TW200424228A - Organic compositions - Google Patents

Abstract

The present invention provides a composition comprising: (a) thermosetting component comprising (1) optionally at least one monomer of Formula I as set forth below and (2) at least one oligomer or polymer of Formula II set forth below where E is a cage compound (defined below); each Q is the same or different and selected from hydrogen, aryl, branched aryl, and substituted aryl wherein the substituents include hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; Gw is aryl or substituted aryl where substituents include halogen and alkyl; h is from 0 to 10; I is from 0 to 10; j is from 0 to 10; and w is 0 or 1; (b) adhesion promoter comprising compound having at least bifunctionality wherein the bifunctionality may be the same or different and the first functionality is capable of interacting with the thermosetting component (a) and the second functionality is capable of interacting with a substrate when the composition is applied to the substrate. The present compositions may be used as a dielectric substrate material, etch stop, hardmask, or air bridge in microchips, multichip modules, laminated circuit boards, or printed wiring boards. The present composition may also be used as a passive coating for enveloping a completed wafer.

Description

200424228 Ο) 5. The description of the invention (the description of the invention should state the technical field of the invention, the prior art, the content, the implementation mode and the simple description of the invention). This application is May 30, 2002. The extension of the pending application No. 10/160773 is Shao Fen, claiming that the pending temporary patent application No. 60 / 294,864 filed on May 30, 2001; No. 60 / 318,503 filed on September 10, 2001 No. 60/350187, filed January 15, 2002; and No. 60/352098, dated January 24, 2002, which is incorporated herein by reference in its entirety. 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. BACKGROUND OF THE INVENTION When working on the performance and speed of semiconductor devices, semiconductor device movers seek to reduce the width and spacing of interconnects while minimizing transmission losses and reducing the threshing coupling of interconnects. One way to reduce power consumption and capacitance is to reduce the dielectric constant of the insulating material (also cited as,, k ,,) or the dielectric of the beta interconnect. I especially need a material with a low dielectric constant, because this material typically allows faster signal transmission, reduces capacitance and crosstalk between conductor lines, and reduces the electricity required to drive integrated circuits, which is gas-based. " The% hanging number is 1 · 〇, one of the main goals is to reduce the dielectric constant of the insulator material to a theoretical limit of 10, and several types of dielectric materials are known in the art to reduce the dielectric constant of the 4H and the mound material. These techniques include the addition of 4 to 5 yuan, and) to reduce the dielectric constant of the loose material. Other (2) (2) 200424228 Description of the Invention Continued ways to reduce k, this ancient includes Alternating dielectric material matrix is used. Therefore, as 1¾ ^ decreases and the interconnect line width decreases, the dielectric constant of the insulating material needs to be reduced. For example: to achieve the desired improved performance and speed of future semiconductor devices. Seek # 1 for interconnection Devices with a line width of 0.13 or 0.10 micrometers and lower ... Insulation materials with an electric constant (k) < 3. At present, it is the use of rare or fluorinated sand fossils (in 〇2) and SiO2 modified products, such as Rail Dioxide These Dielectrics & a mp; breaking field (hereinafter referred to as FSG). In semiconductor devices, FSG is often used as a dielectric with an oxide of 4.0. Although Si02 is mechanically and thermally heated, it is subject to thermal cycling and The processing steps required in the past, and redundantly in the industry, materials with lower dielectric constants are required. Deposition methods (the following methods of accumulating dielectric materials can be divided into two categories. Spin-coating several lower-development dielectrics) ) And chemical vapor deposition (hereinafter referred to as CVD). Organic, inorganic, and / or electrical constant materials include efforts to change the chemical composition (with non-porosity). Table \ discriminator blends) or change the dielectric matrix ( Porosity, (PE = reinforced electrical t; green number f; dielectric constant 2.0 to 3.5; dielectric material disclosed in the development case: high-density plasma). However, effective dielectric materials are announced in Table 1 Materials and substrates cannot exhibit many desired even high thermal stability, ancient spoon, ° σ physical and chemical properties, such as higher mechanical stability, ^ can be solvated, multi-temperature, high modulus or hardness, while still being . Therefore, the axe ^ transferred to Tu Wei or deposited on the substrate, wafer Or other surface compounds, compounds, and materials that can be useful as dielectric materials and layers are not currently available, even if these compounds or materials are in their existing form as dielectric materials. 200424228 (3) Description of the invention Continued Table 1 Dielectric constant of material deposition method (k) Reference material Silicon fluoride (SiOF) PE-CVD; HDP-CVD 3.3-3.5 US Patent No. 6,278,174 Hydrosilsesquioxane (HSQ) SOD 2.0-2.5 US Patent Nos. 4,756,977, 5,370,903, and 5,486,564; International Patent Publication No. WO 00/40637; ES Moyer et al., 'Ultra Low k Silsesquioxane Based Resins'', Concepts and Needs for Low Dielectric Constant < 0.15 μιη Interconnect Materials; Now and the Next Millennium, issued by the American Chemical Society, pages 128-146 (14-17 November 1999) methylsilsesquioxane (MSQ) SOD 2.4-2.7 United States Patent No. 6,143,855 Polyorganic Silicon SOD 2.5-2.6 U.S. Patent No. 6,225,238 Fluoride "Amorphous Carbon (aC: F) HDP-CVD 2.3 U.S. Patent No. 5,900,290 Benzocyclobutane ( BCB) SOD 2.4-2.7 U.S. Patent No. 5,225,586 polyarylene ether (PAE) SOD 2.4 U.S. Patent Nos. 5,986,045, 5,874,516 and 5,658,994 Poly-p-phenylene dimethyl (N and F) CVD 2.4 U.S. Patent No. 5,268,202 Benzene SOD 2.6 U.S. Patent Nos. 5,965,679 and 6,288,188 B1; and "Integration Feasibility of Porous SiLK Semiconductor Dielectric" by Waiterloos et al., Proc. Of the 2001 International Interconnect Tech, Conf., Pp.253-254 ( 2001) Alkane CVD, SOD < 3.9 World Patent No. WO 01/29052 CVD, SOD < 3.9 World Patent No. WO 01 / 29141-10-200424228 (4) Description of the Invention Continued unfortunately, most developments have a dielectric constant SOD systems between 2.0 and 3.5 suffer from some of the shortcomings of mechanical and thermal properties as described above. Therefore, the industry needs to develop improved processing and performance of dielectric films in this range of dielectric constants.

Reichert and Mathias describe compounds and monomers that include adamantane molecules, which are cage-based molecules and are taught to be used as diamond substitutes. (Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1993, Vol. 34 (1), pp. 495-6; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1992, Vol. 33 (2), pp. 144-5; Chem. Mater., 1993, Vol. 5 (1), pp. 4-5; Macromolecules, 1994, Vol. 27 (24 ), pp. 7030-7034; Macromolecules, 1994, Vol. 27 (24)? pp. 7015-7023; Polym, Prepr. (Am. Chem. Soc ·, Div. Polym. Chem ·), 1995, Vol. 36 (1), pp. 741-742; 205th ACS National Meeting Conference

Program, 1993, pp. 312; Macromolecules, 1994, Vol. 27 (24), pp. 7024-9; Macromolecules, 1992, Vol. 25 (9), pp. 2294-306;

Macromolecules, 1991, Vol. 24 (18), pp. 5232-3; Veronica R. Reichert, PhD Dissertation, 1994, Vol. 55-06B; ACS Symp. Ser .: Step-Growth Polymers for High-Performance Materials, 1996 , Vol. 624, pp. 197-207; Macromolecules, 2000, Vol. 33 (10), pp. 3855-3859; Polym, Prepr. (Am. Chem. Soc.? Div. Polym. Chem.) 5 1999, Vol. 40 (2), pp. 620-621; Polym, Prepr. (Am. Chem. Soc. 5 Div. Polym. Chem.), 1999, Vol. 40 (2), pp. 577-78; Macromolecules, 1997, Vol. 30 (19), pp. 5970-5975; J. Polym. Sci, Part A: Polymer Chemistry, 1997, Vol. 3 5 (9), pp. 1743-1751; Polym, Prepr. (Am.

-11-200424228 (5) Description of the invention continued

Chem. Soc.? Div. Polym. Chem.)? 1996, Vol. 37 (2), pp. 243-244; Polym, Prepr. (Am. Chem. Soc., Div, Polym. Chem.), 1996, Vol. 37 (1), pp. 551-552; J. Polym. Sci., Part A: Polymer Chemistry, 1996, Vol. 34 (3), pp. 397-402; Polym, Prepr. (Am. Chem. Soc. 5 Div. Polym. Chem.), 1995, Vol. 36 (2), pp. 140-141; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1992, Vol. 33 (2), pp. 146-147; J. Appl. Polym. Sci., 1998, Vol. 68 (3), pp. 475-482) 0 The adamantyl base compounds and monomers described by Reichert and Mathias Ideal for forming polymers with adamantane molecules in the thermoset core. However, the compounds disclosed in the study by Reichert and Mathias included only one isomer of an adamantyl base compound due to design choices. Structure A shows this symmetry para-isomer 1,3,5,7-tetra [4 '-(phenylethynyl) phenyl] adamantane:

In other words, Reichert and Mathias, in their personal and joint research, are waiting for a useful polymer in the form of an isomer that includes only one target adamantyl monomer. However, when a single isomer form (symmetric "all-para " isomer) from an adamantyl base monomer is formed and processed 1,3,5,7-tetra 200424228 说明 Description of the invention There is an important problem in [4 ·-(phenylethynyl) phenyl] adamantane. According to Reichert's paper (above) and Macromolecules, v〇1 27, (pp 7015_ 7034) (above) '"symmetric all-para-isomer i, 3,5,7 ^ [4, _ (benzene [Ethyl block] phenyl] diamond: Fe " are found to be sufficiently soluble in chloroform to obtain an H NMR spectrum. However, the number of times they are found to be unrealistic for obtaining a solution of% NMR spectrum is indicated. All para-isomers have low solubility. Therefore, the Reichert symmetry, all para, isomer [4,-(phenylethynyl) phenyl] adamantane is insoluble in standard organic solvents. Therefore, for any application that requires solubility or solvent-based processing ( (Such as flow coating, spin coating or dip coating) will not be useful. Patent application PCT / US01 / 22204 for which we applied for co-assignment on October 10, 2001 (U.S. serial number for the pending patent application which we have co-assigned for application on April 7, 2000 No. 09/545058; U.S. Serial No. 09/618945, filed on July 19, 2000; U.S. Serial No. 09 / 897,936, filed on July 5, 2001; U.S. Serial No. 09 /, filed on July 10, 2001 No. 902924; and the present right of International Patent Publication No. WO 01/78 110 published on October 18, 2001), we have found a composition comprising a heterogeneous thermosetting monomer or a polymer mixture, wherein The mixture includes at least one monomer or dimer having a corresponding structure:

Where Z is selected from fluorene-like compounds and silicon atoms; R ,, R'2, R, 3, R 200424228 说明 Description of the Invention Continued, R'5 and R'6 are independently aryl, branched aryl, and At least one of the arylaryl group, the branched aryl group, and the arylene ether having R′7 is an aryl group or a substituted aryl group. We also disclose methods for forming compounds. This novel isomeric thermosetting monomer or dimer is used as a dielectric material for microelectronic applications and is soluble in many ketones. These desirable properties make this isomeric thermosetting monomer useful for forming a thickness of about 0.1 micrometers to about 1.0 micrometers. Although various methods are known in the art to reduce the number, these methods still have disadvantages. Therefore, semiconductors a) provide improved compositions and methods to reduce the dielectric layer and provide dielectric materials with improved mechanical properties (such as thermal stability, glass rotation); and c) produce materials capable of solvating spin or laminated materials The above thermosetting compounds and dielectric materials < Abstract of the Invention In response to technical needs, we have developed the following compositions. In an embodiment, the composition includes: (a) a thermosetting component, which includes (1) at least one base ether option as needed; the acetylene group; and a useful solvent for these thermosetting mixture mixtures, such as cyclohexane or Polymer mixed films are desirable. The dielectric constant of the material The industry still needs the dielectric constant; b) the temperature Tg and the hard transfer coating on the wafer a first concrete monomer of formula I

Q

And (2) at least one oligomer or polymer of formula II -14- 200424228 说明 Description of the invention continued on

-15- 200424228 (9) Description of the invention continued page where E is a cage compound (defined below); each Q is the same or different 'and is selected from hydrogen, aryl, branched aryl and substituted aryl (where The substituents include hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, fluorenyl, block, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxymethyl, Hydroxyalkynyl, hydroxy, or carboxyl); Gw is aryl or substituted aryl (where substituents include halogen and alkyl); h is 0 to 10; i is 0 to 10; j is 0 to 10; and w is 0 or 1; (b) a viscosity promoter comprising a compound having at least bifunctionality, wherein the bifunctionality may be the same or different, when the composition is applied to a substrate, the 'first functionality can be compatible with the thermosetting component (A) Interaction, and the second official moon color can interact with the substrate. It is understood that when w is 0 in Chemical Formula II, the two cage compounds are directly bonded. For each E to which at least one Q is attached, preferably E does not have more than one Q being hydrogen, and more preferably E does not have Q being hydrogen. When Q is substituted Fang Si is more preferably a distant group substituted by an alkenyl group and a decyl group. The most preferred Q groups include (Derylethenyl) phenyl, bis (benzylethynyl) phenyl, phenylethynyl (phenyl block: yl), and (phenylethoxy) phenylphenyl Part. The preferred aromatics include phenyl, biphenyl and triphenyl. A more preferred G group is phenyl. Preferably, w is 10, and preferably, the thermosetting component includes: (1) at least one adamantane monomer of formula III 200424228 (ίο) Summary sheet and (2) at least one adamantane oligomer of formula IV Or polymer

Or (1) at least one adamantane monomer of formula V

Q

And (2) at least one oligomer or polymer of the adamantane of formula VI, -17- 200424228 (ii) description of the invention continued page

Where Q, Gw, h, i, j, and W are as previously defined.

Preferably, the thermosetting component ⑷ includes: (1) at least one chemical formula VIIA

Chemical formula VIIB -18-200424228 (12) Description of the invention continued

Chemical formula VIIC

Or adamantane monomer of formula VIID

Η

And (2) at least one oligomer or polymer of formula VIII, -19- 200424228 (13) description of the invention continued on

-20- 200424228 (14) Description of the invention continued

-21 · 200424228 (15) Description of the invention continued

Or (1) Chemical formula IXA

Chemical formula IXB

、 Chemical formula IXC -22- 200424228 Description of the invention continued (16)

Bisadamantane monomer of chemical formula IXD

And (2) an oligomer or polymer of at least one bisadamantane monomer of formula X. -23- 200424228 (17) Description of the invention continued

-24- 200424228

-25- 200424228 (19) Description sheet of the invention where h is 0 to 10; i is 0 to 10; j is 0 to 10; in the formulas VIIA, VIIB, VIIC, VIID, VIII, IXA, IXB, IXC, IXD and Each & in X is the same or different, and is selected from hydrogen, halo, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, fluorenyl, bulk, fluorenyl, alkoxy, Select by aryl, # present as fluorenyl, decyl, boryl or compound; in the formula VIIA, VIIB, VIIC, VIID, VIII, IXA, IXB, IXC and IXD, each X and γ are the same or different, and Select from hydrogen, alkyl, aryl, substituted aryl or autogen, and (b) the viscosity promoter as described above. Chemical formulae II, IV, VI, VIII and X represent random or irregular structures in which any unit h, i and j can be repeated multiple times or not before the presence of another unit. Therefore, the unit sequences in the above formulae II, IV, VI, VIII, and X are random or irregular. In the adhesion promoter (b), it is preferable that at least one of the first functionality and the second functionality is selected from the group consisting of Si group, n group, C-0 group, hydroxyl group, and C = 0 group. The Si-containing group is preferably selected from Si-H, Si-O, and Si-N; the N-containing group is selected from, for example, C-NH2 or other secondary and tertiary amines, imines, amidines, and amidines; C-0-containing groups are selected from = co, carbonyl (such as ketones and aldehydes), esters, -COOH, alkoxy groups with 1 to 5 carbon atoms, ethers, glycidyl ether, and epoxy groups; the # The base is Huan; and the group containing c == c is selected from propyl and ethyl. In the adhesion promoter (b), it is preferred that the si-containing group is selected from the group consisting of silane (R2) k (R3) lSl (R4) m (R5) n (where r2, R3, R4, and R5 are independently represented Hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkyl, wherein the substituent is amine or epoxy, unsaturated or saturated alkoxy, not -26- 200424228 (20) invention Explain that the saturated or saturated carboxyl or aryl group on the following page, and at least two of R2, R3, H4, and R5 represent hydrogen, hydroxyl, saturated or unsaturated alkoxy, unsaturated alkyl or unsaturated carboxyl group, and k + 1 + m + nS4) or polycarbonylsilane of chemical formula XII: Η " 1 -Si- | ^ 一 is ς; Rj3 1 J j Γ? 1 ~ Si —Ri5 -R? 1 r9 1 〇Rji R14 -P — — q ^ MM r (wherein R6, R12, and R15 each independently represent a substituted or unsubstituted sulfenyl * group, a cycloalkylene group, an ethylene group, a propylene group or an arylene group, R7, R9 , R1G, R13, and R14 each independently represent a hydrogen atom, an alkyl group, an alkyl group, an ethenyl group, a cycloalkyl group, an amidino group, an aryl group, or an arylene group and may be a linear or branched branch; Rn represents an organic Silicon, silyl, Oxygen or organic radicals' and p, q, r and s satisfy the condition of [4Sp + q + r + s < 100,000], and q and S can be collective or zero respectively); the C-0-containing group is from Glycidyl ether or esters containing at least one carboxylic acid group " φ and carboxylic acid esters; the OC-containing group is a vinyl ring oligomer or polymer, where the group group is pyridine, aromatic Or heteroaromatic; and the hydroxyl group is a phenolic resin or oligomer of the formula XIII ·--[R16C6H2 (OH) (R17)] ", wherein R16 is a substituted or unsubstituted member, a pentyl group, a cycloalkane Group, ethenyl, propyl, or aryl, R17 is kynyl, secondary alkyl, ethylene, cycloalkylene, propyl or aryl, and 3-100 ° in another specific implementation In the example, the composition includes: (a) thermosetting component-27-200424228 (21) Description of the invention continued page, which includes at least one oligomer or polymer of formula II, wherein E, (^ and Gw are as As previously defined; h is 0 to 10; i is 0 to 10; j is 0 to 10; and w is 0 or 1; and (b) a viscosity promoter comprising a compound having at least bifunctionality, wherein the Bifunctional The degree can be the same or different. When the composition is applied to a substrate, the first functionality can interact with the thermosetting component (a), and the second functionality can interact with the substrate. In the adhesion promoter (b ), It is preferable that at least one of the first functionality and the second functionality is selected from Si-containing group, N-containing group, C-0-containing group, hydroxyl group and C = C group. The composition preferably includes at least one oligomer or polymer of formula IV (where Q, Gw, h, i, ′ and w are as previously defined). We have also developed an improved thermosetting component that includes (1) at least one monomer of formula I and (2) at least one oligomer or polymer of formula II, where Q, Gw, h, i, j And w are as previously defined) a method for the viscosity of a substrate, comprising the steps of: adding a viscosity accelerator to the thermosetting component, the accelerator comprising a compound having at least difunctionality, wherein the difunctionality It can be the same or different, the first functionality can interact with the thermosetting component, and the second functionality can interact with the substrate to form a composition; and the composition is applied to the substrate. In the adhesion promoter (b), it is preferable that at least one of the first functionality and the second functionality is selected from Si-containing group, N-containing group, C-0-containing group, hydroxyl group, and C = C group. At the same time, we have also developed a method comprising the following steps: combining (a) a monomer comprising at least one or more chemical formula I and (2) at least one oligomer or polymer of chemical formula II (where Q, Gw, h, i, j, and w are thermosetting components as defined in the previous -28-200424228 (22) description of the invention (continued on the following page) and (b) a viscosity promoter that includes at least a bifunctional compound (wherein the bifunctional It may be the same or different, and when the composition is applied to a substrate, the first functionality can be the same as that of the thermosetting component (a)

'I Heteroconductor, screen chip difunctionality can interact with the substrate, function, use), in the bran release accelerator (b), it is preferred that at least one of the first functionality and the second functionality is from Si group, N group, C-0 group, hydroxyl group and C = C group are selected. Here, the term "combination" includes blending or reaction. The composition preferably has improved solubility. As a result, a thin film having a thickness of about 1.5 micrometers or more can be produced from the composition. The present invention is particularly preferred from the following. The detailed description and drawings of the embodiments will make the various objects, features, viewpoints, and advantages of the present invention more obvious. The drawings briefly illustrate FIGS. 1A to 1F illustrate how to manufacture the diamond used in the present invention as the (a) thermosetting component. The base composition. Fig. 2 illustrates a method for producing a bisadamantyl composition useful as the (a) thermosetting component in the present invention. Figs. 3A to 3F illustrate another manufacture useful in the present invention as the (A) Method of bisadamantane composition of thermosetting component. Detailed description of the invention The "cage structure" cage molecule 11 and "cage compound" used herein are intended to be used interchangeably and expressed as a type having at least 8 A molecule of atoms whose arrangement is such that at least one bridge covalently connects two or more atoms in the ring system. In other words, a cage structure, a cage molecule, and a cage compound package Includes many rings formed by covalently bonded atoms, where the structure, molecule, or compound-29-200424228 (23) Description of the Invention Continuation compounds define a volume such that a point within the volume cannot leave the volume without Does not pass through the ring. The bridging and / or ring system may include one or more heteroatoms, and may include aromatic groups, partially cyclic or acyclic saturated hydrocarbon groups, or cyclic or acyclic unsaturated hydrocarbon groups Further covered cage structures include fullerene and crown ether with at least one bridge. For example, monoamantane or bisadamantane is recognized as a cage structure, but in the scope of this definition, Aromatic spiro compounds are not recognized as fluorene-like structures, because the naphthalene or spiro compounds do not have one or more than one bridge, so they are not within the definition of cage compounds above. The cage compounds are preferably of the diamond type And double diamond firing, diamond firing is better. "Bridgehead carbon" is used here to mean any cage-like carbon bonded to the other three carbons. Therefore, for example, adamantane has four Bridgehead carbon, and bisadamantane has eight bridgehead carbons. The π viscosity promoter π used herein means any component. When added to the thermosetting component (a), compared to the thermosetting component (a) only, It improves its adhesion to the substrate. The term "compound having at least bifunctionality" as used herein means any functional group having at least two functional groups that can interact or react or form a bond as follows. The functional group can be Many types of reactions, including addition reactions, nucleophilic and electrophilic substitution reactions or removal reactions, free radical reactions, etc. More alternative reactions can also include the formation of non-covalent bonds, such as Van der Waals , Electrostatic, ionic, and hydrogen bonds. The term "layer" as used herein includes films and coatings. The term “f low dielectric constant polymer” as used herein refers to a dielectric • 30- 200424228

DESCRIPTION OF THE INVENTION Continued Organic, organometallic or inorganic polymers having a constant of about 3.0 or less. The low-dielectric material is typically manufactured in a thin layer thickness of 100 to 25,000 Angstroms (Angstrom), but it can also be used as a thick film, bulk, cylinder, or sphere. Thermoset 4 raw, component (a):

The thermosetting component (a) is a patent application No. 60/347195 in our generally issued application filed on January 8, 2002, No. 60/384303 filed on May 30, 2002, and January 2003 It is disclosed in the 3-day application No. IM06878 that the entire text of the case is incorporated herein by reference. First specific embodiment: In the first specific embodiment, the preferred thermosetting component (a) includes at least one adamantane monomer of formula VIIA, VIIB, VIIC or VIID, and at least one adamantane of formula VIII An oligomer or polymer, wherein at least one of h, i, and j is at least one. Preferably, the thermosetting component (a) includes the bisadamantane monomers of the above chemical formulas IXA, IXB, IXC and IXD and at least one bisadamantane oligomer or polymer of the chemical formula X, wherein at least h, i and j are at least One item is at least 1.

When h, i and j are all 0 in the above chemical formula IV, the adamantane dimer is as shown in the following chemical formula XIV

Where (^ and Gw are as previously defined. When w is 0 in Chemical Formula XIV, examples of adamantane dimers are shown in Table 2 below. -31-200424228 (25) Description of the invention continued page

-32- 200424228 (26) Description of the Invention Continued When w is preferably 1 in Chemical Formula XIV, examples of preferred dimers are shown in Table 3 below. table 3

^ Ri γ ^ γ γ γ-γ Ri 1 ^ γ r? Τ R1 Ri 4 i -ί * | 1 4 4y H. r 4 i Ri / iy fY γ—Η Η 4 ^ HH 4, Η Η HHHYH -33 -200424228 (27) Description of the invention continued when h is 1 and i and j are 0 in the above chemical formula IV.

Where 卩 and Gw are as previously defined. When w is preferably in the chemical formula XV, examples of preferred trimers are shown in Table 4 below. Table 4

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-40- 200424228 (34) I Description of Inventions Continued

The composition preferably includes at least one oligomer or polymer of Formula VI 'wherein Q, Gw, h, i, j and w are as previously defined. When h, i and j are all 0 in the above chemical formula VI, the bisdamantane dimer is as shown in the following chemical formula XVI

Q Q

Where ^ and Gw are as previously defined. The composition preferably includes at least one oligomer or polymer of formula VIII, wherein Ri, Y, h, i, j, and w are as previously defined. Ben-41-200424228 (35) Description of the invention The continuation composition preferably includes at least one bisadamantane oligomer or polymer of formula X, wherein R, Y, h, i, j and w are as previously defined The thermosetting component (a) preferably includes the adamantane monomer of the above chemical formula VIIA, VIIB, VIIC or VIID and the adamantane oligomer or polymer of the following chemical formula XVII, wherein Ri, Y and w are as previously defined And h is 0 or 1.

Preferably, the adamantane structure is as shown in the following chemical formula

The thermosetting component (a) preferably includes the bisadamantane monomer of the above chemical formula IXA, IXB, IXC or IXD and the bisadamantane oligomer or polymer of the following chemical formula XVIII, wherein Ri, Y and w are as previously defined Generally, and h is 0 or 1. -42- 200424228 Description of Invention Continued (36)

Preferably, the bisadamantane structure is as shown in the following chemical formula

The thermosetting component (a) preferably includes the adamantane monomer of the above chemical formula VIIA, VIIB, VIIC or VIID and the adamantane dimer of the following chemical formula XIX, wherein Ri, Y and w are as previously defined. -43- 200424228 (37) Description of the invention continued

The thermosetting component (a) preferably includes the bisadamantane monomer of the above chemical formula IXA, IXB, IXC or IXD and the bisadamantane dimer of the following chemical formula XX, wherein Ri, Y and w are as previously defined.

-44- 200424228 (38) Description of the Invention Continued It is preferable that the bisdamantane dimer is as shown in the following chemical formula

I should understand that the substituents of the types listed in Tables 2, 3 and 4 above can also occur in tetramers and higher oligomers. The thermosetting component (a) preferably includes the adamantane monomer of the above chemical formula VIIA, VIIB, VIIC or VIID and the adamantane trimer of the following chemical formula XXI, wherein Ri, Y and w are as previously defined.

Preferably, the adamantane trimer is as shown in the following chemical formula -45- 200424228 Description of the invention continued (39)

The bisadamantane monomer and the bisadamantane trimer of the following chemical formula XXII, wherein Ri, Y and w are as previously defined.

-46- 200424228 (40) Description of the invention Continuation sheet Thermosetting component (a) preferably includes the adamantane monomer of the above chemical formula VIIA, VIIB, VIIC or VIID, the adamantane dimer of the above chemical formula XIX and at least one chemical formula The adamantane oligomer or polymer of VIII, wherein at least one of h, 1 and j is at least 1. The thermosetting component (a) preferably includes the bisdamantane monomer of the above chemical formula IXA, IXB, IXC or IXD, the bisdamantane dimer of the above chemical formula XX, and at least one bisdamantane oligomer of the chemical formula X or A polymer in which at least one of h, i, and j is at least one. The thermosetting component (a) preferably includes the adamantane monomer of the above chemical formula VIIA, VIIB, VIIC or VIID, the adamantane dimer of the above chemical formula XIX, the adamantane trimer of the above chemical formula XXI, and at least one of the above chemical formula VIII Adamantane oligomer or polymer, wherein at least one of h, i and j is at least a thermosetting component (a) preferably includes a bisadamantane monomer of the above chemical formula IXA, IXB, IXC or IXD, the above chemical formula Bis-adamantane dimer of XX, bis-adamantane trimer of the above chemical formula XXII and at least one bis-adamantane oligomer or polymer of the formula X, wherein at least one of h, i and j is at least 1 . Thermosetting component (a) includes an adamantane monomer of the formula VIIA, VIIB, VIIC or VIID (which is a tetra-substituted adamantane) or a bisadamantane monomer of the formula IXA, IXB, IXC or IHD (which is a tetra-substituted Bis-adamantane). The preferred monomer is the adamantane monomer of formula VIIA. The adamantane network carries a substituted aryl group at positions 1, 3, 5 and 7 each. A compound of formula VIII is an oligomer or polymer which is linked via unsubstituted and / or substituted aryl units and is an adamantane monomer of formula VIIA, VIIB, VIIC or VIID. The compound of formula X is an oligomerization of a bisadamantane monomer of formula IXA, IXB, IXC or IXD via unsubstituted and / or substituted aryl-47- 200424228 (41) Substance or polymer. Usually h, i and j are integers 0 to 10 (preferably 0 to 5, more preferably 0 to 2). Therefore, the simplest adamantane oligomer is the dimer shown in the above chemical formula XIX (in chemical formula VIII, h is 0, i is 0, and j is 0), in which two diamond networks are Substituted or substituted aryl units are linked. Therefore, the simplest bisdamantane oligomer is the dimer shown in the above chemical formula XX (in chemical formula X, h is 0, i is 0, and j is 0), in which two bisadamantane networks pass through a Unsubstituted or substituted aryl units are linked. Second Specific Embodiment ... In the second specific embodiment described above, it is preferable that the thermosetting component (a) includes at least one adamantane oligomer or polymer of formula VIII, where h is 0 to 10 and i is 0. To 10, j is 0 to 10 and w is 0 or 1. Preferably the present thermosetting component (a) comprises at least one bisadamantane oligomer or polymer of formula X, where h is 0 to 10, i is 0 to 10, j is 0 to 10 and w is 0 or 1 . Preferably, the thermosetting component (a) includes at least one bis-adamantine oligomer or polymer of formula VIII, wherein h is 0 or 1, i is 0, j is 0, and w is 0 or 1. This adamantane structure is as shown in the above Chemical Formula XVII. Preferably, the thermosetting component (a) includes at least one bis-adamantine oligomer or polymer of formula X, wherein h is 0 or 1, i is 0, j is 0, and w is 0 or 1. This adamantane structure is as shown in the above Chemical Formula XVIII. Preferably, the thermosetting component (a) includes at least one diamond oligomer or polymer of formula VIII, wherein h is 0, i is 0, j is 0, and w is 0 or 1. This adamantane dimer is as shown in the above Chemical Formula XIX. -48- 200424228 (42) Description of the invention Continuation page It is preferred that the thermosetting component (a) includes at least one bisdamantene oligomer or polymer of formula X, where h is 0, i is 0, j is 0 and w is 0 or 1. This bisdamantane structure is as shown in the above Chemical Formula XX. Preferably, the thermosetting component (a) includes at least one of the adamantane oligomer or polymer of formula VIII, wherein h is 1, i is 0, j is 0, and w is 0 or 1. This adamantane trimer is as shown in the above Chemical Formula XXI. / Preferably, the thermosetting component (a) includes at least one bis-adamantine oligomer or polymer of formula X, where h is 1, i is 0, j is 0, and w is 0 or 1 0. This adamantane structure is as shown in the above chemical formula XXII. Preferably the thermosetting component (a) comprises a mixture of at least one adamantane oligomer or polymer of formula VIII, where h is 2, i is 0 and j is 0 (linear oligomer or polymer) and h is 0, i is 1 and j is 0 (branched oligomer or polymer). Therefore, the composition includes a mixture of Jingang-Jane linear tetramers as shown in the following chemical formula XXIII, wherein I, Y and W are as defined above.

And preferably linear adamantane tetramers of the following chemical formula -49- 200424228 (43) Description of the invention continued page

And the amantadine branched tetramer shown by the following chemical formula χχιν

And preferably branched Vajra tetramers

-50- 200424228 Description of Invention Continued (44)

-51-200424228 (45) Description of the invention continued

2

Bisdamantane branched tetramer as shown in the following chemical formula XXVI

R R R

And preferably a branched bisdamantane tetramer represented by the following chemical formula -52- 200424228 (46) Description of the invention continued page

The preferred thermosetting component (a) comprises the adamantane dimer of the above chemical formula XIX and the adamantane trimer of the above chemical formula XXI. The preferred thermosetting component (a) includes the bisdamantane dimer of the above chemical formula XX and the bisadamantane trimer of the above chemical formula XXII.

The preferred thermosetting component (a) includes the adamantane dimer of the above formula XIX and at least one adamantane oligomer or polymer of the formula VIII, wherein h is 0, i is at least 1, and j is 0. The preferred thermosetting component (a) includes the bisadamantane dimer of the above chemical formula XX and at least one bisadamantane oligomer or polymer of the chemical formula X, wherein h is 0, i is at least 1, and j is 0. . In these two specific embodiments, for the above chemical formulae I and II, the preferred Q group includes an aryl group and an aryl group substituted with an alkenyl group and an alkynyl group, and a more preferred Q group includes a (decylethyl) fluorenyl group , Xylyl (phenylethlyl) phenyl, and (phenyl-53-200424228 (47) Description of the invention continued on ethynyl) phenylphenyl moiety. Preferred aryl groups for G include phenyl, biphenyl, and triphenyl. A more preferred G group is phenyl. Individual reactive groups Ri substituted with acetylene on the benzene ring attached to the R! Tri-C-adamantane or bis-adamantane ring are in the above chemical formula VIIA, VIIB, VIIC, VIID, VIII, IXA, IXB, IXC, IXD , X, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, and XXVI and the following XXVII and XXVIII are the same or different in each case. Ri is selected from hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, fluorenyl, alkynyl, alkoxy, light alkyl, light aryl, vial, via Choice of alkynyl, mesityl, or benzyl. Each Ri may be unbranched or branched and unsubstituted or substituted, and the substituent may be unbranched or branched. Preferably the alkyl, fluorenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyalkenyl and hydroxyalkynyl groups contain from about 2 to about 10 carbon atoms, and the aryl, aryl ether and hydroxyaryl groups contain About 6 to about 18 carbon atoms. If 1 represents aryl, I is preferably phenyl. Preferably, at least two of the R / C groups on the phenyl group are two different isomers. Examples of at least two different isomers include meta-, para- and ortho- isomers. Preferably, the at least two different isomers are meta- and para-isomers. In this preferred monomer 1,3,5,7-tetra [374 '-(phenylethynyl) phenyl] adamantane (represented in Figure 1D), five isomers are formed: (1) the -, Right-, right-, right-; (2) right-, right-, right-, time_; (3) right-, right-, time-, time · (4) right-time, time-, Between-, between- and (5) between-, between-, between-, between-. In the above formulas VIIA, VIIB, VIIC, VIID, VIII, IXA, IXB, IXC, IHD, X, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV and XXVI and the following XXVII and XXVIII examples Each benzene ring-54- 200424228 (48) I Description of the invention continued γ is the same or different 'and is selected from hydrogen, alkyl, aryl, substituted aryl or halogen. When fluorene is aryl, examples of aryl include phenyl or biphenyl. Rhenium is preferably selected from hydrogen, phenyl and biphenyl, and hydrogen is more preferred. At least one of the phenyl groups in the two bridged carbons of the adamantane or bisadamantane is present in at least two different isomer states. Examples of at least two different isomers include meta-para and ortho- isomers. Preferably, the at least two isomers are meta- and para-isomers. In the best dimer L3 / 4-bis {1,, 3,, 5, -reference [3 ”/ 4”-(phenylethynyl) phenyl] adamantane-7, -yl} benzene (in In the table in Figure 1F), 14 isomers are formed as follows. Preferably, the phenyl group located between the two bridgehead carbons of the adamantane is present in the meta- and para-isomer form. For each of the two aforementioned isomers, seven isomers of RlCsC on seven phenyl groups are formed as follows: (1) para_, para-, para-, para-, para_, para_; 2) Right _, right _ right _, right _, right-, time (3) right ·, right _, right ·, right ..., time between ·; (4) right ·, right _, right-, time- (5) right-, right-, right-, right-, right-, right-, right-, right-, right-, right-, right-, (-) 7) Room ·, Room_, Room_, Room ·, Room-, Room-. In addition to the branched adamantane structure of the above chemical formula 乂 along 乂, we should understand that when h is 0, i is 0, j is 1, and ~ is 0 or 1, the above chemical formula νΙπ represents as shown in the following chemical formula XXVII. Further branching. I should understand that because further branching of the hanging adamantane unit in chemical formula XXVII can also occur, the branching can go beyond the structure of chemical formula XXVII. -55- 200424228 (49) Description of the invention continued

R

-56- 200424228 (50) Description of the invention continued The branched adamantane is preferably represented by the following chemical formula.

In addition to the branched bisdamantane structure of the above chemical formula XXVI, we should understand that when h is 0, i is 0, j is 1, and W is 0 or 1, the above chemical formula X represents a step further as shown in the following chemical formula XXVIII Branches. I should understand that because further branching of the hanging bisdamantane unit in chemical formula XXVIII can also occur, the branching can go beyond the structure of chemical formula XXVIII. -57- 200424228 (51) Description of the invention continued

R

-58- 200424228 (52) Description of the invention continuation sheet Preferably, the branched adamantane is represented by the following chemical formula.

The content of the monomer (a) and the oligomer or polymer (b) in the thermosetting component (a) is determined by the gel chromatography technique described in the analytical test method section below. The composition includes an amount of about 80 to about 70 area percent of adamantane or bisadamantan monomer (a) (more preferably about 40 to about 60 area percent, even more preferably about 45 to about 55 area percent) and an amount of about 70. Oligomer or polymer (b) to about 30 area percent (more preferably about 60 to about 40 area percent, even more preferably about 55 to about 45 area percent). The composition preferably includes an amount of about 50 area percent -59- 200424228 (53) invention description page ratio monomer (1) and an amount of about 50 area percent of oligomer or polymer (2). The Analytical Test Methods section lists two gel chromatography methods. Both provide similar results. A skilled artist can choose to use the second method, which produces more detail in dimers and trimers. In general, the proportion of the adamantane or bisadamantane monomer (1) to oligomer or polymer (2) can be set in a desired manner, for example, by changing the starting group during the preparation of the composition according to the invention Molar ratio, by adjusting the reaction conditions and by changing the ratio of non-solvent to solvent during the precipitation / isolation step. A preferred method for preparing the thermosetting component (a) includes the following steps. In step (A), reacting adamantane or bisadamantane with a halobenzene compound of formula XXIX,

(Where Y is selected from hydrogen, alkyl, aryl, substituted aryl, or halogen, and Yi is halogen) to form a mixture, and if adamantane is used, the mixture includes at least one monomer of formula III

And at least one oligomer or polymer of formula IV (where h is 0 to 10, 1 is 0 to 10, j is 0 to 10, and w is 0 or 1), -60- 200424228 Summary Sheet (54)

Preferably, the oligomer or polymer is of the formula XXX -61-200424228 (55) Description of the invention continued page

-62- 200424228 (56) Description of the invention continued or, if bisadamantane is used, the mixture includes at least one monomer of formula V

Q

And at least one oligomer or polymer of formula VI (where h is 0 to 10, i is 0 to 10, j is 0 to 10 and w is 0 or 1),

Preferably the at least one oligomer or polymer is of formula XXXI -63- 200424228 (57) Description of the invention continued on

-64- 200424228 (58) Description of the Invention Continued The reader should understand that reactions can occur on bisdamantane on bridgehead carbons other than those mentioned in Chemical Formulas V and VI above. In step (B), the mixture produced from step (A) is reacted with a terminal alkyne of the formula R1C = CH. Preferably, this method forms a combination of the above formulae VnA, VIIB, VIIC, VIID and VIII or IXA, IXB, IXC, IHD and X. In step (A), adamantane or bisadamantane is reacted with a halobenzene compound of the formula χχχχ. In addition to the halogen group Yi and the previously mentioned reactive group γ, the 12-phenylbenzene compound can also contain more substituents. The phenylbenzene compound is preferably selected from bromobenzene, dibromobenzene, and iodobenzene. Bromobenzene and / or dibromobenzene are preferred, and bromobenzene is even more preferred. Donkey Kong: The reaction of diamanta and halogenated benzene compounds (step (A)) is preferably carried out via a Friedel-Craft reaction in the presence of a Lewis acid catalyst. Although all conventional Lewis acid catalysts can be used, it is preferred that the Lewis acid catalyst contains at least one element selected from the group consisting of aluminum (III) vaporized (A1C13), aluminum bromide (IIl) (AlBr3), and aluminum iodide ( ιπ) (Α1Ι3) selected compounds. Chlorinated (III) (AICI3) is best. Although the aluminum acidity of desertified aluminum (Η) has a higher acidity, but its use is generally poor, because its low sublimation point is only 90%, so it is far more difficult on an industrial scale than aluminumized aluminum (ΙΠ) (for example). operating. In a more preferred embodiment, the Fred-Kleite reaction is performed in the presence of a second catalyst component. The second catalyst component preferably contains at least one secondary halogenated burner having 4 to 20 carbon atoms, a tertiary burner having 4 to 20 carbon atoms, and a secondary alcohol having 4 to 20 carbon atoms. Choice of higher olefins and tertiary halogenated aromatic compounds. Specifically, the second catalyst component contains at least one from 2-A-2-methylpropane (tertiary butyl bromide), 2-chloro-2-methylpropane (tertiary butyl chloride -65- 200424228).

Description of the Invention Continued, 2-methyl-2-propanol (tertiary butanol), isobutylamidine, 2-bromopropane and tertiary butyl bromobenzene selected compounds, with 2-bromomethylpropane (tertiary Butyl Mo) is the best. On the whole, compounds in which the alkyl group includes 5 or more carbon atoms are less suitable because the solid component is precipitated from the reaction solution at the termination of the reaction. Most preferably, the Lewis acid catalyst is aluminum vaporized and the second catalyst component is 2-bromo-2-methylpropane (tertiary butyl bromide) or tertiary butyl bromobenzene. The preferred step for carrying out the Friedel-Crete reaction is to mix adamantane or bisadamantane, a halobenzene compound (such as bromobenzene), and a Lewis acid catalyst (such as chlorin) at a temperature of 50 C (preferably 35 ° C to 45 ° F, especially 40t) is heated. At temperatures below 30 ° C, the reaction is not complete, i.e., a higher proportion of trisubstituted diamonds is formed. In principle, it is desirable to use temperatures even higher than those described above (e.g. 60 ° C), but this in an undesired manner results in a higher proportion of non-halogenated aromatic substances (e.g. benzene ). Thereafter, the second component of the catalyst system (ie, secondary butyl bromide) is usually added to the above reaction solution within a period of 5 to 10 hours (preferably 6 to 7 hours). A conventional temperature range is mixed into the reaction mixture for another 5 to 10 hours, preferably 7 hours. Surprisingly, in addition to monomeric tetraphenylated compounds, for example, 1,3,5,7-tetra (3, / 4, -bromophenyl) adamantine 'is also present in the mixture obtained after step (A). Found its oligomer or polymer. I totally did not expect the proportion of the adamantane monomer of chemical formula III to the oligomeric oligomer or polymer of chemical formula 1V This is controlled by the amount of ramadan or bis-ramadan, ylbenzene compounds (such as bromobenzene) and second catalyst components (such as tertiary butyl bromide) -66-200424228 (60) Continued description of the invention. In the reaction mixture of step (A), the molar ratio of the adamantane or bisadamantyl p-phenylbenzene compound to the second catalyst component is preferably 1: (5-15): (2-10), or even more Good 1: (8-12): (4-8). In the compounds of the formulae XXX and XXXI, the position of the halogen substituent Yi is not defined. Preferably, the mixture includes meta- and para-isomers, unlike all para-isomers, which advantageously results in improved solubility and good film properties. In the reaction mixture of step (A), in addition to the monomers and oligomers or polymers, starting components and by-products (such as incompletely phenylated adamantane) can also occur. The mixture produced from step (A) is optionally prepared by a method known to those skilled in the art. For example, it may be necessary to remove unreacted halogen phenyl compounds (ie, bromobenzene) from the mixture in order to obtain a highly proportioned chemical formula VIIA, VIIB, VIIC or VIID and VIII or IXA, IXB, IXC or IXD for further reactions. And X products. Any solvent or solvent mix that is miscible with halobenzene compounds (ie bromobenzene) and suitable for precipitating compounds of formula VIIA, VIIB, VIIC or VIID and VIII or IXA, IXB, IXC or IHD and X ~ This product was isolated. The mixture produced in step (A) is preferably incorporated into a non-polar solvent or a solvent mixture (e.g. by dropwise incorporation), preferably an aliphatic hydrocarbon having 7 to 20 carbon atoms or a mixture thereof, especially at least One from the heptane fraction (boiling point 93-99 ° C), the octane fraction (boiling point 98-110 ° C), and the spezial Benzin 80-110 ° C (boiling point 80-110 ° C) by Honeywell International Inc. Petroleum ether) is a mixture of alkane sold under the trademark. Spezial Benzin 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 -67- (61) (61) 200424228) Description of the Invention Continued about 1:13, or even better John 1: 7 to John 1:11). Alternatively, a polar solvent or a solvent mixture (such as methanol or ethanol) can be used to finish the mixture obtained in step (A), but it is less preferable because the product mixture precipitates out like a rubber composition. We have found that if the mixture of step (A) is precipitated in some solvents, the peak ratio of the monomers from step (A) to its dimers and trimers and S? Longs in the reaction mixture shifts dramatically. . This finding advantageously enables those skilled in the art to adjust the process conditions to achieve the target ratio of monomer to dimer and trimer and oligomer. In order to reduce this ratio, it is preferable to use a solvent in which monomers and compounds or polymers have different solubility. The preferred solvents to achieve this monomer-to-dimer and trimer ratio shift include Spezial Benzin 80-11 (rc (Hysteresis 8 (Ml (rc petroleum ether), Ligroine) (boiling point 90-1 UTC) And heptane (lag point 98 艽 " a better solvent is

SpezialBenzin. More specifically, in order to achieve a shift from about 3: 1 monomer dimer + trimer + oligomer to about 1: bu, the step (A) mixture is precipitated in

In Spezial Benzin, or in order to achieve a shift from about 3: 1 monomer: dimer + trimer + oligomer to about mOiO, the mixture of step (A) is precipitated in lignine and heptane . We know that the substantial change in the peak distribution during precipitation is explained by the loss of monomer in the precipitation filtrate: 2/3 is lost to Spezial Benzin and u / 3 is lost to petroleum ether and heptane. Volume loss of 50 and 25-33%. In order to keep the ratio of monomer: dimer + trimer + oligomer at 3: 1 constant, the reaction mixture of step (A) was precipitated in A_ which was observed without yield loss t. This was confirmed by the loss of yield and GPC analysis of the filtrate. -68- (62) (62) 200424228 Description of the invention The continuation page is as described by Ortiz ★ ° Creation method, according to a better version of step (A) of this method. The Laite reaction is directly from the diamond burning button that is coupled with a # -based benzene compound. Compared with, for example, the previous one by Reichert et al. 1,3,5,7-tetra (3 '/ 4, non-standard, eight The method of synthesizing i-adamantane, this method is particularly advantageous, because the I4 tetra > odorized diamond is no longer needed, which saves one reaction step. At the same time, less undesired benzene is formed. Those skilled in the art are known , Especially in the compounds of the above formulas III, IV, V and VI, the _ prime I Yi, p is the direct reaction of phenyl compounds with diamond, sintering and hydrazine (for example, with the help of Fred-Kleite reaction) In addition, it can be introduced by multi-stage synthesis, such as by adamantane and phenyl compounds (that is, halogen-free

Yi) coupling 'is followed by the introduction of the reaction group Υ1' by an addition reaction with w (Yi) 2 (e.g., Γ2), although this is less favorable. In step (B) of the preferred method, the mixture obtained after step (A) (sorted as necessary) is reacted with the terminal alkyne of the formula Rlc <: (wherein, as previously defined). In the chemical formula R ^ CbCH, Ri is the same as the reactive group Ri of the adamantane product of the chemical formula VIIA, VIIB, VIIC, or VIID and mn and the bis-r adamantane product of the chemical formulas IXA, IXB, IXC, or ID and X. Therefore, ethylidenebenzene (phenylacetylene) is preferably used as the terminal alkyne for the reaction in step (B). In order to couple the terminal alkyne to the halobenzene reactive group in the adamantane system in step (B), all conventional coupling methods suitable for this purpose can be used, such as in Diederich, F., and Stang, P. J. · (Eds.) &Quot; Metal-Catalyzed Cross-Coupling Reactions "'Wiley-VCH 1998 and March, J.," Advanced Organic Chemistry' 4th Edition, John Wiley & Sons 1992, Nos. 717/718 -69 -200424228 (63) Description of the invention as described on the following pages. When γ on phenyl is attached to two cage-like bridge carbons in the above chemical formula Vin or the above chemical formula χ, γ can be produced by reaction with phenylacetylene Terminal ethynyl. In a preferred version of the method according to the invention, the reaction between the mixture obtained after step (A) (finished as necessary) and terminal alkyne is in the so-called

Sonogashira coupling (compare T〇hda; fjagihara; Trtrahedron

Lett. 1975 ’p. 4467) was performed in the presence of a catalyst system. Using a palladium-triarylphosphine complex containing in each case at least one formula [Ar3p] 2pdX2 (where Ar = square and X == fluorene), a copper halide (such as Cul), a test (such as Trialkylamine), a triarylphosphine, and a co-cement catalyst system are even better. According to the present invention, the preferred catalyst system is similarly composed of the indicated components. The co-solvent preferably contains at least one selected from toluene, xylene, chlorobenzene, N, N-dimethylformaldehyde, and 1-methyl-2-pyrrolidone (N-methylpyrrolidone (NMP)). Selected components. Contains bis (triphenylscale) palladium (III) dichloride (i.e. [Ph3P] 2PdCl2), triphenylphosphine (i.e. [Ph3P]), copper (I) iodide, zhiethylamine and co-solvent The toluene catalyst system is the best. The best step for reacting the mixture obtained from step (A) (finished as necessary) with terminal alkynes is to first mix the mixture with a base (such as triethylamine) and a co-solvent (such as toluene), and leave the mixture at room temperature Stir for a few minutes. Thereafter, a free-triphenylphosphine complex (such as Pd [PPh3] 2Cl2), triphenylphosphine (PPh3), and a copper halide (such as copper (1) iodide) are added, and the mixture is heated at 50 to 90 °: temperature range (better 8 (rc to 85 ° heating). Then add terminal alkyne within 1 to 20 hours (more preferably 3 hours) within the indicated temperature range. End of addition -70- 200424228 (64) Description of the invention After the continuation of the page, 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). Thereafter, a solvent is added to the reaction solution and the Evaporate under reduced pressure. It is best to cool the reaction solution to a temperature of 20 ° C to 30 ° C (more preferably 25 ° C) after filtration. Finally, arrange step (B) by a conventional method known to those skilled in the art. The reaction mixture, especially the removal of trace metals (such as Pd). If the mixture of step (B) precipitates in some solvents, the monomers produced from step (B) above will react with its dimers and trimers in the reaction mixture. The peak ratios of the oligomers and oligomers are shifted. Surprisingly, the reaction sequence starting directly from adamantane results in oligomers in the reaction product of step (A). The polymer or polymer content can be controlled through the use ratio of adamantane, halogenated benzene compound and second catalyst component (ie, tertiary butyl bromide). In a corresponding manner, due to the toxicity of benzene in industrial scale synthesis, Therefore, it is very important that the benzene content in the reaction mixture of step (A) is also successfully adjusted through this use ratio. The oligomer or polymer content allows the same second chemistry as the monomer (for example, 1, 3, 5, 7 · Tetrakis (374, -bromophenyl) adamantine, that is, the oligomer or polymer is just as easily obtained as the monomer that reacts with the terminal alkyne in step (B)). In another specific embodiment, The present invention provides a mixture of at least two different isomers of formula XXXII

Q

Q

And (b) a viscosity promoter as described above. e is a cage-like as defined above-71-200424228 (65) Description of the invention Continuation sheet, and Q is the same or different and is selected from hydrogen, aryl, branched aryl and substituted aryl ( Wherein the substituent includes hydrogen, i-prime, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, fluorenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl , Hydroxyalkynyl, hydroxy, or carboxyl). Examples of at least different isomers include meta-, para- and ortho-isomers. Preferably the at least two different isomers are the meta- and para-isomers. Preferably the mixture includes at least two different isomers of formula XXXIII. Table Η where Q is as previously defined. Preferably the mixture includes at least two different isomers of the chemical formula XXXIV

Different isomers of chemical formula XXXV

-72- 200424228 (66) Description of Invention Continued or Different Isomers of Chemical Formula XXXVI

Η where Υ is the same or different and is selected from hydrogen, alkyl, aryl, substituted aryl or halogen, and each Ri is the same or different, and is selected from hydrogen, halogen, alkyl, aryl, substituted aryl , Heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, via alkyl, aryl, via alkenyl, via block, via or tether. Preferably, the mixture includes at least two different isomers of formula XXXVII.

α where each Q is as previously defined. Preferably the mixture includes at least two different isomers of formula XXXVIII

Η -73-200424228 (67) Description of the invention continuation page Different isomers of chemical formula XXXIX

Where ya and Ri are as previously defined. Viscosity Accelerator (b4: Viscosity Accelerator (b) is disclosed in the pending patent application PCT / US01 / 50182, which I applied for and was jointly assigned on December 31, 2001, which is hereby incorporated by reference in its entirety. In the adhesion promoter (b), it is preferable that at least one of the first functionality and the second functionality is selected from the group consisting of Si group, N group, C-0 group, hydroxyl group and Selection containing C = C group. The Si-containing group is preferably selected from Si-H, Si-O and Si-N; containing 1 ^ group-74- 200424228 (68) Description of the invention The continuation page is for example C-NH2 or Selection of other secondary and tertiary amines, imines, amidines and amidines, containing C-0 groups from = co, carbonyls (such as ketones and aldehydes), esters, -COOH, with 1 to 5 carbon atoms The alkoxy group, glycidyl ether and epoxy group are selected; the hydroxyl group is a phenol; and the C = C group is selected from allyl and acetamyl groups. For semiconductor applications, better functional groups include those containing Base, containing C-0 base, Suiri base and ethynyl. An example of a preferred adhesion promoter with a Si base is the silicon slope of the chemical formula χι: (R2) k (R3) lSi (R4) m (R5 ) n (where R2, R3, 仏, and Chi 5 each independently represent hydrogen Sense group, unsaturated or saturated alkyl group, substituted or unsubstituted alkyl group, wherein the substituent is an amine group or an epoxy group, a saturated or unsaturated alkyl group, an unsaturated or saturated carboxylic acid group or an aryl group; At least two of R2, r3, R4, and Rs represent hydrogen, hydroxyl, saturated or unsaturated alkoxy, unsaturated alkyl, or unsaturated carboxylic acid group; and k + l + m + nM). Examples include ethylene Silanes (such as H2C = CHSi (CH3) 2H and H2C = CHSi (R18) 3, where r18 is CH30, C2H50, AcO, H2C = CH or H2C = C (CH3) 0- or vinylphenylmethylsilane)) ; The chemical formulas H2C = CHCH2-Si (OC2H5) 3 and H2C = CHCH2-Si (H) (OCH3) 2 are propyl silanes glycidyl propoxy ^ silanes (such as (3-glycidyl propoxy) groups) Methyl " monoacetic acid crushing and (3-glycidylpropoxy) trimethoxy sec :): end); methacryl group of chemical formula H2C = (CH3) COO (CH2) 3-Si (OR19) 3 Propoxysilanes (where R19 is alkyl, preferably methyl or ethyl); aminopropylsilane derivatives (including H2N (CH2) 3Si (OCH2CH3) 3, H2N (CH2) 3Si (OH) 3 or H2N (CH2) 3OC (CH3) 2CH = CHSi (OCH3) 3). These silanes are commercially available from Geiest. An example of a preferred adhesion promoter with a C-0 group is glycidyl ether, 200424228 (69) Description of the invention The continuation sheet includes (but is not limited to) 1,1,1-tris (hydroxyphenyl) ethane trishrink Glyceryl ether, which is commercially available from TriQuest. An example of a preferred adhesion promoter having a C-0 group is an ester of an unsaturated carboxylic acid having at least one carboxylic acid group. Examples include trifunctional fluorenyl acrylate, trifunctional propionate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and glycidyl fluorenyl propionate. All of the foregoing are commercially available from Sartomer. An example of a preferred adhesion promoter having a vinyl group is a vinyl cyclic pyridine oligomer or polymer, wherein the cyclic group is pyridine, aromatic or heteroaromatic. Useful examples include (but are not limited to) 2-vinylpyridine and 4-vinylpyridine, available from Reilly; vinyl aromatic compounds; and heteroaromatics, including (but not limited to) acetamidine? Kui Lin, Yi Jun Ye Jun, Yi Jun Mi Jun and Yi Jiu Jun. An example of a preferred adhesion promoter having a Si group is the polycarbosilane disclosed in U.S. Patent Application Serial No. 09/471299, which was filed on December 23, 1999 and is pending co-pending. The entire contents of which are incorporated herein by reference. The poly ^ carbon silane belongs to the chemical formula XII: Η I -Si — R? -Si- R9 Alkylene, cycloalkylene, ethylene, propyl, or arylene; r7, r8, r9 -76- 200424228 (70) Description of the Invention Continued pages, Rio, Ri3, and Ri4 each independently represent hydrogen Atomic or organic groups, including alkynyl, alkynyl, ethenyl'cycloalkyl, propyl or aryl, and may be green or branched; R1 1 represents organosilicon, silanyl, silicon Oxygen or organic group: and p, q, r, and s satisfy the condition of [4Sp + q + r + s < 100,000], and q and coffee can be collectively or independently zero. The organic group may contain up to 18 carbon atoms, but typically contains about 1 to about 10 carbon atoms. Useful alkyl groups include _CH2_ and-(CH2) u-, where U > 1. The preferred polycarbosilanes of the present invention include dihydropolycarbosilanes, where R6 is a substituted or unsubstituted alkylene or phenyl group, r7 is a hydrogen atom and there is no dangling in the polycarbosilane chain Radicals; that is, q, r, and S are all 0. Another preferred group of polycarbons is that in the formula viii, r7, r8, r9, R10, K3, and Ri4 are substituted or unsubstituted alkenyl groups having 2 to 10 carbon atoms. The alkenyl group may be vinyl, propionyl, allyl, butylfluorenyl or any other unsubstituted organic backbone group having up to 10 carbon atoms. The olefin may be essentially a dienyl group, including an unsaturated alkenyl group that is reduced or substituted on the main chain of other alkyl or unsaturated organic polymers. Examples of these preferred polycarbosilanes include polyhydric or dihydro- or polyalkyl-substituted polycarbohydrates (such as polydihydrocarbon silanes and -polyallylhydrocarbyl silanes) and polydihydrocarbons. Fired and polyallyl hydrogenated carbon random copolymers. In the more polycarbosilane, the R7 group of the formula] 1] [is a hydrogen atom and is a methylene group, and the pendant groups q, r, and S are 0. Other preferred polycarbosilane compounds of the present invention are polycarbohydrates of chemical formula XII, where 1 and Ru are hydrogen, R6 and R15 are methylene, and R14 is feminine, and pendant groups q and r are zero. The polycarbosilanes are preferably derived from a well-known prior art method or provided by the manufacturer of the poly-carbosilane composition. In the most preferred polycarbosilane, the R7 group of Chemical Formula VIII is a hydrogen atom; trans 6 is _ch2-; q, r, and s are 0 and P is 5 to 25. These best polycarbosilanes are available from Starfire systems, Inc. Examples of these optimal polycarbosilanes are as follows: polycarbosilane weight average molecular weight polydispersity wave molecular weight (Mw) (Md) 1 400-1,400 2-2.5 330-500 2 330 1.14 320 3 (with 10% propyl propyl ) 10,000-14,000 10.4-16 1160 4 (with 75% propyl propyl) 2,400 3.7 410 It can be observed from Chemical Formula XII that when r> 0, the polycarbosilane used in the present invention may include oxidation in the form of siloxy base. Therefore, when r> 0, 'R π represents an organic fragment, a fragmentary group, a second oxygen group, or an organic group. I have learned that the oxidized version of the depolymerized carbosilane (r > 0) operates very efficiently within the scope of the present invention. It is also obvious that r can be 0, irrespective of p, q, and s. The only condition is that the reactive groups p, q, r, and s of the chemical formula XΠ must satisfy [4 < p + q + r + s < 1.⑽, 〇〇〇] conditions, and q and r can be collectively or independently 0. Polycarbosilane can be produced from materials currently purchased from many manufacturers and by conventional polymerization methods. As an example of synthesizing polycarbosilane, this raw material can be produced from a common organosilane compound, or from a raw material polysilane, and can be produced by heating a blend of polysilane and polyborosiloxane in an inert atmosphere. ; Polymer, or by heating a blend of polysilane and low molecular weight carbon sintered in an inert atmosphere to produce the corresponding polymer, or by the catalyst (such as & side = stupid siloxane) In the presence of an inert atmosphere, a polysilane is heated with a low-78 · 200424228 (72) I. Description of the invention Continuing the blend of molecular weight carbosilane to produce the corresponding polymer. Polycarbosilanes can also be synthesized by the Grignard Reaction proposed in U.S. Patent No. 5,153,295, which is incorporated herein by reference. An example of a preferred viscosity promoter with a hydroxyl group is a phenolic resin or an oligomer of formula XIII:-[R16C6H2 (OH) (Ri7)] t-, where Ri6 is a substituted or unsubstituted alkylene, cyclic Alkenyl, vinyl, propyl or aryl; Rn is alkyl, alkylene, vinylidene, cycloalkylene, alkenyl or aryl; and t = 3-100. Examples of useful alkyl groups include _Ch2- and _ (CH2) v-, where v > 1. A particularly useful phenolic resin oligomer has a molecular weight of 1500 ' and is commercially available from Sehenectady International Inc. The viscosity promoter is preferably added in a small and effective amount of about 0.5% to about 20% by weight of the thermosetting composition (a), and up to about 500% by weight of the composition. Usually better. In order to ensure the affinity for the contact surface of any coating, a composition produced by combining a viscosity promoter and a thermosetting component (a) and subjecting the composition to a heat source or high energy source has excellent viscosity throughout the polymer feature. This adhesion promotion / multi-layering also improves grain control, adhesion and film uniformity. Visual inspection confirmed the existence of improved grain control. The composition may also include additional components such as additional tackifiers, defoamers, cleaners, flame retarders, pigments, plasticizers, stabilizers, and surfactants. Uses: The composition of the thermosetting component (a) and the viscosity promoter (b) can be combined with other specific additives to obtain specific results. Representative of this kind of additives -79- 200424228 (73) Description of the invention: Continuation sheet 疋 Metal compounds, such as magnetic particles (such as barium ferrite, iron oxide, used in magnetic media, optical media or other green recording media, as required) Can be a mixture with words, or other metal-containing particles); or conductive particles (such as metal or carbon) for conductive sealing; conductive adhesives; conductive materials; electromagnetic interference (EMI) / Radio frequency interference (RFI) shielding coatings; static dispersion 'and electrical contact points. When these additives are used, the composition can be used as a spotting agent. The composition can also be used as protection against manufacturing, storage or use (such as coatings), so that metals, semiconductors, capacitors, inductors, solar cells, glass and glass fibers, and quartz and quartz fibers are pure Sex. -The composition of the thermosetting component ⑷ and the adhesion promoter ⑻ is also used in the whole film, preferably as a sealing layer or a gasket layer, for example, around the cotton and linen fabric, and can also be used alone. In addition, the composition has antifouling coatings used on, for example, ship zero power switch housings, bathtubs, and showerhead coatings; anti-smear, anti-fouling coatings; or flame retardation, weathering, or moisture resistance of objects . In the temperature range of the composition, the composition can be coated on low-temperature containers ",, presses, and furnaces: and heat exchangers, and other heating or cooling surfaces, and objects exposed to microwave radiation The composition of the thermosetting component ⑷ and the viscosity promoter ⑻ is useful as a packaging material. The dielectric constant k of the far-dielectric material is preferably lower than or equal to about 30. Jiatian ΛΛ 疋, ', 2, 3 To 3.0. The glass transition temperature of the dielectric material is preferably at least 3500c. The layer of the composition of the thermosetting component (a) and the adhesion promoter (b) can be formed by a technique such as spraying, Roll, dip, spin-coat, flow-coat or scale. 'Spin-coating is best for microelectronics. It is best to dissolve this composition in a solvent Suitable solvents for use in the solution of the composition include any suitable organic, organometallic, or inorganic molecular pure state or mixture that evaporates at the desired temperature. Suitable solvents include aprotic solvents such as cycloketones (cyclopentanone, Cyclohexanone, cycloheptanone, and cyclooctanone), cyclamidine (Such as N-alkylpyrrolidone, where the alkyl group has about 1 to 4 carbon atoms), N-cyclohexylpyrrolidone, and mixtures thereof. Various other organic solvents can be used here as long as they can help Dissolve the viscosity promoter and effectively control the viscosity of the resulting solution as a coating solution. Other suitable solvents include methyl ethyl ketone, methyl isobutyl ketone, dibutyl ether, cyclic dimethyl polysiloxane, butyl Lactones, γ-butyranate, 2-heptanone, ethyl 3-ethoxypropionate, polyethylene glycol (di) methyl ether, propylene glycol methyl ether acetate (PGEMEA), anisole and hydrocarbons Solvents (such as vegetables, xylene, benzene, and toluene). The preferred solvent is cyclohexanone. Typically, the layer thickness is between 0.1 and about 15 microns. As the dielectric inner layer of microelectronics, the layer thickness is usually low. 2 micron. It is best to treat the composition of the thermosetting component (a), the viscosity promoter (b) and the solvent at a temperature of about 30 ° C to about 350 ° C for about 0.5 to about 60 hours. For example, by GPC As it turns out, · road treatment usually forms an oligomeric compound of thermosetting component (a) and viscosity promoter (b). This combination Power means may be used, more specifically, in the combination of a single wafer interconnect integrated circuit ( "ICn) as an inner layer dielectric. An integrated circuit wafer typically has many layers of the composition and multiple metal conductors on the surface. It may also include areas of the composition between discrete metal conductors, or conductive areas within the same layer or level of the integrated circuit. When this polymer is applied to 1C, the conventional wet coating method (such as

-81-(75) (75) 200424228 Description of the Invention (continued on spin coating) Applying a solution of this composition to a semiconductor wafer ^ Other well-known coating techniques such as spray coating can be used under conditions 4 Dynamic coating, or dip coating body. By way of illustration, a framed hexanone solution of this composition is spin-coated on a base in which a dielectric conductive component is assembled, and then, the coated substrate is heat-treated. An example formulation of this composition is prepared by dissolving the composition of the present invention in cyclohexanone under normal temperature conditions, strictly following clean handling to avoid trace metal contamination in any conventional device with a non-metallic lining . The resulting solution includes 1% by weight, preferably 1% by weight of the total solution, τ, a force of 1 to about 50% by weight, a thermosetting component ⑷ and a viscosity promoter ⑽ ′, and about 50 to about 99% by weight of a solvent, More preferably, about 30 weight percent is more than the thermosetting component VII and the viscosity promoter (b), and about 80 to about 97 weight percent of the solvent. The following is a description of one use of the present invention. Applying the composition on a flat or uneven surface == to form a layer can be performed by using any conventional spin coating device, because the composition used here and the two techniques are suitable for the viscosity of this applicator . It can be simply air-dried during this period), by exposure to ambient temperature, or by a combination thereof. This is a solid component ⑷ and a viscosity promoter (b) The substrate included here may include any materials. The substrates that are particularly desirable to bear the solid complaints are metal or coated metal or composite materials. Glass, ceramics, plastics, gold materials include gadolinium or gallium ... tm In specific examples, the base compounds are pitted or Wafer surface, package surface (e.g. -82- (76) 200424228 Description of invention continued)

3 Used as a dielectric base material in circuit boards or printed wiring boards. The circuit board system made of a group of objects in this group is set up on various conductive circuits ~, clothing totems, and strength and excellent adhesiveness. Circuit boards can include a variety of different reinforcing materials, such as woven non-conductive fibers or fiberglass cloth. Such boards may be single-sided as well as double-sided. The layers made from the composition have low dielectric constant, high stability, and high mechanical properties because the adhesion promoter is dispersed in a molecular manner. Liner and cover capping layer or masking layer (such as SiO2 and SisN4 capping layer). The use of this layer precludes additional processing steps in the form of at least one primer layer application to reach the film on the substrate and / or cover the surface.

After the composition is applied to an electronic uneven substrate, the coated surface is subjected to a baking and aging heat treatment from a temperature of about 50 C to a temperature of about 450 C. The aging temperature is at least about 300 ° C 'because lower temperatures are not sufficient to complete the reaction here. Generally, the 'preferably ripening' is carried out at a temperature of about 375 ° C to about 425 ° C -83- 200424228 (77) Description of the invention continued on the following page. The ripening can be performed in a traditional ripening room, such as an electric furnace, a hot plate analog, and usually in an inert (non-oxidizing) atmosphere (under nitrogen) in the ripening room. In addition to the curing of a furnace or a heating plate, the composition can also be cured by exposure to ultraviolet radiation, microwave radiation, or electron beam radiation, such as patent publication PCT / US96 / 〇8678 and US Patent No. 6,042,994 '6,080,526; 6,177,143; and 6,235,353 ",%, the entirety of which is incorporated herein by reference. In the practice of the present invention, it is possible to use a gaseous or reducing atmosphere (such as argon, helium, hydrogen, and nitrogen to process holes &). If it is effective to mature the thermosetting component of the viscosity promotion adjustment, to achieve Here the low-k dielectric layer. Alas, without being limited by limitations, I speculate that the low dielectric constant composition " forms a cross-linking path between the thermosetting component (a) and the viscosity promoter (b). 1 Ben, and the heat treatment < heat treatment due to the better polycarbosilane adhesion promoter (b) of the silane part of Han Zhiba / is methylene silyl / silyl, which is followed by thermosetting, and injury Unsaturated structure of (a) ^. The substrate surface reacts with each other, so that the host tears, and () is a chemical bond bonding interface, which is used throughout the composition. It can be used as a source of attachment to bind and fix Λ @ ^. 化学 any contact interface by chemical bonding. This reaction can also be found before or after the preparation or processing period. As indicated by the first cut, free radicals are scattered throughout the surface of the composition. This layer adheres excellently to the underlying substrate, covering the surface structure for a long time, such as a sealing layer or a masking layer. The materials found here Polycarbonate 2: Yu: Now the better chemical formula 1 Poly ... Adhesion promoter in the special: Reactive hydrogen in the structure instead of silicon. The characteristics of this polycarboxane ensure that its plutonium is reactive with the thermosetting Λ island, and (2) produces a -84. (78) (78) 200424228 Description of the invention The continuation sheet has: a polycarpene with good viscosity properties Burning modified thermosetting component ⑷. As mentioned before, the viscosity promoter of the thermosetting component coating can be used as an inner layer and covered by other coatings, such as other dielectric coatings, 2) coatings, Si0 2 modified ceramic materials, and Coatings, cut carbon coatings, stone-containing nitrogen coatings, silicon-nitrogen-carbon coatings, diamond-like carbon coatings, titanium nitride coatings, tantalum nitride coatings, crane nitride coatings, Ming coatings Coatings, steel coatings, tantalum coatings: silicone coatings, silicone glass coatings and fluorinated silicon glass coatings. Such multilayer coatings are taught in U.S. Patent No. 4,973,526, which is incorporated herein by reference, and, as has been fully explained, the polycarbosilicate modified thermosetting components prepared in this method ⑷ It can be formed on the fly as an interlayer dielectric layer between adjacent conductor paths on an assembled electronic or semiconductor substrate. This film can be used for dual damascene (such as copper) processing of integrated circuit manufacturing and substrate metal (such as chain or inscription / town) processing. The composition can be used as an etching mask, a hard mask, an air bridge, or a passive coating to wrap a complete wafer. The composition can be used for all spin-coated stacked films, such as

As taught in Michael E. Thomas, MSpin-On Stacked Films for Low keff Dielectrics' Sa ^ d State Technology (2001 ^ July), it is incorporated herein by reference. This layer can be used in combination with other layers. This layer includes organosiloxanes (such as US Patent No. 6,143,855 and US Patent No. 10/078919 filed for joint assignment on February 19, 2002) Teaching-like); Honeywell International Inc / s' commercially available HOSP® products; Nanoporous silica (as taught by commonly assigned US Patent No. 6,372,666)

(As shown), NANOGLASS® E products sold by Honeywell International Inc.'s; silicone silsesquioxane (as commonly assigned to world patent No. 01/29052 -85- 200424228 (79) Description of the invention continued on page number General); and fluorosilsesquioxane (as taught by the commonly assigned World Patent No. 01/29141), the entirety of which is incorporated herein by reference. Embodiment Analytical method of probing test 1-Proton NMR '. 2-5 mg of a sample of the material to be analyzed is placed in an NMR test tube. Add about 0 · 7 Aisheng to gas imitation. The mixture was shaken by hand to dissolve the material. It was then analyzed using Varian 400 MHz NMR. Peptide layer folding method (GPC): Waters 2690 separation mold with Water 996 diode array and water 410 differential refractometer detector was used for separation. Separation was performed on two: PLgel 3m Mixed-E 300x7.5mm column with chloroform flowing at 1ml / min. The 25 liter solution was performed twice at a concentration of about 1 mg / ml. Good reproducibility was observed. The column was scaled to a relative monodisperse polystyrene standard with a molecular weight between 20,000 and 500. Nine different components with lower molecular weight standards are capable of dissolving ', which is equivalent to 9 styrene in the butyl monomer in the oligomer. The logarithm of the peak molecular weight of the standard fits the cubic polynomial of the elution time. The ratio of the full width from half to the maximum value to the average dissolution time of toluene is < i The absorbance of the following formulations 1 and 2 is maximum at about 284 nm. Chromatograms have similar shapes at absorbances at wavelengths below about 300 nm. The results present here are equivalent to 254 nm absorbance. The peaks are identified by the molecular weight of the polystyrene that is simultaneously analyzed. These values should not be considered as a measure of the molecular weight of Preparations 1 and 2 oligomers. Higher oligomers, trimers, dimers, oligomers, and incomplete -86-(80) (80) 200424228 invention descriptions that can be successively separated over gradually increasing time can be quantified. Each component is wider than that observed for monodisperse species. Analyze this width from the full width in minutes at half the crest maximum. In order to broaden the calculation of the instrument, we calculated that the width is corrected = [width observation 2-width instrument 2] 1/2 where the width meter g is the observation width of toluene, and the toluene < ratio is corrected by the peak dissolution time. The peak width is converted to the molecular weight width via this scale curve and compared with the Bossin molecular weight width. Because the molecular weight of the acetofluorene oligomer is proportional to the square of its size, the relative molecular weight width can be converted into the relative oligo-oligomer size by dividing by two. This step explains the differences in the molecular configuration of the two. — [: The initial measurement of T 丨 shows the maximum value of 4 s, so the cycle time thus represents the quantitative result. All samples were dissolved in CDCh and 4000 scans were collected. DEPT designates c, CH, and CH # CH3. DEPT clearly recognizes that CH2 is located at 41 ppm, and assigns it to the three non-cantilevered neighbors on the adamantane, and CH is located at 30 ρρη in the unsubstituted position. Adjacent cantilevered leftover CH2 appeared at 46-48 ppm. Similarly, quaternary carbon at 35 ppm and CH at 31.5 ppm; can be regulated to tertiary butyl. In the aromatic region, peak groups between 120 and 123.5 are clearly non-protonated aromatic compounds. Based on chemical shifts, we attribute these to bromoaromatic carbons. We expect that the aromatic ring carbon atom 'quaternary aromatic compound attached to an aliphatic group (in this case, adamantane) is in the range of 45 to 55 ppm. There are more Bossins in some spectra at about 14, 23, 29, and 31.5 ppm. These can be attributed to the amount of heptane I used to clean the sample. The relative amount of heptane burned generally varies from -87 to 200424228 (81). We did not quantify heptane because it is not important for final performance. NMR conditions: • High resolution 13C NMR spectra were obtained on Varian Unity Inova 400. • 13C frequency: 100.572 MHz. • Use WALTZ adjustment to depolarize the gate 1Η. • Spectral width: 25 kHz. • π / 2 pulse at 13C-13ps. • Cycle time: 20 seconds. • #Data points: 1_00032, 2 second acquisition time. • 0 is filled at 131072 points of FT. • 1 Hz exponential flattening. Liquid chromatography-mass spectrometry (LC-MS) · This analysis was performed using the Atmospheric Pressure Ionization (API) interface unit, using a Hewlett-Packard 1050 series HPLC system as the chromatographic entrance, at Finnigan / MAT TSQ7000 three-stage quadrupole On a mass spectrometer system. Obtain mass spectrum ion current and variable single-wave g-long ultraviolet data for time-intensity chromatogram. Chromatography was performed on a Phenomenex Luna 5 micron phenyl-hexyl column (250 x 4.6 mm). Samples are automatically injected between 5 and 20 microliters of concentrated condensate in tetrahydrofuran and without tetrahydrofuran. The preferred formulation of the concentrated sample concentrate for analysis was dissolved in tetrahydrooctane at about 5 mg of solid product per milliliter for 10 microliters of injection. The mobile phase flow through the column was 1.0 ml / min acetonitrile / water, the first 1 minute was 70/30, after which the gradient was arranged to 100% acetonitrile at 10 minutes and held for 40 minutes. -88- 200424228 (82) Description of the Invention Continued In separate experiments, both positive ionization and negative ionization recorded Atmospheric Pressure Chemical Ionization (APCI) mass spectra. Positive APCI is more informative about the molecular structure of these final products. It provides protonated pseudomolecular ions, including additions to the acetonitrile matrix. APCI corona discharge is 5 microamperes, positive ionization is about 5 kV, and negative ionization is about 4 kV. Maintain the heated capillary wire at 200 ° C and the evaporator battery at 400 ° C. The ion detection system after quadrupole mass analysis was set to a voltage of 15 kV conversion double doubling electrode and 1500 V electronic amplifier. Mass spectra for negative ionization are typically recorded from about m / z 50 to 2000 a.m.u. at 1.0 sec / scan, and for positive ionization start at about m / z 150_a.m.u. In individual positive ion experiments, both scan up to 2000 a.m.u. in the low key / scale mode and up to 4000a.m.u in the high key / scale mode. Differential Scanning Calorimetry (DSC): DSC measurements are performed using a TA Instruments 2920 Differential Scanning Calorimeter with a controller and related software. The analysis was performed using a standard DSC battery (inert atmosphere: 50 mL / min nitrogen) over a temperature range of 250 ° C to 725 ° C. Liquid nitrogen is used as a source of cooling gas. Using a Mettler Toledo analytical balance with an accuracy of ± 0.00 gram, a small sample (10-12 mg) was weighed into an automatic DSC aluminum sample pan (part # 990999-901). The tray was covered with a lid previously punched in the center to allow gas to flow out to encapsulate the sample. The sample was heated under nitrogen at a rate of 100 ° C / min from 0 ° C to 450 ° C (cycle 1), and then cooled at a rate of 100 ° C minutes. Immediately operate the second cycle (repeat cycle 1) at a rate of 100 ° C / min from 0 ° C to 450 ° C. The crosslinking temperature was measured from the first cycle. FTIR analysis: Using Nicolet Magna 550 FTIR spectrometer in transmission mode -89- (83) (83) 200424228 Description of the Invention Continued FTIR spectra were obtained. The substrate background spectrum was obtained on an uncoated substrate. The position and intensity of the wave in the spectrum of the thin film were then analyzed. The dielectric constant is obtained by coating an aluminum thin film on the curing layer, and then performing a constant volume-voltage measurement at 1 MHz and calculating the k value based on the layer thickness. Rose-ϋ-transition temperature (T & 1: The glass transition temperature of a film is measured by measuring the film stress as a function of temperature. The film stress measurement is performed on the KLA 3220 Flexus. The uncoated wafer is annealed at 500 C for 60 minutes to avoid any errors due to stress relaxation of the wafer itself. Thereafter, the wafer is deposited with the material to be tested and processed through the necessary method steps. Then the crystal The circle is placed in a stress gauge, which measures the wafer as a function of temperature. The instrument calculates a graph of stress versus temperature with the limitation that the wafer thickness and film thickness are known. The results are shown graphically. To determine Tg Value, draw a horizontal tangent line (the slope value is 0 on the stress versus temperature graph). The Tg value is where the graph crosses the horizontal tangent line. If Tg is measured after the first temperature cycle using the maximum temperature, then It should be mentioned because the measurement method itself can affect Tg.

Isothermal Gravimeter Analysis (ITGA) Weight Loss Center: Total Weight Loss is in TA

Instmment 2950 thermogravimetric analyzer (TGA), and performed with TA Instruments thermal analysis controller and related software. A Platinumel Π thermocouple and a standard furnace with a temperature of 25 ° C to 1000 ° C were used and heated at a rate of 0.TC to 100t / min. A small sample (7 to 12 mg) was weighed on a TGA balance (resolution: 0.1 grams; accuracy: to ± 0.1%) and heated on a platinum pan. The sample was heated at -90- 200424228 (84) Invention Description Continued at a scrubbing rate of 100 ml / min under nitrogen (60 ml / min to the furnace and 40 ml / min to the balance). The sample was equilibrated under nitrogen at 20 ° C for 20 minutes, and then the temperature was increased to 200 ° C at a rate of 10 ° C / minute and held at 200 ° C for 10 minutes. Thereafter, the temperature was rapidly increased to 425 ° C at 10 ° C / minute and maintained at 425 ° C for 4 hours. Calculate weight loss over 4 hours at 425 ° C. Shrinkage: Film shrinkage is measured by the film thickness before and after the measurement method. Shrinkage is expressed as a percentage of the original film thickness. If the film thickness is reduced, the shrinkage is positive. The true thickness measurement was optically performed using a J. A. Woollam M-88 spectrophotometer. The Cauchy model is used to calculate the optimal fit of Psi and Delta (Details on Ellipsometry can be found in, for example, 1999 by H.G. Thompkins and William A. McGahan, John Wiley and Sons, Inc., "Spectroscopic Ellipsometry and Reflectometry" Found). Refractive index _ · Refractive index measurement is performed together with JA Woollam M-88 spectrophotometer and thickness measurement. Cauchy model is used to calculate the best combination of Psi and Delta. Unless otherwise specified, the refractive index is at 633 Proposed at the nanometer (details on EllLp ^ ometry can be found, for example, in 1999 by HG · Thompkins and ^ William A. McGahan, John Wiley and Sons, Inc., "Spectroscopic Ellipsometry and Reflectometry"). Modulus and hardness i Modulus and hardness are measured using instrument identification tests. Measurements were performed using MTS Nanoindenter XP (MTS Systems Corp., Oak Ridge, TN). Specifically, the continuous rigidity measurement method makes it possible to measure the modulus and hardness more accurately and continuously than to measure the discontinuity value from an unloaded curve. The system is calculated using a nominal modulus of 72 ± 3.5 Gpa 200424228 (85) Continued description Condensed second stone. The modulus of the fused silica is obtained by averaging from 500 to 1,000 nanometers of discrimination depth. For films, the modulus and hardness values are obtained from the minimum values of the modulus versus elongation curve, typically between 5 and 15% of the thickness. ¥ K test and tape test are performed according to the guidelines of ASTM D3359-95. A grating is transcribed into a dielectric layer according to the following. The tape test is performed across the grating markings in the following way: (1) Place a piece of tape (preferably Scotch brand # 3m600-l / 2xl296) on the current layer and squeeze down to make good contact ; And (2) the tape is then quickly removed and averaged at an angle of 180 ° relative to the surface of the layer. If the layer remains on the wafer intact on the wafer, the sample is deemed to pass, or if some or all of the film is pulled up with the tape, it fails. Pin pull-up --- test _... Attach an epoxy-coated pin to the surface of a wafer containing the layer of the present invention. A ceramic backing plate is applied on the back of the wafer to avoid substrate bending and inappropriate stress concentration at the edges of the pins. Thereafter, the test pin is pulled up in a direction perpendicular to the wafer by a test device using standard pull-up procedure steps. Thereafter, the stress was applied at the failure point and the interface position. Exhaust. Solvent. The compatibility between the main phase and the solvent is determined by measuring the film thickness, refractive index, FTIR spectrum and dielectric constant before and after solvent treatment. For a compatible solvent, no significant changes should be observed. Formulation: 1 Preparation 1-Preparation of thermosetting ingredient (a) (herein, ρι ") Step b): Preparation of 1,3,5,7-tetrakis (3 '/ 4'-bromophenyl) adamantane ( (Shown in Figure 1)), 1,3 / 'bis [1,3,, 5'_tris (3 ,, / 4 ,,-bromophenyl) adamantane_7, _yl] benzene 92-200424228 invention description page (86) 1C) and at least double {3, / 4,-[Γ, 3 ", 5 ,,-tris (3 ,,, / 4 ,,,-bromophenyl) Adamantane-7 ′, yl] phenylb 5,7-bis (3 ,,,, / 4 ,,,,-bromophenyl) Adamantane (represented in Figure 1C) mixture Step ⑷ product π). A first reaction vessel was charged with adamantane (200 g), bromobenzene (1550 ml) and aluminum trichloride (50 g). The reaction mixture was heated to 40 ° C with a thermostatic water bath. Tertiary butyl bromide (1206 g) was slowly added to the reaction mixture over 4-6 hours. The reaction mixture was stirred at 40 ° C overnight. Load a second reaction vessel with 1000 ml of aqueous hydrogen chloride (5% w / w) ° Gradually unload the contents of the first reaction vessel into the second reaction vessel 'while maintaining the anti-mixture at 25-35 ° with an external ice bath C. The organic phase (dark brown phase) was separated and washed with water (1000 ml). An organic phase of about 1700 ml was maintained. A third reaction vessel was charged with 20.4 liters of petroleum ether (mainly isooctane with a boiling range of 80 ° C to 110 ° C). The contents of the second reaction vessel were slowly 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 washed twice with 300 ml of the petroleum ether described above each time. The ¥ washed filter cake was dried at 45 ° C and 40 mbar overnight. The yield in step (a) of product P1 was 407 g dry weight. This reaction is shown in the following schemes 1A to 1C. Figure 1A shows the monomers produced. Figure 1B shows the general dimers and higher products produced, while Figure 1C shows the specific dimers and trimers produced by covering the structure of Figure 1B. The products were identified using analytical techniques including LC-MS, NMR 13C, and GPC. LC-MS showed that the product was a complex of a single monobloc and an oligomeric star. The following table shows the identified structure (Ad == King Kong fire; Ph = C6H6; Βι * = Bromo; t-Bu = -C (CH3) 3): -93- 200424228 (87) Description of the invention continued on 1E1 step 骡 ( a) HPLC-MS analysis of product HPLC retention time M + wave ♦ Proposed 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 16.P3 AdPh4Br6 16.5 908 AdPh4Br6 17.1 808 AdPh4Br4 (t-Bu) 17.3 886 AdPh4Br5 (t-Bu) 18.4 864 AdPh4Br4 1 (Ad-Ph4Br6 1114 Ad2Ph7Br4 1116 Ad2Ph6Br6P5 11 Ad2Ph4Br5 1118 Ad2P hyB Γ7 1426 Ad2Ph7Br8 wide ~ 21 + 1 1096 Ad2Ph5Br5 (t-Bu) 1172 Ad2Ph6Br5 (t-Bu) 1174 Ad2Ph5Br6 (t-Bu) 1250 Ad2Ph6Br6 (t-Bu) 1326 Ad2Ph7Br6 (t-Bu) 1328 Ad2Ph7Br6 (t-Bu) 1328 Bu) 1404 Ad2Ph7Br7 (t-Bu) 1482 Ad2Ph7Br8 (t-Bu) -94- 200424228 (88) Description of the invention Continued NMR 13C analysis results in the following peak assignment

13C NMR peak position, ppm structures 153.6, 151.8, 151 ″, 148.3, 147.6 bonded to the quaternary aromatic carbons 136.0, 134.5, 134.2, 133 ″, 131.6 aromatic CH, 131.1, 130.2, 130.0, 129.6, 129.3, 128.5, 126.9, 123.8 123.1, 123.0, 122.9, 122.6, 121.4 Aromatic C-Br, 121.1, 120.3 47.7 Three c-h2 4δ of trisubstituted adamantane c-h2 41.0 c-h2 of the adamantane adjacent to the unsubstituted adamantane 39.3, 39.0, 38.9, 38.4, 38.1 quaternary (aliphatic) carbon of adamantane 35.2 quaternary (aliphatic) tertiary butyl CH GPC analysis result of c-h3 30 tri-substituted adamantane with 31.4 carbons. 1 -1,3,5,7-tetra (f / W-bromophenyl) adamantane (represented in FIG. 3A) The peak molecular weight is about 360; -1,3 / 4-bis [1,3,, 5'-tris (3 '' / 4 ',-bromophenyl) adamantane-7, -yl] benzene (in Figure 30 The molecular weight of the peak is about 620; -1,3-bis {374,-[1 ”, 3 '', 5” -tris (3 '" / 4 | " -bromophenyl) adamantane-7, , Yl] phenyl} -5,7-bis (3 " '' / 4 '"' _ Phenyl) adamantane (represented in FIG. 3C) has a peak molecular weight of about 900 (shoulder) -95- 200424228 (89) Description of the invention Continuation step ⑻: Preparation 丨, 3,5,7 · Tetra [3V4,-( Bromophenyl) phenyl] adamantane (represented in FIG. 1D), 1,3 / 4-bis {1,3,, 5, _tri [3 ”/ 4 " _ (phenylethynyl) phenyl] Adamantine-7-yl} table (indicated in FIG. 1F) and at least 13-bis (^ ,, ^ ,,, ^,-tris [3/4 (phenylethynyl) phenyl] adamantane_7 " ] Phenylbenzene 5,7_bis [3/4 (phenylethynyl) phenyl] adamantane (represented in Figure 1F) (collectively, the product of step P1 ,,) The first reactor was charged with toluene (1500 ml), triethylamine (4000 ¾ liters), and the product of the above-prepared step ⑷ (1000 g dry). The mixture was heated to 80. (: and bis (triphenyl) was added Phosphine) palladium dichloride (π) (ie [Ph3P] 2PdCl2) (7i5 g) and triphenylphosphine (ie [Ph2P]) (15 g). After ten minutes, copper (I) iodide was added ( 7.5 g). A solution of phenylacetylene (750 g) was added to the first reactor over a period of three hours.The reaction mixture was at 80. (: Stir for 12 hours to confirm that the reaction is complete. Toluene (4750 ml) was added. After that, the solvent was distilled off under reduced pressure and the maximum reactor temperature and the reaction mixture was cooled to about 50. The tribromide was filtered off Ethyl ammonium (approximately 1600 ml). The filter block was washed with toluene (500 ml each time). The organic phase was 1750 milli # HC1 (10 w / w%), followed by water (2000 ml) Wash. Add water (1000 ml), ethylenediaminetetraacetic acid (EDTA) (100 g) and dimethylethylene dioxane (20 g) to the washed fragrance machine phase. Add about 50 ml of NH4OH (25w) / w%) to reach pH 9. The reaction was mixed and stirred for 1 hour. The organic phase was separated and washed with water (1000 ml). An azeotrope was passed through a Dean-Stark trap Dry until the water stops flowing. Add filter dolomite (100 g) (trademark Tonsil). Heat the mixture to 100 ° C for 30 minutes. Filter the dolomite through a pore filter cloth and remove the residue with toluene ( 200 ml) 200424228 (90) Description of the invention Continued cleaning. Add silica (100 g). Stir the reaction mixture for 30 minutes. A filter cloth with fine pores was used to remove the silica and the residue was washed with toluene (200 ml). 2,500 liters of aqueous NH3 (20 w / w%) and 125 g of N • acetamidinecysteine were added. The phases were separated. The organic phase was washed with 1000 liters of HC1 (10% w / w), followed by washing twice with water (1000 ml each time). The toluene was distilled off under reduced pressure of about 120 mbar. Pot The temperature does not exceed about 70.0. A dark brown viscous oil (1500-1700 ¾ liters) is left. Add isobutyl acetate (2500 ml) to the hot mass in the pot and form a dark brown solution ( 4250 ml). Load a second reaction vessel with 17,000 ml of petroleum ether (mainly isooctane with a boiling range of 80 C -110 C). Slowly add the contents of the first reaction vessel to the 'second reaction vessel and Stir off overnight. Filter the precipitate and wash the filter cake with 500 ml of petroleum ether as described above. The cleaned filter cake is dried at 45 C and 80 C for 5 hours. The yield of pi step (b) is 85- 900 g. The reaction is shown in the following schemes 1D to 1F. Fig. 1D shows the monomers produced. Fig. 1E shows the general dimers produced and comparisons. High product, while Figure 1F shows the specific dimers and trimers produced by covering the structure of Figure IF. The products were identified using analytical techniques including LC-MS, NMR 4, NMR 13C, GPC, and FTIR. LC-MS It shows that the compound is a complex of monomer and oligomeric star compound and adamantane core. The following table shows the identified structure (Ad = adamantidine-like; T is diphenylethynyl-PhC = CC ^ H4 -; t.Bu = -C (CH3) 3): # M + wave structure proposed by 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 AdT6 (C6H4) 200424228 (91) Description of the invention continued on a. These general structures are observed with MW ± 100a.u. (plus or minus PhC = C-based). NMR of phenylethynyl cantilever (-176a.u.) recognizes aromatic protons (6.9-8 ppm, 2.8 ± 0 · 2Η) and adamantane cage protons (1.7-2.7 ppm, 1 ± 0 · 2Η). 13C NMR analysis results in the following peak assignments:

13C NMR peak position, ppm structure 151.3, 151, 150, 149.9, 149.8 Bonded to quaternary aromatic carbon of adamantane, 149.3- '149 · 2 132-131, 128 · 5, 125 · 3, 125 · 2 CH Aromatic carbons 129.6- 129.1 Aromatic ring carbons 123.7-122.9, 121.8, 121 ″, 120.9 Four-stage aromatic carbons attached to acetylene 93.6 Four-stage acetylene carbons (on disubstituted rings) 90.7, 90 · 3, 90.1 89.7, 89.5 quaternary acetylene carbon, 89.4, 89.1, 88.8, 88.7 47.5 $ 46.7 c-h2 of tetra-substituted adamantane 47.1 c-h3 of tetra-substituted adamantane c-h2 of tri-substituted adamantane 39.6 of tri-substituted adamantane c-h3 39.5, 39.2-39.0, 38.6, 38.2, quaternary carbons of tetra-substituted adamantine 35 32 tertiary butyl on aromatic ring c-h3 30 tri-substituted adamantan CH -98- 200424228 ㈣ I Description of the Invention Continued " PC QPC Analysis Results · "7 Tetrakis [3 74 _ (phenylethynyl) phenyl] adamantane (represented in Figure 3D) has a peak molecular weight of about 744;-1, 3/4 -BisM, v — '′ -phenylethylblock) phenyl] adamantine · 7, _yl] benzene (represented in FIG. 3F) has a Boxin molecular weight of about 13,000; 1′3bis {3 / 4-[1,3 ', 5 "· tri [3 ,,, / 4", _ (phenylethynyl) phenyl] adamantane] phenyl} 5,7-bis [3 "" / 4 " "-( phenyl Ethynyl) phenyl] adamantane (represented in FIG. 3F) has a peak molecular weight of about 1680 (shoulder). It is known from GPC that the ratio of monomer molecules and small molecules to oligomeric compounds is 50 ± 5%. 0 FTIR Shows the following: ----_____ The peak in cm · 1 (turbid peak strong read structure 3050 (weak) __aromatic CH _ 2930 (weak) aliphatic CH 2200 on adamantane (very weak, --- L_ Acetylene 1600 (very strong) Aromatic C = C 15, 0 (strong) 145 (F (medium) 1350 (medium) Preparation 2-Preparation of JL .. Solid. Properties of faH are cited here as " P2 ,,, Step (A): Preparation of 1,3,5,7 · tetra (3, / 4, -bromophenyl) adamantane (represented in FIG. 1A), 1,3 / 4-bis [1 ', 3 *, 5 '_Tris (3 "/ 4 ,,-bromophenyl) adamantane-7, -yl] benzene (represented in Figure 1C) and at least 1,3-bis {3, / 4'-[1 ,,, 3 ,,, 5 ”-tris (3 ,,, / 4, " -bromophenyl) adamantane-7 · 'yl] phenyl} -5,7-bis (3' " '/ 4” π -Bromophenyl) adamantane ( Shown) of the mixture (93) Continued invention is described on page table -99-200424228 FIG 1C (collectively ,, P2 is step (a) product "). A first reaction vessel was charged with 1,4-dibromobenzene (587.4 g) and aluminum trioxide (27.7 g). The reaction mixture was heated to 90 ° C with a constant temperature water bath without stirring. The temperature was maintained at this temperature for 1 hour, and the mixture was stirred for 1 hour. The reaction was cooled to 50 ° C. To the cooled reaction mixture was added adamantane (113.1 g). Tributyl bromide (796.3 g) was added to the reaction mixture over 4 hours. The reaction mixture was stirred for another 12 hours. A second reaction vessel was charged with HC1 (566 ml, 10% aqueous w / w). The contents of the first reaction container were gradually discharged into the second reaction container, 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 is a dark brown lower phase and is separated from the reaction mixture. The separated organic phase was washed with water (380 ml). After this washing, about 800 ml of the organic phase remained. A third reaction vessel was charged with heptane (5600 ml). The contents of the second reaction vessel were slowly added to the third reaction vessel over 1 hour. The suspension was stirred for at least 4 hours and the precipitate was filtered off. The filter block was washed twice with 300 ml of heptane each time. The yield of P2 step # ⑷ product was 526.9 g (wet) and 470.1 g (dry) dry. : Identify products using analytical techniques including LC-MS, NMR 13C, and GPC. LC-MS showed that the product was a complex of monomeric and oligomeric star compounds with an adamantane core. The following table shows the identified structures (Ad = adamantane; Ph = C6H5; Br = bromo; t-Bu = -C (CH3) 3): 200424228 (94) Description of the invention Continued HPLC- MS analysis HPLC retention time M + peak proposed structure 21.8 598 AdPh3Br3 14 674 AdPh4Br3 14 676 AdPh3Br4 15.3 752 AdPh4Br4 15.8 830 AdPh4Br5 16 830 AdPh4Br5 16 810 AdPh3Br4 41 6Br 616 908 AdPh5Br4 1808 -Bu) 17.3 886 AdPh4Br5 (t-Bu) 18.4 864 AdPh4Br4 (t-Bu) 2 wide ~ 19 + 1040 Ad2Ph5Br5 1114 Ad2P hyB Γ4 1116 Ad2Ph6Br5 1118 Ad2Ph5Br6 1192 Ad2P2P2P2Ph6Br2 〜2 1 +1 1096 Ad2Ph5Br5 (t-Bu) 1172 Ad2Ph6Br5 (t-Bu) 1174 Ad2Ph5Br6 (t-Bu) 1250 Ad2Ph6Br6 (t-Bu) 1326 Ad2Ph7Br6 (t-Bu) 1328 Ad2Ph6Br7 (t-Bu) 1404 Ad2Ph7 t-Bu) 1482 Ad2Ph7Br8 (t-Bu)

-101-200424228 (95) Description of the invention Continued NMR nC analysis results in the following peak assignments:

13C NMR peak position, ppm structure 153.6, 151.8, 151. 148.3, 147.6 bonded to the fourth-order aromatic carbon 136.0, 134.5, 134.2, 133.1, 131.6 aromatic CH, 131 ″, 130.2, 130 · 0, 129.6, 129.3, 128.5, 126.9, 123.8 123.1, 123.0, 122.9, 122.6, 121.4 Aromatic C-Br, 121.1, 120.3 47.7 Three c-h2 -46.S trisubstituted adamantane C-h2 41.0 c-h2 of the adamantane adjacent to the unsubstituted adamantane position 39.3, 39.0, 38.9, 38.4, 38.1 aquatane (aliphatic) carbon 35.2 amantane Grade (aliphatic) carbon 31.4 tert-butyl c-h3 30 tri-substituted adamantane CH GPC analysis results 3 -1,3,5,7-tetrakis (3〒 / 4 ^ bromophenyl) adamantane (in The peak molecular weight shown in Figure 3A) is about 360; -1,3 / 4-bis [1 ', 3', 5'_tris (3 '' / 4 ''-bromophenyl) adamantane-7,-group ] Benzene (represented in FIG. 3C) has a peak molecular weight of about 570; -1,3-bis {3 '/ 4 ·-[1Π, 3Π, 5Π-tris (3,, 74… -bromophenyl) adamantane- 7,, yl] phenyl} -5,7-bis (3 "'74" "_ bromophenyl) adamantine (Indicated in FIG. 3C) The peak molecular weight is about 860 (shoulder). 200424228 (96) Description of the invention Step (b): Preparation of 1,3,5,7-tetra [3V4,-(bromophenyl) Phenyl] adamantane (shown in Figure 1D), 1,3 / 4-bis [1,3,5, -tri [3 " / 4 ,,-(phenylethynyl) phenyl] adamantine- 71-yl] benzene (represented in FIG. 1F) and at least ι, 3-bis {3, / 4,-[1, ·, 3, ·, 5Π-tri [3 " 74m- (phenylethynyl) benzene Radical] adamantane-7 " yl] phenyl5,7-bis [3π74 " π- (phenylethynyl) benzyl] adamantane (represented in Fig. 1F)-a compound (collectively Π 2 step) (B) Product ") ·: A first reactor was charged with toluene (698 ml), triethylamine (1860 · ml) and the P2 step ⑷ product (465 g dried) prepared above under nitrogen. The mixture was heated at 80 ° C and a palladium-triphenylphosphine complex (ie, (Ph (PPh3) 2Cl2) K4.2 g) was added to the reaction mixture. After 10 minutes, J: -triphenylphosphine (ie, PPh3) (8.4 g) was added to the reaction mixture. After waiting another ten minutes, copper (1) 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 three hours. The reaction mixture was stirred at 80 ° C. for 12 hours to confirm that the reaction was complete. Toluene (2209 ml) was added to the reaction mixture, followed by evaporation under reduced pressure at the maximum reactor temperature. The reaction mixture was cooled to about 50 ° C and triethylammonium bromide was filtered off. The blocks were washed with toluene (250 ml each). The organic phase was washed with HC1 (10 w / w%) (500 ml) and water (500 ml). To the organic phase was added water (500 ml), EDTA (18.6 g) and dimethylethylene difluoride (3.7 g). Add about NH4OH (25w / w%) (about 93 ml) to maintain pH = 9. The reaction was mixed and stirred for 1 hour. Separate the organic phase from the insoluble material and the emulsion containing the palladium complex. The separated organic phase was washed with water (500 ml). Dry azeotropically with a Dean-Stark trap until the water stops flowing. Add filter dolomite (50 g) (trademark Tonsil). The mixture was heated to 100 ° C. for 30 minutes -103 · (97) 200424228 Description of the Invention Continued / ,, pores / contained dolomite and washed the residue with toluene (200 ml) / co-wash. Add silicon oxide (50 g). The reaction mixture was stirred for minutes. Filter out the silica with a filter cloth with "Tian Kong" and wash the residue with toluene (2⑼ml) ~ add water NH3 (20w / w%) (250ml) and N-acetamidine (12.5 grams). The phases are separated. The organic phase was washed with HC1 (10% w / w) (500 ml). The organic material was washed twice with water (500 ml each time). The toluene was distilled off under reduced pressure of about 120 mbar. The pot temperature does not exceed about 701. Dark brown viscous oil (about 500-700 ml) remained. Isobutyl acetate (1162¾ liters) was added to the hot mass in the pot and a dark brown solution (about 1780 ml) was formed. A second reaction pot was charged with heptane (7-20 ml). The content of the first reaction steel was slowly added to the second reaction pot over an hour. The suspension was stirred for at least 3 hours and the precipitate was filtered off. The filter block was washed four times with 250 ml of heptane each time. The product was dried at 80 ° C. under a reduced pressure of 40 mbar. The yield of the plutonium product in step P2 is 700 g wet or 419 g dry. The products were identified using analytical techniques including LC-MS, NMR 4, NMR 13C, GPC, and FTIR. LC-MS analysis # showed that the product was a mixture of monomers and oligomeric star compounds with a 3 complex of the diamond core. The following table shows the identified structures (Ad = adamantane cage; T is diphenylethynyl-PhCECC6H4-; t-Bu = -C (CH3) 3): # M + the structure proposed by the peak la 664 AdT3H 2a 840 AdT4 3a 1 720 Ad (H) T3 (t-Bu) 4a, b 896 AdT4 (t-Bu) 5a'b 1326 Ad2T6 6a, b 1402 AdT6 (C6H4) 200424228 (98) IInstruction sheet & these general structures Both analogs of MW ± 100a.u. (Addition and subtraction of PhC triC · group) were observed. These structures were observed by analogs without diphenylethynyl cantilever (-176a u.). 1H NMR identified aromatic protons (6.9-8 ppm, 2 · 8 ± 0 · 2Η) and adamantane cage protons (1.7-2.7 ppm, 1 ± 0Η 2Η). The 13cnmr sub-I peaks are assigned. · 13C NMR peak position, ppm structure 151.3, 151, 150, 149.9, 149.8, 149.3, 149.2 bonded to the fourth-order aromatic carbon of adamantane 132-131, 128 · ^, 125.3 , 125.2 CH aromatic carbon 129.6-129.1 aromatic ring carbon 123.7-122.9, 121.8, 121.1, 120.9 '-" a fourth-stage technique attached to acetylene μ 93.6 --- fourth-stage acetylene carbon Ban · 90 · 7, 90 · 3, 90.1, 89.7, 89.5, 89 · 4, 89.1, 88.8, 88.7 '--- Fourth-grade acetylene charcoal 47.5_, 46.7 Γ ~ ^^ Four substitutions Ττ 47.1-Γ of tetra-substituted adamantane ^ 41 --- r of tri-substituted adamantane ΐτ 39.6 -------------- r of tri-substituted adamantane ττ 39 · 5, 39.2- 39.0, 38 · 6, 38.2, 35 m_ 32 of the tetra-substituted adamantane * ---- Tertiary Ding on the aromatic ring; 30 Three-substituted adamantane. 〇ττ GPC analysis results: four [3 '/ 4 The peak molecular weight of '-(phenylethlyl) phenyl] Vajra tiger (Table-105-200424228 (99) I in the figure) is shown in the figure below. The peak molecular weight is about 763;' i, 3 / 4-bis [1 ,, 3,, 5'-tri [3, '/ 4 ,,-(phenylethynyl) benzene The peak molecular weight of the base] adamantane-7, -yl] benzene (represented in FIG. 3F) is about 1330; • bis {3, / 4,-[1,, 3 ”, 5, -tris [3 ,, '/ 4' ''-(phenylethynyl) phenyl] adamantine-7 ”yl] phenyl} _5,7_bis (phenylethynyl) phenyl] adamantane (shown in Figure 3F) The peak molecular weight is about 1520 (shoulder). It is known from GPC that the ratio of monomer molecules and small molecules to oligomer compounds is 50 to 5%. F TIR is not less than the following: peak breaking in cm · 1 (peak intensity ) Structure 3050 (weak) aromatic CH 2930 (weak) aliphatic CH 2200 on adamantane (very weak) acetylene 1600 (very strong) aromatic c = c 1500 (strong) 1450 (medium) 135 philosophy (medium) 3 Solvents for 1,3,5,7-tetra [3, / 4, · (phenylethynyl) phenyl] adamantane (represented in Figure 1D) for 1,3 / 4-bis [1,3 ,, 5, -tris [3 ”/ 4, di (phenylethynyl) phenyl] adamantine: ^-7-yl] benzene (represented in the figure if) and at least j, 3 • bis {3, / 4 , _ [1 ,,, 3 ,,, 5, di [3 / 4--(phenylethynyl) phenyl] adamantane-7,, yl] phenylbis [3 (phenylethyl block ) Phenyl] adamantane (represented in Figure 1F) -106- 200424228 (100) Description of the Invention Continued The 850¾ liter P1 step (a) product is divided into four equal parts, and in petroleum ether, petroleum ether (Ligroine), heptane and methanol. The parts were precipitated in 2520 ml of solvent 'vacuum filtration (Bllchner funnel with a diameter of 185 mm)' and washed twice with 150¾ liters of solvent on the filter, and then dried in a vacuum oven at about 20 ° C for 2 hours , Overnight at 40 ° C and at 70-80 ° C to a fixed weight. Precipitation in hydrocarbons results in very scattered light brown powder that does not require complex drying. Precipitation in methanol gave heavy brown solid particles (particle size about 1 mm), which formed coal when dried at 20 ° C. This product was further dried. The reaction was mixed for analysis by GPC during the reaction and before precipitation. All filtrates and final solids were analyzed by gpc. The results are shown in Table 5. In Table 5, ρρτ represents precipitation, and the monomer is 1,3,5,7 · tetra (3, / 4, -bromophenyl) adamantine (represented in FIG. 1A); the dimer is 1,3 / 4-bis [1 ', 3,, 5, -reference (3 ,, / 4 ,,-bromophenyl) adamantane-7, -yl] benzene (represented in FIG. 1C); and the trimer is丨, 3-bis {3V4,-[1 ”, 3”, 5 ”-tris (3,” / 4 ",-auphenyl) adamantane_7 ,, _ yl] phenylbu 5,5, bis ( 3 ', ·' / 4 · ...- bromophenyl) adamantane (represented in FIG. 1C). Table 5 Peak ^ ratio before PPT (monomer pair (dimer + trimer)) PPT solvent PPT Later Bossin ratio (monomer pair (dimer + trimer)) 75.0: 25.0 petroleum ether 52.5: 47.4 75.0: 25.0 petroleum ether (Ligroine) 64.0: 36.0 75.0: 25.0 heptane 66.2: 33.8 75.0: 25.0 methanol 75.0: 25.0 200424228 (101) Description of the Invention To extract these results, the peak ratio of monomer pair (dimer + trimer) in the reaction mixture is about 3: 1. Most of the products lost in the hydrocarbon filtrate (> 90%) are monomers. At the same time, the losses in the washing filtrate are negligible. No product was present in the methanol precipitation filtrate. After precipitation, the ratio of monomer to (dimer + trimer) was increased in the order of petroleum ether, petroleum ether, heptane, and methanol (1: 1 " > 3: 1), and Monomer loss in the filtrate was reduced (56 + 0%).劁 Breath 4-preparation of the pupa component '' Using Preparative Liquid Chromatography (PLC) to separate and prepare 1,3 / 4-bis {1,, 3,5, -see [3V4 ''- (Phenylethynyl) phenyl] adamantane-7, -yl} benzene (shown in Figure 1F). PLC is similar to the HPLC method described above, but uses larger columns to separate larger mixtures (from a few grams to hundreds of grams). The isolated 1,3 / 4-bis {1,, 3,, 5'-reference [3 " / 4 "-(phenylethynyl) phenyl] adamantane-7, -yl} is stupid (in Figure 1F (Indicated in Chinese) is dissolved in a solvent, spin-coated on a silicon wafer, then baked and cured into a thin film, and used in a microchip or multi-chip module. Preparation 5_Preparation of thermoset bonds (al using preparative liquid chromatography (PLC) separation and preparation of 1,3-bis {3, / 4 _ $ [1 ”, 3,, 5, || -reference [3 '' '/ 4' ''-(phenylacetylene Phenyl) phenyl] adamantine-7, '-yl] phenyl: Γ-5,7-bis [3 "" / 4 ,,,,-(phenylethynyl) phenyl] adamantane (in Figure 1F (Indicated in)). The separated 1,3-bis {3, / 4, _ [1 ,,, 3 ", 5" -reference [3 ,,, / 4 ,,,-(phenylethyl block) benzene Base] adamantine-7 ''-based] phenyl 5,7 · bis [3 ,,, // 4 ,,,,,-(phenylethyl block) phenyl] adamantane (shown in FIG. 1F) Dissolved in solvent, spin-coated on Japanese yen, then baked and cured into thin film, and used in microchip or multi-chip module. Greek thermosetting component (a) -108- (102) 200424228 Description of the invention Page

The following methods are used to prepare oligomeric monomers or bis-manganese monomers of chemical formulas IXA and IXD and bis-adamantane monomers of chemical formulas VI, X, XV !, xvm, XX, and XXII.组合。 The compound. As shown in Figure 2, bisdamantane was converted to the brominated bisdamantane product using bromine and a Lewis acid catalyst. The brominated bisadamantane product is then reacted with voltam in the presence of a Lewis acid catalyst to form bromophenylated bisadamantane. And then as

The catalyst system used in the Sonogashira coupling reaction reacts bromophenylated bisdamantane with a terminal alkyne. The products of each step are arranged as described in our pending patent application pCT / US01 / 22204, which was filed on October 21, 2001. _-. Preparation of thermosetting components: The oligomers of bisdamantane monomers of formula ^ and IXA, IXB, IXC ^ IXD and bisdamantene monomers of formula VI, χ, XVI, χνιπ, χχ and χχιΙ Or polymer. As shown in Figures 1 to 1F, bisdamantane is converted to a bisdamantane / styrenated composition using similar procedures as described in Preparations 1 and 2. In FIGS. 1A to 1C, in the presence of the 0 · 'Lewis acid catalyst as described in Preparation 1 and 2 and / or the second catalyst component as described in Preparation 2- ^ Substituted p-phenyl compounds for reaction. After finishing the reaction 孑 · mixture, a mixture of monomers, dimers, trimers and higher oligomers is obtained. In Figs. 1D to 1F, the bromophenylated bisdamantyl- ^ -membered compound is then reacted quickly with the terminal in the presence of a catalyst to produce the block-substituted bisdamantamine composition of the present invention. ijj method: Example 1 -109 · 200424228 (103) Description of the invention continued page About 180-210 grams of the thermosetting component ⑷ from Preparation 1 or 2 above was added to the flask and dissolved by shaking and flask. The viscosity promoter (b) used is polycarbosilane (CH2SiH2) q (where q is 20-30). The desired viscosity promoter (b) concentration was measured and added to the flask 'and the weight ratio was changed between 0.5 and 7%. The required amount of xylene was added to the flask. The temperature was set at 155 ° C. The reaction mixture was refluxed overnight for about 14-16 hours. The solution was evaporated by evaporation at 60 ° C to a thick oil (350-450 g). Cyclohexanone (1000 ml ± 10 ml) was added to the flask. Repeat the previous two steps three times. In addition to the GPC results of Preparation 1 or 2 above, GPC showed formation of oligomers with a peak molecular weight of 30,000 and oligomers with a peak molecular weight table of 0.00. Inventive Example 2 About 180-210 grams of the thermosetting component ⑷ from Preparation 1 or 2 above was added to a flask and dissolved by shaking and the flask. The viscosity promoter (b) used is o-methyl varnish resin with a molecular weight of 1760, which is commercially available from Schenectady International Inc. Based on the desired 3 weight ratio viscosity accelerator (b), the required amount of the viscosity accelerator (b) was calculated to be 6 g and added to the flask. Stir the contents of the flask until the viscous g agent is dissolved (about 1 to 2 hours). The GPC results are similar to Preparation 1 or 2 above: Γ. Invention Example 3 Control A is a polyarylene ether taught by Honeywell, U.S. Patent No. 5,986,045. Regarding Invention Example 3, the composition of Invention Example 3 was applied to a substrate using typical coating conditions known to those skilled in the art.

The resulting spin-coating composition was baked at N2 (< 50 ppm 〇2) for 1 minute at each of the following temperatures: 125 ° C, 250 ° C, and 350 ° C. Furnace curing conditions are 400 ° C 200424228 (104) Description of the invention continued on N2 60 minutes (15 liters / minute), jumping from 250 ° C at 5 ° K per minute. The curing temperature is 350 ° C to 450 ° C. Alternatively, a hot plate aging condition at 350 ° C to 450 ° C in N2 for 1-5 minutes can be used. The resulting layers were analyzed in accordance with the analytical test method described above. The properties of this layer are presented in the table. Table 6 Property Control A Invention Example 3 Electricity: Dielectric Constant @ 1ΜΗχ 2.85 2.60 Soil 0.2 Thermal: Shrinkage after 425 ° C / 10 hours (% y 4.0 3.5 ITGA weight after 425 ° C / 0-30 minutes Loss 1.2 < 1 ITGA weight loss after 425 ° C / 30-150 minutes 1.6 1.5-2 Machinery: Tg (° C) 400 in the first cycle 400 > 400 Jg (° c) 400 in the second cycle > 450 modulus (Gpj) 5.0 (thin film thickness = 0 · 8 microns) 6 · 0 ± 0 · 2 (thin film thickness = 1 · 6 microns) hardness (Gpa) 〇 · 4 (thin film thickness = 0 · 8 microns) 6 · 0 ± 0 · 1 (thickness of film = 1. 6 microns) Pull up strength of pushpin (kpsi) > 11 > 11 Adhesive tape test passed refractive index @ 633nm 1.675 1.62 Compatibility with solvents is 200424228 (105) Invention Note that the continuation sheet is important for the improvement of Tg in the ultra-high temperature processing environment, and the improvement of the modulus is attributed to the mechanical stability. Inventive Examples 4-10 Regarding Inventive Examples 4-7, the compositions of Table III were produced according to Inventive Example 2 In addition to changing the adhesion promoter (b) of o-cresol varnish resin, the invention examples 8 to 10 are in accordance with the invention Example 1 produces the composition of Table 7, except for changing the amount of polycarbosilane promoter (b). Table 7 Properties Invention Invention Invention Invention Invention Invention Invention Practice 'Example 5 Example 6 Example 7 Example 8 cases 9 cases 10 o-cresol varnish 0.5 1.0 2.0 3.0 — —… fat (wt%) polycarbon calcined (heavy…… —-… 1.0 2.0 3.0 volume%) inflation% 6.48 5.92 5.80 5.62 5.39 5.08 4.92 shrinkage Degree (425 ° C 2.97 2.45 2.44 2.54 2.28 2.34 2.49 / 10 hours) The tape test passes the pass, the pass passes the pull pin (flat 9.7, 10.7, 9.1, 11.7 10.4, 8.5 »11.4 7.0, 9.7 7.9, 10.0 all, ksi) 11.3 11.2 11.4 Therefore, specific specific examples and applications of compositions and methods for producing low dielectric constant polymers have been disclosed. However, it should be apparent to those skilled in the art that in addition to those already described, there can be many without departing from this. Modifications to the concept of the invention. Therefore, the subject matter of the present invention is not limited, except for the spirit of the patent scope of the application for application of 200424228 (106) Continuation Sheet of the Invention. In addition, in interpreting both the specification and the scope, all terms should be used as closely as possible to this document. In particular, the term "ncomprisesn * " comprising" shall refer to a component, component, or step in a non-exclusive manner, which means that the component, component, or step may exist, or be used, or be used with other components, components, or components. Or the steps are combined. The patent application is to be interpreted broadly as the interpretation is not explicitly cited -113-

Claims (1)

200424228 Scope of patent application 1. A composition comprising: (a) a thermosetting component comprising (1) at least one monomer of formula I as required Q And (2) at least one oligomer or polymer of Chemical Formula II 200424228 P Patent Application Park Continued 〇 200424228 Continued patent application range where E is a cage compound; each Q is the same or different and is selected from hydrogen, aryl, branched aryl and substituted aryl (where the substituent includes hydrogen, || Element, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, fluorenyl, decyl, alkoxy, alkynyl, aryl, fluorenyl, alkynyl, hydroxy, or carboxyl ); The Gw is an aryl or a substituted aryl (wherein the substituent includes a halogen and an alkyl group); the h is 0 to 10; i is 0 to 10; j is 0 to 10; and w is 0 or 1; ( b) a viscosity promoter comprising a compound having at least difunctionality, wherein the difunctionality may be the same or different, when the composition is applied to a substrate, the first functionality can be compatible with the thermosetting component (a) Interaction, and the second functionality is capable of interacting with the substrate. 2. The composition according to item 1 of the patent application scope, wherein the thermosetting component (a) comprises: at least one adamantane monomer (1) of formula III And the at least one oligomer or polymer of formula IV (2) 200424228 Scope of Patent Application Continued And at least one oligomer or polymer of formula VI (2) 200424228 3. The composition according to item 2 of the scope of patent application, wherein the at least one oligomer or polymer (2) is an adamantane dimer of the chemical formula χιν n Q Q 4. The composition according to item 2 of the scope of patent application, wherein the at least one oligomer or polymer (2) is an adamantane trimer of the chemical formula χν 5 · The composition according to item 2 of the scope of patent application, wherein the thermosetting component 200424228 scope of patent application continued (a) includes chemical formula VIIA Chemical formula VIIB Chemical formula VIIC Or adamantane monomer of formula VIID 6- -6- 200424228 »-Scope of Patent Application Continued ^ (2XCV« ^ VIII ^ ridge 2 Jiang Banxiao 蓥 > 殚 命 参 200424228 or (1) Chemical formula IXA Chemical formula IXB Patent Application Continued 200424228 Patent Application Continued ， Chemical Formula IXC Bisadamantane monomer of chemical formula IXD And (2) bisadamantane oligomer or polymer of chemical formula X 200424228 -10-200424228 Continued patent application range where the h is 0 to 10; i is 0 to 10; j is 0 to 10; each 1 ^ is the same or different, and is selected from hydrogen, halide, alkyl, and aryl , Substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyblock, hydroxy, or carboxyl; each Y and is the same Or different, and select from hydrogen, alkyl, aryl, substituted aryl, or molybdenum. 6. A composition according to item 5 of the patent application, wherein the monomer is present. 7. The composition according to claim 5 or 6, wherein Ri is an aryl or substituted aryl and Y is hydrogen, phenyl, or biphenyl. 8. The composition according to item 7 of the scope of patent application, wherein the adamantane monosystem of the formula VIIA, VIIB, VIK: or VIID is present in an amount of about 30 to about 70 area percent, and the adamantane oligosaccharide of the formula VIII The polymer or polymer is present in an amount of about 70 to about 30 area percent, preferably in an amount of about 40 to about 60 area percent, and the adamantane oligomer or polymer of formula VIII is about 60 to An amount of about 40 area percent is present, more preferably about 45 to about 55 area percent, and the adamantane oligomer or polymer of formula VIII is present in an amount of about 55 to about 45 area percent. 9. The composition according to claim 7 of the application, wherein the (2) the adamantane oligomer or poly 1 is of formula XVII, where h is 0 or 1 R -11-200424228 Continued patent application scope or the (2) bisdamantane oligomer or polymer is of formula XVIII, where h is 0 or 1 10. The composition according to item 9 of the scope of patent application, wherein the (2) adamantane oligomer or polymer is a dimer of chemical formula XIX Or the (2) bisadamantane oligomer or polymer is a dimer of chemical formula XX -12- 200424228 Scope of Patent Application Continued -13- 200424228 Scope of Patent Application Continued 12. Composition according to item 7 of the scope of patent application Polymer or polymer is a chemical formula XXIII where (2) adamantane oligo R 2 Y R f mixture of chemical formula X5CV R R II R or the (2) bisadamantane oligomer or polymer J -14- 200424228 Scope of Patent Application Continued F-portion mixture of chemical formula XXVI A R R R R 13. The composition according to item 7 of the scope of patent application, wherein in the thermosetting component (a), the monomer (1) and the oligomer or polymer (2) are diamond-based monomers. -15-200424228 \ Application for patent scope continued 200424228 Continued patent application range and mixture of bisdamantane trimer of chemical formula XXII R R R 15. The composition according to item 14 of the scope of application, wherein at least two of the RiC ^ C groups on the phenyl group are two different isomers, and the two bridgehead carbons of the adamantane monomer are At least one of the phenyl groups is present as two different isomers. 16. A composition according to item 15 of the scope of patent application, wherein the at least two isomers are meta- and para-isomers. 17. A composition according to claim 16 of the scope of patent application, which comprises at least two such oligomers or poly-f compounds. 18. The composition according to item 17 of the application, wherein at least one of the first functionality and the second functionality of the adhesion promoter (b) is selected from the group consisting of Si group, N group, Choice of C-0 group, hydroxyl group and C = C group. 19. The composition according to item 18 of the application, wherein the Si-containing group is preferably selected from the group consisting of Si-H, Si-O, and Si-N; the N-containing group is selected from the group consisting of amines and imines. Group consisting of hydrazone, amidine, and amidine; CC group is selected from carbonyl, ester, -COOH, alkoxy group with 1 to 5 carbon atoms, ether-17- 200424228 «Application for patent A group; the hydroxyl group is a phenol; and a group consisting of. 'Wherein the Si-containing group is selected from the group consisting of glycidyl-oleyl ether and epoxy group, and the c = c-containing group is selected from the group consisting of allyl and acetamidine 20 · According to the combination of item 19 in the scope of patent application It is derived from silane (R2) k (R3) lSi (R4) m (R5) n of chemical formula XI; wherein &, &, & and Rs each independently represent hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted Or an unsubstituted system (where the substituent is an amine group or an epoxy group), an unsaturated or saturated alkoxy group, an unsaturated or saturated carboxylic acid group, or an aryl group, at least one of I, R3, R4, and R5 Two are polycarbonylsilanes representing hydrogen, hydroxyl, saturated or unsaturated oxo, unsaturated alkyl or unsaturated carboxyl, and k + 1 + ni + 1 ^ 4) or chemical formula χιΐ: p--Η 1 Γ ** Ming ^ 10 r _ C: _Χί, 1 -Q; 1 C: _1¾ ΟΙ R12— -Si —Ris- 1. I [7 I Rl4 —-Ρ — One q — Plane r —i — where R6, 1 ^ _2 and each independently represent a substituted or unsubstituted alkylene group, a cycloalkylene group, an ethylene group, an allyl group or an arylene group; r7, Rg, R9, " Ri0, Rl3, and Rl4 Independent representation Atom, alkyl, alkylene, ethenyl, cycloalkyl, methyl, aryl, or arylene and may be linear or branched; Rn means organic, crushed, oxy, or organic And p, q, r, and s satisfy the conditions of [4Sp + q + r + s < 100, 00], and q, r, and s may be collectively or individually zero; the C-0-containing group It is selected from glycidyl ethers or esters of unsaturated carboxylic acids containing at least one carboxylic acid group; 200424228 Application for a patent application continued page The .c = c group is a vinyl ring family oligomer or polymer in which the ring The group is a pyridine, aromatic or heteroaromatic group; and the hydroxyl group is a phenolic resin or oligomer of chemical formula XIII: _ [R16C6H2 (OH) (R17)] ", where R16 is a substituted or unsubstituted · Alkyl, cycloalkylene, ethylfluorenyl, methylpropyl, or aryl, R17 is alkyl: V, alkylene, vinylidene, cycloalkylene, methylidenepropyl, or aryl, and \ t = 3-100 〇21. The composition according to item 20 of the scope of patent application, wherein the viscosity promoter (b) is a phenolic resin or oligomer. —> 22. —An oligomer 7 including according to Please apply for the composition in the scope of patent item 7. ^ 23. — A spin-coating composition, which includes an oligomer and a solvent (preferably cyclohexanone) according to the scope of patent application in scope 22. 24. — species A polymer prepared from a spin coating composition according to item 23 of the scope of patent application. 25. A seed layer comprising a composition according to item 24 of the scope of patent application. 26. The layer according to item 25 of the scope of patent application, wherein the thickness of the layer is as high as or greater than about 1,5 # meters. 27. The layer according to item 25 of the application, wherein the polymer is aged. 28. The layer according to item 25 of the scope of patent application, wherein the dielectric constant of the layer is lower than 3.0. 29. The composition according to item 25 of the application, wherein the glass transition temperature of the layer is at least about 350 ° C. 30. A substrate having at least one layer according to item 25 of the scope of patent application. -19- 200424228 Scope of Patent Application Continued Page 31. A microchip including a substrate according to item 30 of the scope of patent application. 32 · — A method for improving (a) the viscosity of a thermosetting component on a substrate, the (a) thermosetting component includes: (1) a monomer of formula I Q Q and (2) at least one oligomer or polymer of chemical formula II -20- 200424228 __ Patent application scope continued -21-200424228 Continued patent application range where E is a cage compound; the Q is the same or different and is selected from hydrogen, aryl, branched aryl, and substituted aryl, where the substituent includes hydrogen, element , Alkyl, aryl, substituted aryl, heteroaryl, aryl ether, fluorenyl, decyl, allyloxy, fluorenyl, aryl, alkenyl, rosenyl, light or Leptin; the Gw is an aryl or a substituted aryl, wherein the substituents include a prime and an alkyl; the h is 0 to 10; i is 0 to 10; j is 0 to 10; and w is 0 or 1) ; The method includes the steps of: adding (b) a viscosity promoter to the thermosetting component, which includes a compound having at least difunctionality, wherein the difunctionalities may be the same or different, and the first one functionality Capable of interacting with the thermosetting component (a), and having a second functionality capable of interacting with the substrate to form a composition; and applying the composition to the substrate. 33. The method according to item 22 of the scope of patent application, wherein the thermosetting component (a) comprises: at least one monomer (1) of formula III And the at least one oligomer or polymer of formula IV (2) -22- 200424228 ^ Application for patent scope continued Q And at least one oligomer or polymer of formula VI (2) • 23- 200424228 Scope of Patent Application Continued 34. The method according to claim 33, wherein the at least one oligomer or polymer (2) is adamantane dimer of chemical formula XIV Q 35. The method according to claim 33, wherein the at least one oligomer or polymer (2) is an adamantane trimer of chemical formula XV 36. The method according to item 33 of the scope of patent application, wherein the thermosetting component--24- 200424228 application for patent scope continued page includes (1) chemical formula VIIA Ri Chemical formula IXB -25-200424228 Scope of Patent Application Continued or Adamantane Monomer of Chemical Formula IXD And (2) Adamantane oligomer or polymer of chemical formula-VIII -26- 200424228 Scope of patent application continued -27- 200424228 Continued patent application range or (1) Chemical formula IXA Chemical formula IXB -28- 200424228 Scope of patent application continued, chemical formula IXC Bisadamantane monomer of chemical formula IXD And (2) bisadamantane oligomer or polymer of chemical formula X -29- 200424228 5〇-30- 2〇〇424228 ____ I apply for a patent continuation page where the h is 0 to 10; i is 0 to 10; j is 0 to 10; each of these 仏 is the same or different 'and from gas, _ prime , Radical, aryl, substituted aryl, heteroaryl, aryl ether, fluorenyl, block, alkoxy, alkynyl, aryl, alkenyl, hydroxyalkynyl, hydroxy, or carboxyl; Each γ and γ are the same or different and are selected from hydrogen, alkyl, aryl, substituted aryl, or hydrogen. 37. The method according to the scope of patent application, further comprising the steps of: curing the composition by using a furnace, a hot plate, an electron beam, microwave or ultraviolet radiation. 38. The method according to item 37 of the application, wherein the monomer is present. 39. The method according to item 36 or 38 of the application, wherein it is an aryl group or a substituted aryl group and the Y is hydrogen, phenyl, or biphenyl. 40. The method according to item 39 of the scope of patent application, wherein the adamantane single system of the chemical formula νπΑ, VIIB, VIIC, or VIID is present in an amount of about 30 to about 70 area percent, and the adamantane of the chemical formula VIII The oligomer or polymer is present in an amount of about 70 to about 30 area percent, preferably in an amount of about 40 to about 60 area percent, and the adamantane oligomer or polymer of the chemical formula νίπ is An amount of 60 to about 40 area percent is present, more preferably in an amount of about 45 to about 55 ¾ percent, and a diamond-fired oligomer or polymer of the chemical formula νίπ is present in an amount of about 55 to about 45 area percent. 41. The method according to item 39 of the scope of patent application, wherein the (2) diamond oligomer or polymer is of formula XVII, where h is 0 or 1 200424228 Or the (2) bisadamantane oligomer or polymer is of formula XVIII, where h is 0 or 1 42. The method according to item 39 of the application, wherein the (2) adamantane oligomerization >-substance or polymer is a dimer of chemical formula XIX · R R 200424228 Scope of Patent Application 43. The method according to item 39 of the scope of patent application, wherein the (2) adamantane oligomer or polymer is a terpolymer Y of the chemical formula XXI R R R or the (2) bis-adamantane oligomer or polymer is a terpolymer of chemical formula XXII R R R -33- 200424228 Scope of patent application continuation 44. The method according to item 39 of the scope of patent application, wherein the (2) adamantane oligomer or polymer is a chemical formula XXIII Mixture with chemical formula XXV -34- 200424228 Scope of Patent Application Continued Mixture with chemical formula XXVI R R Y / ^ / = \ R 45. The method according to item 39 of the application, wherein in the thermosetting component (a), the monomer (1) and the oligomer or polymer (2) are adamantyl monomer. -35- 200424228 Patent Application Range Page 46. The method according to item 39 of the patent application range, wherein in the thermosetting component (a), the oligomer or polymer (2) includes an adamantane di of the chemical formula XIX Polymer R R With adamantane trimer of chemical formula XXI R -36- 200424228 Scope of Patent Application Continued 47. The method according to item 46 of the scope of patent application, wherein at least two of the RiC ^ C groups on the phenyl group are two different isomers, and the benzene between the two bridgehead carbons of the adamantane monomer is At least one of the radicals exists as two different isomers. 48. The method according to item 47 of the application, wherein the at least two isomers are meta- and para-isomers. 49. A method according to item 48 of the application, which includes at least two such oligomers or polymers. 50. The method according to item 39 of the application, wherein at least one of the first functionality and the second functionality of the adhesion promoter (b) is selected from the group consisting of Si group, N group, and C- 0 group, hydroxyl and OC group-containing choice. 51. The method according to item 50 of the patent application, wherein the Si-containing group is preferably selected from the group consisting of Si-H, Si-O, and Si-N; the N-containing group is selected from the group consisting of amine, imine, and amidine A group consisting of amines and amidines; C-0-containing groups are selected from the group consisting of carbonyl, hydrazone, -COOH, alkoxy groups with 1 to 5 carbon atoms, ethers, shrinkage -37- 200424228 Continued on the group consisting of glycerol and epoxy groups; the hydroxyl group is signed; and this group is selected from the group consisting of propyl and ethyl. β 土 52 · According to the method of item 51 of the scope of patent application, the chemical group containing Si group is selected from Shi Xiyan (R2) k (R3) iSi (R4) m (R5) n of formula XI And R 夂 & > T K2 'KK3' R4 each independently represents hydrogen, hydroxyl, unsaturated hept + 4 saturated alkyl, taken, or substituted: (wherein the substituent is an amine or (Epoxy group) all: saturated or ... oxy, unsaturated or saturated polyacid or aryl, at least two of Λ2, R3, ~ and r5 are hydrogen saturated Or un & polysilynes with succinyl, unsaturated alkyl or unsaturated carboxyl groups, and k + H_m + ^ 4 'or chemical formula -XII: 0-si-R7 -R6 Its φ, R6, Ri2, and R! 5 each independently represent a substituted or unsubstituted sub-situ A-ring stilbene, ethynyl, phenyl, or arylene; R ?, R9, and R1. , R13 and R14 each independently represent a hydrogen atom, an alkyl group, a fluorenylene group, a vinyl group, a cycloalkyl group, an amidinopropyl group, an aryl group or an arylene group, and may be fluorene or branched, and R1 1 represents an organic second, A second group, a second oxy group, or an organic group; and p, q, r, and S satisfy the condition of [4Sp + q + r + s < 10.0, 0〇〇], and q and r and s may be collectively or Each is zero; the C-0-containing group is selected from glycidyl ether or an ester of an unsaturated polyacid containing at least one carboxylic acid group; Group oligomers or polymers, wherein the ring group is said to be an aromatic, aromatic or heteroaromatic group; and the hydroxyl group is a phenolic resin or oligomer of the formula XIII ··-[R16C6H2 (OH) (R17)] ", Where R16 is a substituted or unsubstituted alkylene, cycloalkylene, ethylfluorenyl, methylpropyl, or aryl, and R17 is an alkyl, alkylene, vinylidene, cycloalkylene, Allylic or aryl, And t = 3-100. 53. The method according to item 52 of the scope of the patent application, wherein the adhesion promoter (b) is a phenolic resin or an oligomer. 54.-at least two different isomers of the old chemical formula XXXIII mixture Where E is a cage compound and each Q is the same or different and is selected from hydrogen, aryl, branched aryl, and substituted aryl. 55. The mixture according to item 54 of the application, wherein the mixture includes at least two different isomers of the formula XXXIII 56. A mixture according to item 55 of the scope of patent application, wherein the mixture includes at least two chemical formulas XXXIV -39- 200424228 Chemical formula XXXVI Or different isomers of formula XXXVII Wherein each Y is the same or different, and is selected from hydrogen, alkyl, aryl, substituted aryl, or functional element, and each R is the same or different, and is selected from hydrogen, halogen, alkyl, aryl, substituted aryl Group, heteroaryl, aryl ether, fluorenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyaryl, hydroxyfluorenyl, hydroxyalkynyl, hydroxy, or carboxyl. 57. The mixture according to item 54 of the scope of patent application, wherein the mixture includes -40-200424228. The scope of patent application continues on at least two different isomers of chemical formula XXXVII Q 58. A mixture according to item 57 of the scope of patent application, wherein the mixture includes at least two chemical formulas XXXVIII -41-200424228 Continued page for patent application Fanyuan or different isomers of chemical formula XXXX Where each Y is the same or different and is selected from hydrogen, alkyl, arylaryl or halogen, each R is the same or different and is selected from alkyl, aryl, substituted aryl, heteroaryl, aryl ether Radical, alkoxy, light fe, via aryl, via fluorenyl, via or carboxyl. Radical, substituted hydrogen, halogen, fluorenyl, decanyl, hydrocarbyl