrylate and vinyl ether. 28. The composition of claim 24, wherein the pore-forming agent is selected from the group consisting of unfunctionalized polyfluorene homopolymer, functionalized polyfluorene homopolymer, polyurea copolymer, and polyorborneol. A group of associations and associations. 29. The composition according to item 26 of the patent application, comprising (1) at least one adamantane monomer of formula III Q and (2) the at least one adamantane oligomer or polymer of formula IV 200406031 Patent Application Continued And (2) the oligomer or polymerization of the at least one bisadamantane monomer of formula VI 200406031 30. The composition of claim 29, wherein the at least one oligomer or polymer (2) is an adamantane binary of the following formula VII 31. The composition of claim 29, wherein the at least one oligomer or polymer (2) is an adamantane triad of the following formula VIII 32. The composition of claim 26, wherein the thermosetting component (a) comprises (1) an adamantane monomer of formula XA 200406031 Ri XC Or XD Ri Patent Application Continued on page and (2) at least one oligomantan oligomer or polymer of formula XI 200406031 Patent Application Achievement Sheet Or (1) at least one bisadamantane monomer of formula XIIA 200406031, type XIIC Or XIID Patent Application Achievement Sheet and (2) at least one bisadamantane oligomer or polymer of formula XIII 200406031 Continued patent application range where the h is 0 to 10; the i is 0 to 10; the j is 0 to 10; the R! Are each the same or different and are selected from the group consisting of hydrogen, halogen atom, alkyl, aromatic Aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxy, or carboxyl; and Y is each Identical or different and selected from hydrogen, alkyl, aryl, substituted aryl or i atom. 33. The composition of claim 32, wherein the monomer is present. 34. The composition according to any one of claims 32 or 33, wherein the &amp; is an aryl group or a substituted aryl group; and the Y is hydrogen, phenyl, or biphenyl. 35. The composition of claim 34, wherein the (2) adamantane oligomer or polymer is a binary compound of formula XVI Or the (2) bisadamantane oligomer or polymer is a binary compound of formula XVII 200406031 36. The composition as claimed in claim 34, wherein the amantadine oligomer or polymer is a triad of formula XνΠΙ -12- 200406031 Patent Application Continued 37. If the composition of Patent Application No. 34 is applied, here the thermosetting component (a), the oligomer or polymer (2) contains the adamantane binary of formula XVI -13-200406031 Scope of Patent Application Continued Mixture with bisadamantane triad of formula XIX In point (a), the monomer (1) and the oligomer or polymer (2) are monomers mainly composed of adamantane. 39. The composition of claim 38, wherein at least two of the RiOC groups of the phenyl group are two different isomers; and a phenyl group between the two bridgehead carbons of the adamantane monomer There are two different isomers in at least one of them. 40. The composition of claim 39, wherein the at least two isomers are meta- and para-isomers. 41. If the composition according to item 34 of the patent application scope further comprises (c) an adhesion promoter comprising a compound having at least a difunctional group, wherein the difunctional groups may be the same or different, and the first functional group may be Interaction with the thermosetting ingredient rhenium, and the second functional group may interact with the substrate when the composition is applied to the substrate. 42. The composition according to item 41 of the scope of patent application, wherein the adhesion promoter -14-200406031. The scope of the patent application continued page is selected from the group consisting of: Formula XXXVI Silane: (R2) k (R3) iSi ( R4) m (R5) n, where R2, R3, R4 and R5 each independently represent hydrogen, a hydroxyl group, an unsaturated or saturated fluorenyl group, a substituted or unsubstituted alkyl group (where the substituent is an amine group or a ring (Oxy), unsaturated or saturated epoxy, unsaturated or saturated acid group, or aryl group, wherein at least two of R2, R3, R4, and R5 represent hydrogen, hydroxyl, saturated or unsaturated alkoxy Group, unsaturated alkyl group, or unsaturated carboxylic acid group, and k + l + m + n &lt;4; polymethylsilylsilane of formula XXXVII: Qin 10 Η I-Si- -Si- R 11 i12 r14- o— —R13 Ris, one Rir Rl6 P Wherein, r8, r14, and r17 each represent a substituted or unsubstituted alkylene, cycloalkylene, vinylene, propylene, or aryl group; r9, R10, Rn, R 丨 2, R15, and Ri6 each represents a hydrogen atom, an alkyl group, an alkylene group, a vinyl group, a cycloalkyl group, a propenyl group, an aryl group, or an arylene group, and may be linear or branched; Ri3 represents an organic silicon, a silyl group, a siloxy group, or Organic groups; and p, q, r, and s satisfy the conditions [4 邱 + q + r + s ^ l00,000] and q and r and s may be common or zero respectively; unsaturated carboxylic acid containing at least one carboxylic acid group Glycidyl ethers or esters of acids; vinyl cyclic oligomers or polymers, where the cyclic group is ethenyl, aromatic or heteroaromatic; and -15-200406031 Page XXXVIII Phenol-formaldehyde resins or oligomers:-[R18C6H2 (〇H) (Ri9)] u, where r18 is substituted or unsubstituted alkylene, cycloalkylene, vinyl, propylene Aryl or aryl; R19 is alkyl, alkylene, vinylidene, cycloalkylene, propenyl, or aryl; and 11 = 3-100. 43. The composition according to claim 42 in which the adhesion promoter (c) is the phenol-formaldehyde resin or oligomer. 44. A spin coating precursor comprising the composition as claimed in claim 41 and the solvent is preferably cyclohexanone. 45. A thermosetting matrix prepared from a spin-on precursor as described in claim 44 of the patent application. 46. —Layer, which contains a thermosetting matrix as described in claim 45. 47. The layer as claimed in item 46, wherein the thermosetting base system is hardened. 48. For example, the layer of the scope of application for item 46, wherein the layer has a dielectric constant of less than 2.7, preferably less than 2.5, preferably less than 2.2, and most preferably less than 2.0. 49. The layer according to item 46 of the patent application, wherein the layer has an average pore size and a diameter of less than 20 nm. 50. A substrate with at least one layer such as the 46th item in the patent application scope. 51. A microchip including a substrate such as the scope of application for item 50. 52. A composition comprising: (a) a compound having at least a difunctional group, wherein the difunctional groups may be the same or different, and at least one of the first functional group and the second functional group is selected from the group consisting of: A group consisting of a silicon-containing group, a nitrogen-containing group, a carbon bond to an oxygen-containing group, a hydroxyl group 200406031 patent application, a continuation group, and a carbon-containing double bond bond to a carbon-containing group; and (b) a porogen, which Containing at least two fused aromatic rings, wherein each of the fused aromatic rings has at least one alkyl substitution based thereon, and at least two of the alkynyl substituents present on a neighboring aromatic ring with a bond. 53. The composition as claimed in claim 52, wherein the porogen is selected from the group consisting of unfunctionalized polyfluorene homopolymer, functionalized polyfluorene homopolymer, polyfluorene copolymer, poly (2 -A group consisting of vinyl fluorene), vinyl E, and adducts thereof. 54. The composition of claim 53 in which the pore-forming agent is a polyfluorene copolymer made of rhenium and a monomer, and the single system is selected from vinyl isovalerate, third butyl acrylate, Phenethylhydrazone, α-methylstyrene, tert-butylstyrene, 2-ethylfluorenylfluorene, 5-vinyl-2-orbornene, vinylcyclohexane, vinylcyclopentane, 9- Vinyl anthracene, 4-vinyl biphenyl, tetraphenyl stilbene, stilbene, tert-butyl stilbene, indene, polymethylsilyl silane substituted with propenyl, vinyl acetate, methyl acrylate, methyl Group consisting of methyl methacrylate and acetamyl ether. 55. The composition of claim 54 in which the adhesion promoter is selected from the group consisting of: Formula XXXVI Silanes: (R2) k (R3) iSi (R4) m (R5) n, where R2, R3, R4, and R5 each independently represent hydrogen, a hydroxyl group, an unsaturated or saturated alkyl group, a substituted or unsubstituted alkyl group (where the substituent is an amine group or an epoxy group), and an unsaturated or saturated epoxy Group, unsaturated or saturated acid group or aryl group 17-200406031 Application for continued patent application, in which at least two of R2, R3, R4 and &amp; represent hydrogen, meridian, saturated or unsaturated alkoxy , Unsaturated alkyl, or unsaturated carboxylic acid groups, and k + l + m + n &lt;4; RlO R12 R15 Sj-Rs --- one P one Si- R11 &quot; Si ~ R14 o——r13 Si --R17 I R16 Among them, r8, r14, and r17 each independently represent a substituted or unsubstituted alkylene, cycloalkylene, vinylidene, propenyl, or aryl; R9, R1G, Ru, R12, R15, and Ri6 each independently Represents a hydrogen atom, an alkyl group, an alkylene group, an ethenyl group, a cycloalkyl group, a propionyl group, an aryl group, or an arylene group, and may be linear or branched; R13 represents a silicone, a silyl group, a siloxy group, or an organic Basis; and p, q, r, and s satisfy the condition [4 ^ p + q + r + sSl00,000], and q and r and s may be zero or common; Glycidyl ethers or esters of unsaturated unsaturated acids containing at least one polyacid group; vinyl cyclic oligomers or polymers, where the cyclic group is ethenyl, aromatic or heteroaromatic; And phenol-formaldehyde resins or oligomers of the formula XXXVIII, Propenyl or aryl; R19 is alkyl, alkylene, ethylidene, cycloalkyl, propenyl or aryl; and u = 3-100. 56. The composition according to item 55 of the patent application, wherein the adhesion promoter -18-200406031 patent application release page (C) is the phenol-formaldehyde resin or oligomer. 57. The composition as claimed in claim 55, wherein the compound (I) interacts with the porogen (b). 58. The composition according to item 55 of the patent application additionally includes a dielectric material. 59. A composition comprising: (a) a thermosetting component comprising: at least two different mixtures of isomers of formula XXVII Q Here E is a cage compound; each Q is the same or different and is selected from the group consisting of hydrogen, aryl, branched aryl, and substituted aryl, wherein these substituents include hydrogen, atom, alkyl, aryl , Substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, dialkyl, light alkyl, aryl, or aryl; Gw Is aryl or substituted aryl, where substituents include halogen atoms and alkyl groups; h is 0 to 10; i is 0 to 10; "is 0 to 10; and w is 0 or 1; and (b ) Pore-forming agent. 60. The composition of claim 59, wherein the mixture comprises at least two different isomers of formula XXVIII -19- 200406031, formula XXIX Or XXX Patent Application Continuation Sheet Here Y is each the same or different and is selected from hydrogen, alkyl, aryl, substituted aryl or atom; and Ri is each the same or different and is selected from hydrogen and halogen Atoms, alkyls, aryls, substituted aryls, heteroaryls, aryl ethers, alkenyls, alkynyls, alkoxys, hydroxyalkyls, hydroxyaryls, sulfonyls, sulfonyls, Jingji or Jiji. 61. The composition of claim 59, wherein the mixture comprises at least two different isomers of the formula XXXI , Formula XXXII -20- 200406031 R Or formula XXXIV Patent application page: Here Y is each the same or different and is selected from hydrogen, alkyl, aryl substituted aryl or halogen atom; and Ri is each the same or is selected from hydrogen, halogen atom, alkane Aryl, aryl, substituted arylaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl aryl, hydroxyfluorenyl, hydroxyalkynyl, hydroxy, or carboxyl. Base, hetero-, hetero, rear