JP2013173916A - Composition for antireflective coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an improved composition for an antireflective layer composition which exhibits increased stability and improved BARC performance.SOLUTION: A composition includes at least (A) a curing catalyst selected from formula A: [NR1'R2'R3'R4']X(formula A); and (B) a prepolymer formed of a first composition containing formula 1 and formula 2.

Description

REFERENCES TO RELATED APPLICATIONS This application is a benefit of US Provisional Application No. 61 / 578,282, filed December 21, 2011, and US Patent Application No. 13 / 596,191, filed August 28, 2012. Insist on profit.

  The present invention relates to compositions, particularly bottom antireflective coating compositions (or “BARC”) used in microelectronic applications. There continues to be a need in the microelectronics industry for microchips with smaller and more defined lithographic patterns. Problems currently encountered in these developments include degradation of the developed photoresist profile due to reflection at the photoresist layer-substrate interface, as well as adequate etch resistance to accommodate shorter exposure wavelengths. There is a need for a thin resist layer having Antireflection coatings can be used to address the above problems.

  The curing catalyst plays an important role in the properties of the final antireflective coating, such as photospeed and pattern collapse limit. However, the stability and litho performance of silsesquioxane prepolymer solutions using conventional curing catalysts has been undesirable. There is a need for an improved cure catalyst that is used in improved SiARC formulations and provides improved stability and improved litho performance.

  US Patent Application Publication No. 2008/274432 discloses the following: (A-1) a silicon-containing compound obtained by hydrolytic condensation of a hydrolyzable silicon compound in the presence of an acid catalyst, and (A-2) in the presence of a base catalyst. A silicon-containing compound obtained by hydrolytic condensation of a hydrolyzable silicon compound, (B) a hydroxide or organic acid salt of Li, Na, K, Rb or Ce, or a sulfonium, iodonium or ammonium compound, (C) an organic Disclosed is a “silicon-containing film” formed from a thermosetting composition comprising an acid, (C) a cyclic ether-substituted alcohol, and (E) an organic solvent.

  US Patent Application Publication No. 2010/0210765 discloses a resist underlayer film forming composition comprising: a polymer having a silicon atom in the main chain; a compound having a polycyclic structure; and an organic solvent. A compound having a polycyclic structure has at least two carboxyl groups as substituents, and the two carboxyl groups are adjacent to each other and individually bonded to two carbon atoms to form a polycyclic structure. Both of the two carboxyl groups have an endo configuration or an exo configuration or a cis configuration.

  U.S. Pat. No. 8,299,974 discloses a “thermosetting“ metal oxide-containing film-forming composition for forming a metal oxide-containing film ”formed in a multilayer resist method. The thermosetting “metal oxide-containing film-forming composition” comprises at least: (A) a “metal oxide-containing compound” obtained by hydrolysis condensation of a hydrolyzable silicon compound and a hydrolyzable metal compound, and (B) heat A crosslinking accelerator, (C) a monovalent, divalent or higher organic acid having 1 to 30 carbon atoms, (D) a trivalent or higher alcohol, and (E) an organic solvent.

  WO 2009/133456 discloses an absorption graded silicon-based antireflective coating and a method for forming the same. The method includes the steps of coating a substrate with an anti-reflective coating composition comprising a clear siloxane and a light absorbing dye, and the coated substrate is sub-uniformly absorbed in part by sublimation of the dye from the composition. A step of heating at a temperature at which the protective coating layer is formed.

  US Pat. No. 8026038 describes (A) a metal oxide-containing compound obtained by hydrolytic condensation of a hydrolyzable silicon compound and a hydrolyzable metal compound, (B) water of Li, Na, K, Rb or Cs. Disclosed is a “metal oxide-containing film” formed from a thermosetting composition comprising an oxide or organic acid salt, or a sulfonium, iodonium or ammonium compound, (C) an organic acid, and (D) an organic solvent.

  European Patent Application Publication No. 2172807A1 is a “silicon-containing compound” obtained by forming a silicon-containing film in a multilayer resist method and hydrolyzing and condensing a hydrolyzable silicon compound using at least an acid (A) as a catalyst. , (B) a thermal crosslinking accelerator, (C) a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms, (D) a trivalent or higher alcohol, and (E) an organic solvent A thermosetting composition is disclosed.

  US Patent Application Publication No. 2011/0117746 discloses a coating composition comprising an organopolysiloxane, a solvent and a quaternary ammonium salt or quaternary phosphonium salt; or a polysilane, a solvent, and a crosslinking agent, a quaternary ammonium salt, Disclosed is a coating composition comprising at least one additive selected from the group consisting of a quaternary phosphonium salt and a sulfonic acid compound. Polysilane has a silanol group at the terminal together with a silanol group or a hydrogen atom.

US Patent Application Publication No. 2008/0196626 includes (a) at least one formula — [(SiO _{n / 2} ) (R ¹ ) _4-n ] — (wherein R ¹ is a non-hydrolyzable group; n is an integer ranging from 1 to 3); and (b) a composition comprising a crosslinking catalyst. The composition is disclosed as being useful for the formation of low-k dielectric materials, and underlayer materials having hard mask and antireflective properties.

  US Patent Application Publication No. 2009/0011372 describes (A) a silicon-containing compound obtained via hydrolysis condensation of a hydrolyzable silicon compound in the presence of an acid catalyst; (B) Li, Na, K, Rb or Formed from a thermosetting composition comprising a hydroxide or organic acid salt of Ce or a sulfonium, iodonium or ammonium compound; (C) an organic acid; (D) a cyclic ether-substituted alcohol; and (E) an organic solvent. A silicon-containing film is disclosed.

  Additional compositions for antireflective coatings and / or other electronic applications can be found in the following references: U.S. Pat. Nos. 7,507,783, 7,303,785, 7,736,837, 5,100,503, 5,612,034 7417104, 6268457; US Patent Application Publication Nos. 2005/0031964, 2009/0148789, 2009/0148789, 2007/0185298, 2010/0086872, 2010/0261097, 2005/0277058, 2006/0278158, 2011/0045404; International Publication Nos. 2009/0888600, 2008/061258; European Patent Application Publication No. 2196858A1; and KR2009908474 A (Abstract), disclosed in KR2010058591A (Abstract). However, there remains a need for compositions for improved anti-reflective layer compositions having increased stability and improved BARC performance. These needs and others are met by the following invention.

US Patent Application Publication No. 2008/274432 US Patent Application Publication No. 2010/0210765 U.S. Pat. No. 8,299,974 International Publication No. 2009/133456 U.S. Patent No. 8026038 European Patent Application Publication No. 2172807A1 US Patent Application Publication No. 2011/0117746 US Patent Application Publication No. 2008/0196626 US Patent Application Publication No. 2009/0011372 U.S. Pat. No. 7,507,783 U.S. Pat. No. 7,303,785 U.S. Pat. No. 7,736,837 US Pat. No. 5,100,503 US Pat. No. 5,612,034 US Pat. No. 7,417,104 US Pat. No. 6,268,457 US Patent Application Publication No. 2005/0031964 US Patent Application Publication No. 2009/0148789 US Patent Application Publication No. 2007/0185298 US Patent Application Publication No. 2010/0086872 US Patent Application Publication No. 2010/0261097 US Patent Application Publication No. 2005/0277058 US Patent Application Publication No. 2006/0278158 US Patent Application Publication No. 2011/0045404 International Publication No. 2009/0888600 International Publication No. 2008/061258 European Patent Application Publication No. 2196858A1 KR20090884748A (abstract) KR2010058591A (abstract) US Patent Application Publication No. 2007/0238052 US Pat. No. 6,042,997 US Pat. No. 5,492,793 US Pat. No. 5,929,176 US Pat. No. 6,090,526 US Pat. No. 5,843,624 US Pat. No. 6,048,664 US Pat. No. 6,057,083 European Patent Application Publication No. 01008913A1 European Patent Application Publication No. 0100542A1 US Pat. No. 6,048,662

The present invention provides at least A) Formula A:
[NR1′R2′R3′R4 ′] ⁺ X ⁻ (Formula A)
[R1 ′, R2 ′, R3 ′, R4 ′ are each independently selected from hydrogen, alkyl (straight or branched), substituted alkyl, aryl, or substituted aryl;
X is a monovalent anion,
Wherein in formula A, at least one of R1 ′, R2 ′, R3 ′ or R4 ′ is methyl]
A curing catalyst selected from:
B) The following:
a) Formula 1:

［式中、Ｒａは、１つ又は複数の多重結合を含むが、但しＲａが２つ以上の多重結合を含む場合、これらの多重結合は、共役配置ではなく；Ｒ１、Ｒ２及びＲ３は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］
から選択される化合物Ｆ１；
ｂ）式２：

[Wherein Ra includes one or more multiple bonds, provided that when Ra includes two or more multiple bonds, these multiple bonds are not in conjugated configuration; R1, R2 and R3 are alkoxyl , Hydroxyl, halide, OC (O) R or OC (O) OR each independently, where R is alkyl or substituted alkyl]
Compound F1 selected from:
b) Equation 2:

［式中、Ｒｂは、Ｈ又はアルキル、アルキレン若しくはアルキリデンを含む飽和基から選択され；Ｒ４、Ｒ５及びＲ６は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］
から選択される化合物Ｆ２；
ｃ）式３：

Wherein Rb is selected from H or a saturated group including alkyl, alkylene or alkylidene; R4, R5 and R6 are each independently alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR Wherein R is alkyl or substituted alkyl]
Compound F2 selected from:
c) Equation 3:

［式中、Ｒｃは、２つ以上の多重結合を含み、これらの多重結合は共役配置にあり；Ｒ７、Ｒ８及びＲ９は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］
から選択される化合物Ｆ３；
ｄ）式４：

[Wherein Rc contains two or more multiple bonds, and these multiple bonds are in a conjugated configuration; R7, R8 and R9 are alkoxyl, hydroxyl, halide, OC (O) R or OC (O) Each independently selected from OR, where R is alkyl or substituted alkyl]
Compound F3 selected from:
d) Equation 4:

［式中、Ｒ１０、Ｒ１１、Ｒ１２及びＲ１３は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］
から選択される化合物Ｆ４
を含む第１組成物から形成されるプレポリマーと
を含む組成物を提供する。

Wherein R10, R11, R12 and R13 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR, wherein R is alkyl or substituted alkyl ]
Compound F4 selected from
And a prepolymer formed from a first composition comprising:

As discussed above, the present invention provides at least A) Formula A:
[NR1′R2′R3′R4 ′] ⁺ X ⁻ (Formula A)
[R1 ′, R2 ′, R3 ′, R4 ′ are each independently selected from hydrogen, alkyl (straight or branched), substituted alkyl, aryl, or substituted aryl;
X is a monovalent anion,
Wherein in formula A, at least one of R1 ′, R2 ′, R3 ′ or R4 ′ is methyl]
A curing catalyst selected from:
B) The following:
a) Formula 1:

［式中、Ｒａは、Ｃ＝Ｃ、Ｃ≡Ｃ、Ｃ＝Ｏ、Ｃ＝Ｎ及びＣ≡Ｎを含む１つ又は複数の多重結合（すなわち、二重結合又は三重結合）を含むが、但しＲａが２つ以上の多重結合を含む場合、これらの多重結合は共役配置ではなく；
Ｒ１、Ｒ２及びＲ３は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］
から選択される化合物Ｆ１；
ｂ）式２：

[Wherein Ra includes one or more multiple bonds (ie, double bonds or triple bonds) including C═C, C≡C, C═O, C═N and C≡N, provided that If Ra contains two or more multiple bonds, these multiple bonds are not in conjugated configuration;
R1, R2 and R3 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR, where R is alkyl or substituted alkyl]
Compound F1 selected from:
b) Equation 2:

［式中、Ｒｂは、Ｈ又はアルキル、アルキレン若しくはアルキリデンを含む飽和基から選択され；Ｒ４、Ｒ５及びＲ６は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］
から選択される化合物Ｆ２；
ｃ）式３：

Wherein Rb is selected from H or a saturated group including alkyl, alkylene or alkylidene; R4, R5 and R6 are each independently alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR Wherein R is alkyl or substituted alkyl]
Compound F2 selected from:
c) Equation 3:

［式中、Ｒｃは、Ｃ＝Ｃ、Ｃ≡Ｃ、Ｃ＝Ｏ、Ｃ＝Ｎ及びＣ≡Ｎを含む２つ以上の多重結合を含み、これらの多重結合は共役配置にあり；Ｒ７、Ｒ８及びＲ９は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］
から選択される化合物Ｆ３；
ｄ）式４：

[Wherein Rc comprises two or more multiple bonds including C═C, C≡C, C═O, C═N and C≡N, and these multiple bonds are in a conjugated configuration; R7, R8 And R9 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR, where R is alkyl or substituted alkyl]
Compound F3 selected from:
d) Equation 4:

［式中、Ｒ１０、Ｒ１１、Ｒ１２及びＲ１３は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］
から選択される化合物Ｆ４
を含む第１組成物から形成されるプレポリマーと
を含む組成物を提供する。

Wherein R10, R11, R12 and R13 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR, wherein R is alkyl or substituted alkyl ]
Compound F4 selected from
And a prepolymer formed from a first composition comprising:

As used herein, R1 refers to R _1, R2 means R _2, is other similar.

  The composition of the present invention can comprise a combination of two or more embodiments as described herein.

  In one embodiment, the first composition comprises less than 2 weight percent of a trihydric or higher polyhydric alcohol based on the weight of the prepolymer.

  In one embodiment, the first composition comprises less than 1 weight percent of a trihydric or higher polyhydric alcohol based on the weight of the prepolymer.

  In one embodiment, the first composition comprises less than 0.5 weight percent of a trihydric or higher polyhydric alcohol based on the weight of the prepolymer.

  In one embodiment, the first composition comprises less than 0.1 weight percent of a trihydric or higher polyhydric alcohol based on the weight of the prepolymer.

  In one embodiment, the first composition comprises less than 0.05 weight percent of a trihydric or higher polyhydric alcohol based on the weight of the prepolymer.

  In one embodiment, the first composition comprises less than 0.01 weight percent of a trihydric or higher polyhydric alcohol based on the weight of the prepolymer.

  In one embodiment, the first composition comprises less than 0.005 weight percent of a trihydric or higher polyhydric alcohol based on the weight of the prepolymer.

  In one embodiment, the first composition does not include a trihydric or higher polyhydric alcohol based on the weight of the prepolymer.

  Some trihydric or higher polyhydric alcohols are described in, for example, S. 8029974 and EP 2172807 A1.

  In one embodiment, in Formula A, at least two of R1 ', R2', R3 ', or R4' are each methyl.

  In one embodiment, in Formula A, R1 ', R2', R3 'or R4' is each independently selected from hydrogen, C1-C3 alkyl or aryl.

  In one embodiment, the composition comprises less than 1 ppm metal oxide based on the weight of the composition.

  In one embodiment, the composition does not include a metal oxide. Metal oxides tend to cause gelation, film coating defects, poor chemical stability and / or refractive index that is outside the target range for anti-reflective coating applications. Some compositions containing metal oxides are described, for example, in US Pat. S. 8026038B2.

  In one embodiment, the composition comprises less than 1 ppm “light absorbing dye” based on the weight of the composition.

  In one embodiment, the composition does not include a “light absorbing dye”.

  “Light absorbing dyes” include, for example, bis-phenol compounds and derivatives thereof. For example, see WO2009 / 133456 for examples of “light absorbing dyes”.

  In one embodiment, the first composition comprises 5 weight percent or more Si, 10 weight percent or more Si, or 15 weight percent or more Si, based on the combined weight of compounds F1, F2, F3, and F4.

  In one embodiment, the total molar amount of compound F2 and compound F4 is 40 mole percent or more based on the total moles of compounds F1, F2, F3 and F4.

  In one embodiment, the total molar amount of compound F2 and compound F4 is greater than or equal to 85 mole percent or less than or equal to 80 mole percent, based on the total moles of compounds F1, F2, F3, and F4.

  In one embodiment, compound F4 is present in an amount of 10 mole percent or more based on the total moles of compounds F1, F2, F3 and F4.

  In one embodiment, the molar ratio of F1 / F4 is 1/20 to 1/1 or 1/15 to 1/1 or 1/10 to 1/1.

  In one embodiment, in the first composition, F1 is in the range of 5-50 weight percent or 10-30 weight percent; F2 is in the range of 5-50 weight percent or 10-40 weight percent; F3 is in the range of 2-20 weight percent or 2-10 weight percent; F4 is in the range of 20-80 weight percent or 30-80 weight percent. Each weight percentage is based on the weight of the first composition.

  In one embodiment, in the first composition, compound F1 is 10 to 90 mole percent, further 15 to 90 mole percent, or even 20 to 90, based on the total moles of compounds F1, F2, F3 and F4. It is present in an amount of mole percent, even 25 to 90 mole percent.

  In one embodiment, in the first composition, compound F1 is present in an amount greater than 10 mole percent, even greater than 12 mole percent, based on the total moles of compounds F1, F2, F3 and F4.

  In one embodiment, in the first composition, compound F4 is 10 to 65 mole percent, further 10 to 60 mole percent, or even 10 to 55 moles based on the total moles of compounds F1, F2, F3 and F4. It is present in an amount of mole percent, or even 10 to 50 mole percent.

  In one embodiment, in the first composition, compound F4 is present in an amount of less than 65 mole percent, or even less than 60 mole percent, based on the total moles of compounds F1, F2, F3 and F4.

  The first composition can comprise a combination of two or more embodiments as described herein.

  In one embodiment, the prepolymer is formed at least by hydrolyzing the first composition to form a hydrolysis product and condensing the hydrolysis product.

  In one embodiment, the prepolymer has a Mw of 1,000 to 20,000 g / mol or 1,000 to 10,000 g / mol or 1,000 to 5,000 g / mol as determined by conventional GPC. Have.

  In one embodiment, the prepolymer has a Mw / Mn of 1.1-6 or 1.2-5 or 1.5-4.

  The prepolymer can comprise a combination of two or more embodiments described herein.

  The present invention also provides a crosslinked composition formed from the second composition.

  The present invention also provides an article comprising at least one component formed from the composition of the present invention.

  In one embodiment, the article is a membrane.

  The present invention also provides a membrane comprising at least one layer formed from the composition of the present invention. In further embodiments, the membrane comprises at least two layers. In a further embodiment, the second layer is formed from another composition comprising at least one polymer.

  The present invention also provides a film comprising at least two layers, at least one of which is an antireflective layer formed from the composition of the present invention. In a further embodiment, the other layer is a photoresist layer.

  The present invention also provides a film comprising at least two layers, at least one of which is an antireflective layer formed from the composition of the present invention. In a further embodiment, the other layer is a photoresist layer.

  Articles of the present invention can include a combination of two or more embodiments as described herein.

  The membranes of the present invention can comprise a combination of two or more embodiments described herein.

The present invention is a method of forming a film on a substrate, comprising at least preparing the substrate,
Forming an underlayer comprising at least one polymer on a substrate;
Applying the composition of the invention on the underlayer,
Also provided is a method comprising curing the composition to form a coating. In a further embodiment, multiple layers of composition are applied over the underlayer.

  In one embodiment, the coating is an antireflective layer.

The present invention is a method of forming a film on a substrate, comprising at least preparing the substrate,
Applying the composition of the invention on at least a part of the substrate or on one or more intermediate layers applied on said substrate;
There is also provided a method comprising curing the first composition or the second composition to form a coating. In further embodiments, multiple layers of the composition are applied on at least a portion of the substrate or on one or more intermediate layers applied on the substrate.

  In one embodiment, the coating is an antireflective layer.

  The methods of the invention can include combinations of two or more embodiments described herein.

Curing catalyst The curing catalyst has the formula A:
[NR1′R2′R3′R4 ′] ⁺ X ⁻ (Formula A)
[R1 ′, R2 ′, R3 ′, R4 ′ are each independently selected from hydrogen, alkyl (straight or branched), substituted alkyl, aryl, or substituted aryl;
X is a monovalent anion, preferably a halide selected from Br, Cl, I or F, more preferably Br, Cl, more preferably Cl.
Wherein in formula A, at least one of R1 ′, R2 ′, R3 ′ or R4 ′ is methyl]. In a further embodiment, at least two of R1 ′, R2 ′, R3 ′ or R4 ′ are each methyl.

  In one embodiment, R1 ', R2', R3 ', R4' are each independently selected from alkyl (straight or branched), substituted alkyl, aryl or substituted aryl.

  In one embodiment, R1 ', R2', R3 ', R4' are each independently selected from hydrogen, alkyl (linear or branched) or aryl.

  In one embodiment, R1 ', R2', R3 ', R4' are each independently selected from alkyl (linear or branched) or aryl.

  In one embodiment, R1 ', R2', R3 ', R4' are each independently selected from C1-C3 alkyl (straight or branched) or aryl. In a further embodiment, aryl is C5-C6 aryl.

  In one embodiment, R1 ', R2', R3 ', R4' are each independently selected from C1-C2 alkyl (straight or branched) or aryl. In a further embodiment, aryl is C5-C6 aryl.

  In one embodiment, at least three of R1 ', R2', R3 'or R4' are each methyl.

  In one embodiment, each of R1 ', R2', R3 'or R4' is methyl.

  In one embodiment, the curing catalyst is selected from the group consisting of benzyltrimethylammonium chloride, benzyldimethylhexadecylammonium chloride, phenyltrimethylammonium chloride, tetramethylammonium chloride, or combinations thereof.

  “Substituted alkyl” refers to an alkyl having one or more hydrogens that are substituted with another group containing at least one heteroatom.

  “Substituted aryl” means aryl having one or more hydrogens replaced with another group containing at least one heteroatom.

  The curing catalyst can comprise a combination of two or more embodiments as described herein.

Compounds F1-F4
Compounds F1, F2, F3 and F4 are described below.
A) Formula 1:

［式中、Ｒａは、Ｃ＝Ｃ、Ｃ≡Ｃ、Ｃ＝Ｏ、Ｃ＝Ｎ及びＣ≡Ｎを含む１つ又は複数の多重結合を含むが、但しＲａが２つ以上の多重結合を含む場合、これらの多重結合は共役配置ではなく；Ｒ１、Ｒ２及びＲ３は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］から選択される化合物Ｆ１。更なる実施態様において、Ｒはアルキルである。

[Wherein Ra includes one or more multiple bonds including C═C, C≡C, C═O, C═N and C≡N, provided that Ra includes two or more multiple bonds. Where these multiple bonds are not in a conjugated configuration; R1, R2 and R3 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR, where R is A compound F1 selected from the group consisting of alkyl and substituted alkyl. In a further embodiment, R is alkyl.

In one embodiment, Ra comprises one or more alkenyl groups, alkynyl groups, imides, nitriles, ketones, esters, amides or carbonates and comprises 2 to 10 carbon atoms; R1, R2 and R3 Are each independently selected from OH, OR or OC (O) R, wherein R is C ₁ -C ₁₀ alkyl or C ₁ -C ₁₀ substituted alkyl.

In one embodiment, Ra comprises one or more alkenyl groups, alkynyl groups, imides, nitriles, ketones, esters, amides or carbonates and comprises 2 to 10 carbon atoms; R1, R2 and R3 Are each independently selected from OH, OR or OC (O) R, wherein R is C ₁ -C ₁₀ alkyl.

  In one embodiment, Ra is selected from vinyl, allyl, propenyl, butenyl, acetoxyl, cyanoethyl, acetoethyl or acetamidopropyl; R1, R2 and R3 are each OR, wherein each R is independently , Methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl or 2-butyl.

  In one embodiment, compound F1 is selected from vinyltrimethoxysilane or vinyltriethoxysilane.

Ｂ）式２：

B) Formula 2:

［式中、Ｒｂは、Ｈ又はアルキル、アルキレン若しくはアルキリデンを含む飽和基から選択され；Ｒ４、Ｒ５及びＲ６は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］から選択される化合物Ｆ２。更なる実施態様において、Ｒはアルキルである。

Wherein Rb is selected from H or a saturated group including alkyl, alkylene or alkylidene; R4, R5 and R6 are each independently alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR Wherein R is alkyl or substituted alkyl]. In a further embodiment, R is alkyl.

  In one embodiment, Rb is selected from saturated groups including alkyl, alkylene or alkylidene; R4, R5 and R6 are each independently from alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR Where R is alkyl or substituted alkyl. In a further embodiment, R is alkyl.

In one embodiment, Rb represents a substituted or unsubstituted _C 1 _{-C 10} cyclic alkyl, substituted or unsubstituted _C 1 _{-C 10} acyclic alkyl, substituted or unsubstituted _C 1 _{-C 10} cyclic alkylene, substituted Or unsubstituted C ₁ -C ₁₀ acyclic alkylene, substituted or unsubstituted C ₁ -C ₁₀ cyclic alkylidene, substituted or unsubstituted C ₁ -C ₁₀ acyclic alkylidene or H; or unsubstituted C ₁ -C ₁₀ cyclic alkyl, unsubstituted _C 1 _{-C 10} acyclic alkyl, unsubstituted _C 1 _{-C 10} cyclic alkylene, unsubstituted _C 1 _{-C 10} acyclic alkylene, unsubstituted _C 1 _{-C 10} cyclic alkylidene, unsubstituted _C 1 _{-C 10} acyclic alkylidene or H; or unsubstituted _C 1 _{-C 10} cyclic alkyl, unsubstituted _C 1 _{-C 10} acyclic alkyl or H; or unsubstituted _{C 1} It is or unsubstituted _C 1 _{-C 10} saturated group containing acyclic alkyl; C ₁₀ cyclic alkyl or unsubstituted _C 1 _{-C 10} acyclic alkyl;
R4, R5 and R6, OH, are each independently selected from OR or OC (O) R, where R _is a C 1 _{-C 10} alkyl or _C 1 _{-C 10} substituted alkyl. In a further embodiment, R is _C 1 _{-C 10} alkyl.

  In one embodiment, Rb is selected from methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl or 2-butyl; R4, R5 and R6 are each OR, wherein each R Are independently selected from methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl or 2-butyl.

  In one embodiment, compound F2 is selected from methyltrimethoxysilane or methyltriethoxysilane.

Ｃ）式３：

C) Formula 3:

［式中、Ｒｃは、Ｃ＝Ｃ、Ｃ≡Ｃ、Ｃ＝Ｏ、Ｃ＝Ｎ及びＣ≡Ｎを含む２つ以上の多重結合を含み、これらの多重結合は共役配置にあり；Ｒ７、Ｒ８及びＲ９は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］から選択される化合物Ｆ３。更なる実施態様において、Ｒはアルキルである。

[Wherein Rc comprises two or more multiple bonds including C═C, C≡C, C═O, C═N and C≡N, and these multiple bonds are in a conjugated configuration; R7, R8 And R9 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR, wherein R is alkyl or substituted alkyl]. In a further embodiment, R is alkyl.

In one embodiment, Rc is conjugated with aryl or substituted aryl, conjugated diene or conjugated triene, conjugated diketone, conjugated ketoester, α, β unsaturated ester, α, β unsaturated ketone, alkene conjugated nitrile, ketone. Including nitriles, nitriles conjugated to esters, alkynes conjugated to alkenes, alkynes conjugated to ketones or alkynes conjugated to esters;
R7, R8 and R9, OH, are each independently selected from OR or OC (O) R, where R _is a C 1 _{-C 10} alkyl or _C 1 _{-C 10} substituted alkyl. In a further embodiment, R is _C 1 _{-C 10} alkyl.

In one embodiment, Rc is phenyl, naphthyl, anthracene, phenanthrene, fluorene, pyridine, quinoline, imidazole, benzimidazole, indole, carbazole, furan, benzofuran, dibenzofuran. Group, acryloxyl group, acrylamide group, methacryloxyl group or methacrylamide group;
R7, R8 and R9 are each OR, where each R is independently selected from methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl or 2-butyl.

  In one embodiment, compound F3 is selected from phenyltrimethoxysilane or phenyltriethoxysilane.

Ｄ）式４：

D) Formula 4:

［式中、Ｒ１０、Ｒ１１、Ｒ１２及びＲ１３は、アルコキシル、ヒドロキシル、ハロゲン化物、ＯＣ（Ｏ）Ｒ又はＯＣ（Ｏ）ＯＲからそれぞれ独立して選択され、ここでＲは、アルキル又は置換アルキルである］から選択される化合物Ｆ４。更なる実施態様において、Ｒはアルキルである。

Wherein R10, R11, R12 and R13 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR, wherein R is alkyl or substituted alkyl F4 selected from In a further embodiment, R is alkyl.

In one embodiment, R10, R11, R12 and R13, OH, are each independently selected from OR or OC (O) R, wherein R _is, C 1 _{-C 10} alkyl or _C 1 _{-C 10} substituted Alkyl. In a further embodiment, R is _C 1 _{-C 10} alkyl.

  In one embodiment, R10, R11, R12 and R13 are OR, wherein each R is independently methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl or 2-butyl. Selected from.

  In one embodiment, compound F4 comprises tetramethyl orthosilicate or tetraethyl orthosilicate:

から選択される。

Selected from.

  “Substituted alkyl” refers to an alkyl having one or more hydrogens that are substituted with another group containing at least one heteroatom.

  “Substituted aryl” means aryl having one or more hydrogens replaced with another group containing at least one heteroatom.

Three-layer coatings Three-layer coatings, such as three-layer resists, typically comprise: (a) a curable underlayer composition on a substrate; (b) a hard mask composition applied over the curable composition (eg, A hard mask layer formed from the composition of the present invention described herein); and (c) a photoresist composition layer applied over the hard mask composition. The substrate is suitably any substrate used in methods involving photoresist. For example, the substrate can be a silicon, silicon dioxide, aluminum-aluminum oxide microelectronic wafer. Gallium arsenide, silicon carbide, ceramic, quartz or copper substrates can also be used. Substrates for liquid layer displays or other flat panel display applications are also suitably used, such as glass substrates, indium tin oxide coated substrates, and the like. Substrates for optical and optoelectronic devices (eg, waveguides) can also be used. Coating compositions and lithographic methods are described in US Patent Application Publication No. 2007/0238052 and US Patent Application Publication No. 2009/0148789, each incorporated herein by reference.

  A variety of photoresists can be used in combination (ie, overcoated) with the coating composition of the present invention. Preferred photoresists include chemically amplified resists, particularly positive-acting or negative-acting photoresists containing one or more photoacid generator compounds, and photoacid-labile esters, acetals. , Resin components containing units that undergo a deblocking or cleavage reaction in the presence of a photogenerated acid, such as ketal or ether units.

  Negative photoresists such as resists that crosslink (ie, harden or harden) upon exposure to activating radiation can also be used with the coating compositions of the present invention. Preferred photoresists for use with the coating compositions of the present invention have relatively short wavelength radiation, such as radiation having a wavelength of less than 300 nm or less than 260 nm, such as about 248 nm, or a wavelength of less than about 200 nm, such as 193 nm. Can be imaged with radiation.

  Suitable photoresists contain an imaging effective amount of a photoacid generator compound and one or more resins. Suitable resins include i) phenolic resins containing acid labile groups (see, eg, US Pat. Nos. 6,042,997 and 5,492,793); ii) vinylphenol, hydroxyl Or polymers containing polymerized units of alkyl acrylates such as unblocked groups described with optionally substituted vinylphenyl (eg, styrene) and polymers of i) above that do not contain carboxyl ring substituents, eg, US Polymers described in US Pat. No. 6,042,997; iii) polymers containing a repeat unit containing an acetal or ketal moiety that reacts with a photoacid and optionally an aromatic repeat unit such as a phenyl or phenol group (such as New polymers are described in US Pat. Nos. 5,929,176 and 6,090,526. Are) include, but are not limited to.

  Additional resins provide resins that are substantially or completely free of phenyl or other aromatic groups and chemically amplified resists that are particularly suitable for imaging at wavelengths below 200 nm, such as 193 nm. Resins that can be included. Preferred resins of this class include: i) polymers containing polymerized units of non-aromatic cyclic olefins (intracyclic double bonds) such as optionally substituted norbornene, such as US Pat. No. 5,843, Polymers described in 624 and 6,048,664; ii) for example t-butyl acrylate, t-butyl methacrylate, methyl adamantyl acrylate, methyl adamantyl methacrylate, and other acyclic alkyls And polymers containing alkyl acrylate units such as cycloaliphatic acrylates (such polymers are described in US Pat. Nos. 6,057,083, European Patent Application Publication Nos. 01008913A1 and 01005422A1); And iii) European Patent Application Publication No. 01008913A1 and US Pat. No. 6,0 Such as those disclosed in JP 8,662, polymerized anhydride units include polymers containing particular polymerization of maleic anhydride and / or itaconic anhydride units.

  Other resins contain repeating units containing heteroatoms, especially oxygen and / or sulfur (but no anhydrides, ie the units do not contain carbonyl ring atoms), preferably substantially or Completely free of any aromatic units. Preferably, the heteroalicyclic unit is condensed to the resin backbone, and more preferably, the resin is a condensed carbon alicyclic unit such as that resulting from polymerization of a norborene group and / or maleic anhydride or itacon. Those containing anhydride units such as those resulting from polymerization of acid anhydrides. It is also a fluorinated aromatic group such as a fluorostyrene compound that can be brought about by polymerization of a resin (fluoropolymer) containing fluorin substitution, for example, tetrafluoroethylene.

Definitions The term “composition” as used herein includes a composition and a mixture of materials including reaction products and decomposition products formed from the materials of the composition.

  The term “polymer” as used herein means a polymeric compound prepared by polymerizing monomers, whether of the same or different types. Thus, the general term polymer refers to the term homopolymer (used to mean a polymer prepared from only one monomer and it is understood that trace impurities can be incorporated into the polymer structure) And the term interpolymer as defined below.

  The term “interpolymer” as used herein means a polymer prepared by the polymerization of at least two different types of monomers. The general term interpolymer includes copolymers (used to mean polymers prepared from two different monomers) and polymers prepared from three or more different types of monomers.

  The term “prepolymer” as used herein is, for example, from about 500 g / mole to 100,000, g / mole, preferably 500 to 50,000 g / mole (determined by conventional GPC as described below. A) having a molecular weight Mw (weight average).

  The term “multiple bond” as used herein can mean either a double bond or a triple bond.

  The term “conjugated configuration” as used herein refers to an alternating pattern in which two multiple bonds are separated by one single bond (eg, “double bond-single bond-double bond” or “triple”. Bond-single bond-double bond "or" double bond-single bond-triple bond ") means the arrangement of multiple bonds occurring in the compound. In the conjugated configuration, multiple bonds can independently be double or triple bonds. Two or more alternating patterns can exist in a compound having a conjugated configuration of bonds. Examples of compounds having a conjugated bond are benzene, 1,4-butadiene, furan, acrylonitrile and acrylic acid.

  The terms “comprising”, “including”, “having” and their derivatives exclude the presence of any additional ingredients, steps or procedures, regardless of whether they are specifically disclosed. Not what you want. For the avoidance of doubt, all compositions claimed by use of the term “comprising” include any additional additives, auxiliaries or compounds, unless otherwise stated, Whether or not. In contrast, the term “consisting essentially of” excludes from the enumeration of any enumeration that follows any other components, steps or procedures, except those not essential for operability. The term “consisting of” excludes any component, step or procedure not specifically delineated or presented.

Determination of molecular weight by test method GPC (conventional) The molecular weight of the prepolymer was monitored by gel permeation chromatography (GPC), also called size exclusion chromatography (SEC). The instrument was equipped with a column set suitable for measuring molecular weights in the range of about 500 g / mol to at least about 100,000 g / mol based on polystyrene calibration standards. A particularly effective one is Thomson Instrument Co. Set of two “SHODEX LF-804 GPC columns”, 8 mm in diameter and 300 mm in length, installed in series. The mobile phase was tetrahydrofuran and was pumped at a rate of 1 mL / min. The instrument was also equipped with a refractive index detector. Calibration was performed using polystyrene standards available from Polymer Standards Service GmbH, Mainz, Germany. Mn, Mw and MWD are available from Agilent Technologies, Inc. Calculations were performed using ChemStation software “GPC-addon” available from:

Single layer coating Each prepolymer was spin coated onto a silicon wafer to obtain a single layer thin film coating for analysis. In a clean room environment (about 72 ° F., about 50% RH, class 100), WaferNet Inc. A non-primed “200 mm” diameter silicon wafer was used as the substrate. The composition was manually distributed on a Si wafer and spin coated to a nominal film thickness of 35 nm (measured with a THERMA-WAVE spectroscopic ellipsometer) by Tokyo Electron's “TEL ACT-8 Coat Track”. The coated wafer was baked at the specified temperature for 60 seconds (see Table 2) to obtain the formulation ID presented in Table 2. The wafer was then subjected to evaluation by water contact angle, strip test and refractive index measurement.

Measurement of water contact angle As discussed above, single layer coatings were analyzed within 1 hour of coating. A DATAPHYSICS Instruments GmbH OCA20 angle finder was used for all contact angle measurements. Deionized water was used as the test solution. One microliter droplet was used for each contact angle determination. After dispensing the droplets on the surface of the monolayer coating, the droplet movements were recorded for a minimum of 10 seconds with each measurement using a goniometer camera with a minimum speed of 3 frames / second. The contact angle was determined using the initial drop image when the clinometer needle was completely removed from the field of view and there was no drop movement. The contact angle was evaluated using a circular model of OCA software. A minimum of three separate measurements were made throughout the monolayer coating (3 droplets per monolayer coating). A typical standard deviation for contact angle measurements is about 0.2 degrees.

  Film quality is important to obtain a good pattern during the photolithography process. The layer of the present invention may be used in a multilayer scheme in which another layer is coated over the layer of the present invention. If the surface energy of the inventive layer is too low as indicated by the high water contact angle, defects such as dewet that occur when the membrane does not completely cover the coated area are Can appear in the film layer. In order to minimize surface defects in adjacent layers, the water contact angle of the layers of the present invention is preferably less than 87 °.

Strip Value Measurement After spin coating to form a single layer, the film was inspected for solvent resistance by a solvent strip test using a TEL ACT8 track. The prepared wafer was exposed to PGMEA with a “90 second puddle” followed by a soft bake at 110 ° C. for 60 seconds. The change in thickness was measured with a Thermowave Optiprobe. Positive values were indicated as film thickness loss. The same sample is then exposed to MF26A developer (tetramethylammonium hydroxide solution, TMAH) in a “60 second paddle”, followed by soft baking at 110 ° C. for 60 seconds, and the difference in thickness is again measured using the Thermowave Optiprobe Measured using. In the developer strip test, a positive value indicating the film thickness was obtained. A minimum strip value is desirable to indicate resistance to stripping or expansion.

Refractive Index Measurement The experimental section describes two refractive indices: n ₁₉₃ and n ₆₃₃ .

n ₁₉₃
The optical properties and thickness of the films were measured using a WOOLAM VUV-VASE VU-302 ellipsometer (Woolam, NE). The membrane was coated on a “200 mm” diameter bare silicon wafer as described above in a single layer coating process. Polarization data was collected at three angles over the wavelength range of 170 nm to 900 nm. Data is automatically generated to obtain the film thickness and refractive index (n, k) at 193 nm, where n is the real part of the complex refractive index and k is the imaginary part of the complex refractive index. It is.

n ₆₃₃
For faster screening, some samples were analyzed only by coating, strip test, contact angle and refractive index at 633 nm. After spin coating as described in the single layer method, the wafer was subjected to strip testing using a TEL ACT8 track. The wafer was then subjected to contact angle measurement. Finally, the refractive index was determined by a Thermawave Optiprobe at a wavelength of 633 nm.

Experimental Materials The materials used in the present invention were obtained from commercial suppliers and used as received. Raw material abbreviations and suppliers are:
V = VTMS: vinyltrimethoxysilane (Sigma Aldrich, Dow Corning),
M = MTMS: methyltrimethoxysilane (Sigma Aldrich, Dow Corning),
Ph = PTMS: phenyltrimethoxysilane (Sigma Aldrich, Dow Corning),
TEOS: tetraethyl orthosilicate (Sigma Aldrich, Dow Corning),
PGMEA: Propylene glycol monomethyl ether acetate (DOWANOL PMA, The Dow Chemical Company),
BTEAC: benzyltriethylammonium chloride (Sigma Aldrich),
BTMAC: benzyltrimethylammonium chloride (Sigma Aldrich),
BTBAC: benzyltributylammonium chloride (Sigma Aldrich),
BTEABr: benzyltriethylammonium bromide (Sigma Aldrich),
BDHDAC: benzyldimethylhexadecyl ammonium chloride (Sigma Aldrich),
PhTMAC: phenyltrimethylammonium chloride (Sigma Aldrich),
TMAC: Tetramethylammonium chloride (Sigma Aldrich),
AC: ammonium chloride, NH ₄ ⁺ Cl ⁻ (Sigma Aldrich),
GuanHCl: guanidine hydrochloride (Sigma Aldrich) and THMP: trishydroxymethylpropane (Sigma Aldrich).

  A “3N aqueous acetic acid solution” was prepared in the laboratory. Glacial acetic acid was supplied by JT Baker.

  “0.1N aqueous hydrochloric acid solution” was prepared in the laboratory. Concentrated hydrochloric acid was supplied from Fisher.

The curing catalyst structure is shown below.
BTEAC:

ＢＴＭＡＣ：

BTMAC:

ＢＴＢＡＣ：

BTBAC:

ＢＴＥＡＢｒ：

BTEABr:

ＢＤＭＨＤＡＣ：

BDHDAC:

ＰｈＴＭＡＣ：

PhTMAC:

ＴＭＡＣ：

TMAC:

及びＧｕａｎＨＣｌ：

And GuanHCl:

  The prepolymer was synthesized by a typical sol-gel procedure in which the silane monomer is first hydrolyzed with water and acid and then condensed to a prepolymer network. The synthesis section details the synthesis of each prepolymer batch used in the test. The composition of each prepolymer is shown in Table 1. The formulation and spin coating section details how the prepolymer was diluted for single layer coating of the wafer. The last section details the evaluation of wafers prepared by coating and annealing. Table 2 shows the formulation ID, and Table 3 represents the evaluation of these formulations after coating.

Synthetic prepolymer 1 of the present invention and comparative prepolymer 1
A three-necked 500 mL flask was equipped with a temperature probe, an overhead stirrer with a 2 inch TEFLON paddle and a syringe pump addition adapter. The flask was initially charged with acetic acid (3N, 24.31 g). Silane monomers (PTMS 8.95 g, VTMS 11.11 g, MTMS 24.49 g, TEOS 41.60 g) and the first aliquot (65 g) of PGMEA are weighed into NALGENE bottles and placed in a reaction flask over 1 hour at room temperature with a syringe pump. Moved. The syringe adapter was then replaced with a Dean-Stark trap and cooler under nitrogen flow. The reaction mixture was heated with an oil bath (set point 100.0 ° C.) for distillate collection. After 45 minutes, another aliquot of PGMEA (50 g) was added and the temperature ramped to 125 ° C. while continuing to collect distillate. After 1 hour, the Dean Stark trap was removed and the reaction was cooled. At this point, the GPC aliquot was removed to give Mw 3018 g / mol. The flask was reheated in a 125 ° C. oil bath until the target molecular weight was obtained. When the polymer solution reached a molecular weight close to the target (5000 g / mol), the solution was diluted with a third charge of PGMEA (20 g) and cooled to room temperature. Samples were prepared for analysis by diluting the solution to 5% solids with PGMEA. (Solid content concentration of 23.01%, weight average molecular weight of 5925 g / mol according to PS standard).

Prepolymer 2
A three-neck 250 mL flask was equipped with a temperature probe, constant RPM overhead stirrer with 2 inch TEFLON paddle and syringe pump addition adapter. Distilled silane monomers phenyltrimethoxysilane (7.03 g, 35.4 mmol), methyltrimethoxysilane (38.12 g, 279.8 mmol) and tetraethyl orthosilicate (16.42 g, 78.8 mmol) were weighed to give a plastic. Place in bottle, transfer to reaction flask and dilute with 65.5 mL PGMEA. Hydrochloric acid (0.1N, 3.95 mL, 3.95 mmol) is diluted with HPLC grade water (19.49 mL, 1082 mmol), mixed with a graduated cylinder, and then the silane solution is syringe pumped at ambient room temperature over 30 minutes. Added dropwise. When the “acid / water solution addition step” was completed, the syringe pump addition adapter was replaced with a short path distillation head fitted with a nitrogen line, and then the solution was then heated in an oil bath at the set point of 100 ° C. Reaction aliquots (0.2 mL) were frequently removed and diluted with THF (1.0 mL) for analysis by GPC. The polymer solution reached a molecular weight close to the target (5000 g / mol) after heating for 75 minutes. The solution was diluted to 21.9 wt% solids based on the total weight of the solution by addition of PGMEA (46.8 mL, 342 mmol) and cooled to room temperature. The solution was added to Dow Chemical Co. Stirred with an excess equivalent of DOWEX MARATHON MR-3 mixed ion exchange resin produced by, and then filtered through a “0.2 μm” PTFE syringe filter. Molecular weight was determined by GPC: Mw 4079 g / mol; Mn 1798 g / mol; MWD 2.27.

Prepolymer 3
A three-necked 500 mL flask was equipped with a temperature probe, an overhead stirrer with a 2 inch TEFLON paddle and a syringe pump addition adapter. The flask was initially charged with acetic acid (3N, 73.30 mL). Silane monomers (PTMS 18.85 g, VTMS 23.49 g, MTMS 37.42 g, TEOS 110.05 g) and the first aliquot (175 mL) of PGMEA are weighed into NALGENE bottles and placed in a reaction flask with a syringe pump at room temperature for 1 hour. Moved. The syringe adapter was then replaced with a Dean-Stark trap and cooler under a stream of nitrogen and the reaction continued to stir at ambient temperature for 15 minutes. The reaction mixture was heated for 3 hours with an oil bath (set point 100.0 ° C.) for distillate collection. After 3 hours, the temperature was ramped to 110 ° C. with continued distillate collection. When distillation stopped, the polymer solution solution was diluted with a second charge of PGMEA (125 mL) and cooled to room temperature. Samples were prepared for analysis by diluting the solution to 5% solids with PGMEA. (According to PS standard, solid content concentration of 20.19%, weight average molecular weight of 3474 g / mol).

Prepolymer 4
A three-neck 250 mL flask was equipped with a temperature probe, constant RPM overhead stirrer with 2 inch TEFLON paddle and syringe pump addition adapter. Distilled silane monomers phenyltrimethoxysilane (7.77 g, 39.0 mmol), vinyltrimethoxysilane (9.69 g, 65.1 mmol) and tetraethyl orthosilicate (68.68 g, 329.7 mmol) were weighed into a plastic. Place in bottle, transfer to reaction flask and dilute with 70.0 mL PGMEA. Hydrochloric acid (0.1N, 2.17 mL) was diluted with HPLC grade water (23.63 mL), mixed with a graduated cylinder, and then added dropwise to the silane solution by syringe pump at ambient room temperature over 30 minutes. When the “acid / water solution addition step” was completed, the syringe pump addition adapter was replaced with a short path distillation head fitted with a nitrogen line and stirred for 45 minutes at ambient temperature. The solution was then heated in the oil bath at the set point of 100 ° C. Reaction aliquots (0.2 mL) were frequently removed and diluted with THF (1.0 mL) for analysis by GPC. The polymer solution reached a molecular weight close to the target (5000 g / mol) after heating for 3.5 hours. The solution was diluted to “21.8 wt% solids” based on the total weight of the solution by addition of PGMEA (50.0 mL) and cooled to room temperature. The solution was stirred with an excess equivalent of DOWEX MARATHON MR-3 mixed ion exchange resin manufactured by The Dow Chemical Company and then filtered through a “0.2 μm” PTFE syringe filter. Molecular weight was measured by GPC: Mw 3701 g / mol; Mn 1442 g / mol; MWD 2.57.

Prepolymer 5
A three-necked 500 mL flask was equipped with a Dean-Stark trap and condenser, an overhead stirrer with a 2 inch TEFLON paddle and a syringe pump addition adapter. The flask was initially charged with distilled silane monomer (PTMS 16.34 g, VTMS 20.36 g, MTMS 32.43 g, TEOS 95.38 g) and the first aliquot of PGMEA (151.67 g). Glacial acetic acid (11.55 g) and HPLC grade water (51.98 g) were weighed into a NALGENE bottle and added dropwise by syringe pump over 30 minutes at ambient temperature and transferred to the reaction flask. The reaction mixture was stirred for an additional 60 minutes at ambient temperature. The syringe adapter was then replaced with a temperature probe and the reaction mixture was heated with an oil bath (set point 100.0 ° C.) for distillate collection. Distillate was collected until a pot temperature of about 90 ° C. was achieved. The solution was then diluted with PGMEA (108.38 g) and cooled to room temperature. The solution was filtered through a “0.2 μm” PTFE syringe filter. Molecular weight was measured by GPC: Mw 3333 g / mol; Mn 1580 g / mol; MWD 2.11 [solids concentrate 19.0 wt%].

Prepolymer 6
A three-necked 500 mL flask was equipped with a temperature probe, an overhead stirrer with a 2 inch TEFLON paddle and a syringe pump addition adapter. The flask was initially charged with distilled silane monomer (PTMS 16.34 g, VTMS 20.36 g, MTMS 32.44 g, TEOS 95.39 g) and the first aliquot of PGMEA (151.69 g). Glacial acetic acid (11.55 g) and HPLC grade water (51.98 g) were weighed into a NALGENE bottle and added dropwise by syringe pump over 30 minutes at ambient temperature and transferred to the reaction flask. The reaction mixture was stirred for an additional 60 minutes at ambient temperature. The syringe adapter was then replaced with a Dean-Stark trap and a condenser, and the reaction mixture was heated with an oil bath (set point 100.0 ° C.) for distillate collection. Distillate was collected until a pot temperature of about 90 ° C. was achieved. The solution was then diluted with PGMEA (108.33 g) and cooled to room temperature. The solution was filtered through a “0.2 μm” PTFE syringe filter. Molecular weight was measured by GPC: Mw 2864 g / mol; Mn 1417 g / mol; MWD 2.02 [solids concentrate 18.6 wt%].

Composition First Composition-Prepolymer Solution Formulation Table 1 presents a different first composition of the prepolymer used in the present invention. Amount units are mole percent based on the total number of moles added to prepare the composition. The corresponding synthesis is discussed in the section “Synthesis of the invention and comparative prepolymers”.

Formulation and Spin Coating Before spin coating, the prepolymer solution is diluted from the concentrated solution with PGMEA to a 2 wt% solution, unless otherwise indicated, 1 wt% malonic acid and 0.1 wt% curing catalyst. Was added (based on solids). The curing catalyst was prepared as an equimolar solution (0.004M) for better comparison among the samples of the first set (Formulations 1-9). Other comparative examples were formulated with either 0.02 wt% curing catalyst or 0.1 wt% curing catalyst based on the polymer (see Table 2). The formulation was filtered through a “0.2 micron” PTFE filter to form a SiARC formulation ID.

  For Formulations 1-9, Prepolymer 1 (5 wt% assay with PGMEA, 5.934 g, 98.9% of "2 wt% solids"), malonic acid (1.0 wt% assay with PGMEA, 0.30 g, 1% of “2 wt% solids) and curing catalyst (0.1 wt% assay with ethyl lactate, 0.3 g, 0.1% of“ 2 wt% solids ”) PGMEA Dilute with (8.466 g).

  In Formulation 10, Prepolymer 2 (5 wt% assay with PGMEA, 5.939 g, 98.98% of “2 wt% solids”), malonic acid (1.0 wt% assay with PGMEA, 0. 30 g, 1% of “2 wt% solids” and curing catalyst (0.1 wt% assay with ethyl lactate, 0.060 g, 0.02% of “2 wt% solids”) were added to PGMEA (8 .701 g).

  In formulations 11-14, the corresponding prepolymer (5 wt% assay with PGMEA, 5.934 g, 98.9% of "2 wt% solids"), malonic acid (1.0 wt% assay with PGMEA) 0.30 g, 1% of “2 wt% solids) and curing catalyst (0.1 wt% assay with ethyl lactate, 0.3 g, 0.1% of“ 2 wt% solids ”), Dilute with PGMEA (8.466 g).

  In formulations 15-18, the corresponding prepolymer (5 wt% assay with PGMEA, 5.936 g, 92.9% of "2 wt% solids"), malonic acid (1 wt% assay with PGMEA, 2 .237 g, 7% of “2 wt% solids” and curing catalyst (0.1 wt% assay with ethyl lactate, 0.320 g, 0.1% of “2 wt% solids”) were added to PGMEA ( 4.625 g), ethyl lactate (0.415 g) and oleyl alcohol (1.468 g).

  Table 2 summarizes all the formulations used in this study. Refer to data in different sections for a better comparison. It is ideal to compare the set of Formulations 1-9, Formulation 10, Set of Formulations 11-13, Formulation 14 and Formulations 15-18, as each set is annealed under different conditions. This is because they are blended or differently (specified in the headers of Tables 2 and 3).

Characterization of film properties SiARC thin films were formed by spin-coating onto a “200 mm” HQ silicon substrate followed by curing for 60 seconds at the reported temperature (° C.) on a hot plate. All wafers were processed with TEL ACT8 Coat Track.

  After blending the formulation according to Table 2, the filtered solution was spin coated onto a silicon wafer and subjected to strip test, contact angle and infrared measurements.

Summary Screening suggested that denser films showed increased contact angle, decreased refractive index and decreased strip value, each resulting from improved crosslinking. As can be seen from Table 3, the formulations of the present invention (Formulations 2, 5, 6, 7) in which at least one R group of the curing agent is methyl are comparative examples (Formulations 1, 3, 4, 8, Compared to 9), it had better solvent resistance and developer strip. The comparative formulation does not show optimum strip performance, which indicates a lower degree of cure. It is hypothesized that the formulations of the present invention provide a higher degree of cure and therefore a smaller amount of free silanol remains in the film. Also, the contact angle (CA) should change as a function of curing. As silanols (lower CA) condense to form siloxane bonds (higher CA), the contact angle increases to form a more hydrophobic surface. Table 3 shows that the formulation of the present invention increased the contact angle compared to the comparative formulation. However, the contact angle can be too high, causing surface defects and poor coverage. The preferred contact angle range is preferably less than 87 °. The formulations of the present invention form materials having low strip values, reduced refractive index values and water contact angles within the required range.

  When the formulation contains polyhydric alcohol THMP, the strip increases compared to the control composition and the contact angle decreases, indicating a lower degree of cure in the membrane. (See Formulations 11-13 in Table 3). Those skilled in the art will expect similar trends for the other curing catalysts disclosed herein because the alcohol did not improve performance.

  In addition, as can be seen from formulations 10 and 14 containing only three silane monomers, their properties were not improved. In formulation 10, which lacks VTMS monomer and has a large increase in MTMS, the film lacks the refractive index required for electronic applications, and the contact angle exceeds the preferred range discussed above, which Results in poor coating performance. Formulation 14 lacking MTMS and having a large increase in TEOS showed reasonable contact angle values, strip values, met refractive index requirements, but surface defects were present in the film.

Claims (15)

At least A) Formula A:
[NR1′R2′R3′R4 ′] ⁺ X ⁻ (Formula A)
[R1 ′, R2 ′, R3 ′, R4 ′ are each independently selected from hydrogen, alkyl, substituted alkyl, aryl, or substituted aryl;
X is a monovalent anion,
Wherein in formula A, at least one of R1 ′, R2 ′, R3 ′ or R4 ′ is methyl]
A curing catalyst selected from:
B)
a) Formula 1:

[Wherein Ra includes one or more multiple bonds, provided that when Ra includes two or more multiple bonds, these multiple bonds are not in conjugated configuration; R1, R2 and R3 are alkoxyl , Hydroxyl, halide, OC (O) R or OC (O) OR each independently, where R is alkyl or substituted alkyl]
Compound F1 selected from:
b) Equation 2:

Wherein Rb is selected from H or a saturated group including alkyl, alkylene or alkylidene; R4, R5 and R6 are each independently alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR Wherein R is alkyl or substituted alkyl]
Compound F2 selected from:
c) Equation 3:

[Wherein Rc contains two or more multiple bonds, and these multiple bonds are in a conjugated configuration; R7, R8 and R9 are alkoxyl, hydroxyl, halide, OC (O) R or OC (O) Each independently selected from OR, where R is alkyl or substituted alkyl]
Compound F3 selected from:
d) Equation 4:

Wherein R10, R11, R12 and R13 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R or OC (O) OR, wherein R is alkyl or substituted alkyl ]
Compound F4 selected from
And a prepolymer formed from a first composition comprising:   The composition of claim 1, wherein the first composition comprises less than 2 weight percent of a trihydric or higher polyhydric alcohol based on the weight of the prepolymer.   3. A composition according to claim 1 or claim 2 wherein in formula A, at least two of R1 ', R2', R3 'or R4' are each methyl.   The composition according to any one of claims 1 to 3, wherein R1 ', R2', R3 ', R4' are each independently selected from hydrogen, C1-C3 alkyl or aryl.   5. A composition according to any one of the preceding claims comprising less than 1 ppm metal oxide based on the weight of the composition.   6. A composition according to any one of the preceding claims comprising less than 1 ppm "light absorbing dye" based on the weight of the composition.   A crosslinked composition formed from the composition according to claim 1.   An article comprising at least one component formed from the composition of any one of claims 1-7.   A film comprising at least one layer formed from the composition according to claim 1.   The membrane of claim 9, further comprising a second layer formed from a third composition comprising a polymer. A method of forming a coating on a substrate, comprising at least preparing the substrate,
Forming an underlayer comprising at least one polymer on a substrate;
Applying the composition according to any one of claims 1 to 6 on the lower layer,
Curing the composition to form a coating.   The method of claim 11, wherein multiple layers of the composition are applied on an underlayer.   13. A method according to claim 11 or claim 12, wherein the coating is an antireflective layer. A method of forming a coating on a substrate, comprising at least preparing the substrate,
Applying the composition according to any one of claims 1 to 6 on at least a part of the substrate or on one or more intermediate layers applied on the substrate;
Curing the first composition or the second composition to form a film.   15. The method of claim 14, wherein a multilayer of the composition is applied on at least a portion of the substrate or on one or more intermediate layers applied on the substrate.