TW201001080A - Resist underlayer forming composition for lithography comprising resin containing aromatic fused ring - Google Patents

Abstract

Disclosed is a resist underlayer film-forming composition for lithography, which is effective during processing of a semiconductor substrate. Also disclosed are a resist pattern forming method using the resist underlayer film-forming composition, and a method for manufacturing a semiconductor device. The resist underlayer film-forming composition contains a polymer containing structural units represented by formula (1) and formula (2), a crosslinking agent and a solvent. When the total number of all structural units constituting the polymer is taken as 1.0, the ratio of the number (a) of the structural units represented by formula (1) and the ratio of the number (b) of the structural units represented by formula (2) are respectively within the following ranges: 0.3 ≤ a ≤ 0.95 and 0.05 ≤ b ≤ 0.7. The composition contains 3-30% by mass of the crosslinking agent relative to the solid content which is obtained by excluding the solvent from the composition.

Description

[Technical Field] The present invention provides a micro-layer film forming composition which is effective in processing a semiconductor substrate, a composition pattern forming method using the photoresist underlayer film, and a method of manufacturing a semiconductor device. [Prior Art] In the past, in the manufacture of a semiconductor device, fine processing was performed using a photoresist composition. The microfabrication is to form a thin film of a photoresist composition on a substrate such as a tantalum wafer, and irradiate active light such as ultraviolet rays through a pattern of a pattern of a drawing device, and use the obtained photoresist pattern as a protective film. A method of etching and processing a wafer substrate. However, in recent years, the active light of the semiconductor device has a tendency to be short-wavelength from the KrF excimer laser (248 nm) toward the laser (1 93 nm). The influence of the disordered reflection or standing wave from the substrate along with this line becomes a big problem. An anti-reflection film (BARC Anti-Reflective Coating) is placed between the photoresist and the substrate to be processed. . In the future, if the miniaturization of the photoresist pattern continues to progress, the problem of difficulty in improving the resolution and the pattern of the photoresist pattern are required for development. Therefore, it is desirable to form a thin film of the photoresist film. However, it becomes more difficult to obtain a sufficient photoresist pattern film by processing a film sheet. The photoresist which is not used for the photoresist is processed into a semiconductor, and is processed by development. ArF quasi-fraction, active light. Therefore, the :Bottom method is widely used due to the collapse of the damage, based on the photoresist pattern only -5 to 201001080 type, and the photoresist film under the photoresist film and the processed semiconductor substrate also has a substrate as a substrate. The process of the function of the reticle during processing is also necessary. As the photoresist underlayer film for such processes, it is required to have a photoresist for lithography having a selectivity ratio close to the dry etching rate of the photoresist film different from the conventional high etching (fast etching speed) photoresist underlayer film. The lower film, the lower etch rate than the photoresist film, the lithographic underlayer film or the lithographic underlayer film having a dry time speed smaller than that of the semiconductor substrate (for example, refer to Patent Documents 1 to 4). ). Further, it is also possible to impart anti-reflection energy to the photoresist underlayer film, and it is also required to have the function of the conventional anti-reflection film. Patent Document 1: JP-A-2002-296789 Patent Document 2: JP-A-2004-177668 Patent Document 3: JP-A-2004-271838 Patent Document 4: JP-A-2005-250434 [Summary of the Invention] In order to solve these problems, the present invention provides a composition for forming a lithographic underlayer film which is effective for processing a semiconductor substrate. Moreover, the present invention provides a lithographic photoresist underlayer film having a selection ratio of a dry etching rate close to a dry etching rate of the photoresist film, and a dry etching rate smaller than that of the photoresist film or A lithographic underlayer film having a smaller dry etching rate than a semiconductor substrate. Furthermore, the present invention provides a photoresist pattern forming method -6-201001080 using a photoresist underlayer film forming composition, and a method of manufacturing a semiconductor device. [Means for Solving the Problems] The present inventors have found and completed the present invention as a result of actively studying the above problems. In other words, the first aspect is a photoresist underlayer film forming composition used in a lithography process for manufacturing a semiconductor device, characterized in that the composition includes each unit structure represented by the following formulas (1) and (2). Polymer: [Chemical 1]

Ri R2

R3 R4

Μ

I (C=〇)n I ^ O'C-〇-Rg CH-Re r7 (In the above formula, X represents a hydrogen atom or an aromatic condensed ring, Y represents an aromatic condensed ring, and further, X and Y may bond each other The condensed ring is formed, and Ri, R2, R3, R4 and R5 each represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, and R6, R7 and R8 represent a hydrogen atom or a carbon atom number of 1 to 10, respectively. An alkyl group, R9 represents an alkyl group having 1 to w carbon atoms, and R7 and R8 may be bonded to each other to form a ring, Μ represents a direct bond or a linking group, and 201001080, η represents 0 or 1), and is constituted by When the total number of all unit structures of the polymer is 1.0, the ratio of the ratio of the unit structure number (a) expressed by the above formula (1) to the unit structure number (b) expressed by the above formula (2) is 〇.3Sa each of 0.95, 0.05 Sb$0.7 of the polymer, and the composition further contains a crosslinking agent and a solvent, and the composition contains 3 to 30% by mass based on the solid content of the composition from which the solvent is removed. The second viewpoint is a photoresist underlayer film forming composition used in a lithography process for manufacturing a semiconductor device, and its characteristics The composition includes, in addition to the polymer having a unit structure represented by the above formulas (1) and (2), and further comprising at least two protected carboxyl groups or protected hydroxyl groups represented by the following formula (3) in the molecule. Compound: [Chemical 2] (c=〇) n I Re Formula (3) 0~C—O—Rg ch-r8 r7 (In the above formula, R6, R? and Rs respectively represent a hydrogen atom or a carbon number of 1 to An alkyl group of 10, R9 represents an alkyl group having 1 to 1 carbon atom, and R7 and R8 may also be bonded to each other to form a ring 'n represents 0 or 丨)' and is constructed in all units constituting the polymer. When the total number of the compounds and the number of the compounds is 1.0, the ratio of the unit structure number (a) expressed by the above formula (1) and the unit structure number represented by the above formula (2) are expressed by the above formula (3). The total number of compounds (b) is 上述· 3 S a $ 0 · 9 5, -8-201001080 0.05 ^b ^ O.7 of the above polymer and the above compound, and the composition further contains a crosslinking agent And the solvent, wherein the composition contains 3 to 30% by mass of the crosslinking agent based on the solid content of the solvent from which the composition is removed. The third viewpoint is a photoresist underlayer film forming composition as described in the first aspect or the second aspect, wherein the unit represented by the above formula (1) is selected from the group consisting of ethylene naphthalene, ethyl phthalate (Acenaphthylene), and B. Unit structure of dilute oxime, N-vinylcarbazole or such derivatives. The fourth aspect is the photoresist underlayer film forming composition according to any one of the first aspect to the third aspect, further comprising an acid or an acid generator. The fifth aspect is a photoresist underlayer film obtained by applying the photoresist underlayer film forming composition according to any one of the first to fourth aspects onto a semiconductor substrate and firing. The sixth aspect is a method for forming a photoresist pattern, which is characterized in that the photoresist underlayer film forming composition according to any one of the first aspect to the fourth aspect is coated on a semiconductor substrate and fired. In the semiconductor fabrication of the step of forming an underlayer film. The seventh aspect is a method of manufacturing a semiconductor device, comprising the step of forming a lower film by a photoresist underlayer film forming composition according to any one of the first aspect to the fourth aspect, and a step of forming a photoresist film, a step of forming a photoresist pattern by light or electron beam irradiation and development, a step of etching the underlayer film according to the formed photoresist pattern, and a layer film according to the pattern A step of processing a semiconductor substrate. The eighth aspect is a method of manufacturing a semiconductor device, characterized in that the package of the underlayer film forming composition of any one of the first to fourth aspects is formed on the semiconductor substrate. a step of forming a hard mask thereon, and then forming a photoresist film thereon, the step of forming a photoresist pattern by light or electron beam irradiation and development, by forming the photoresist pattern The step of honing the hard mask, the step of drilling the underlying film according to the patterned hard mask, and the step of processing the semiconductor substrate according to the patterned underlying film. [Effect of the Invention] The lithographic underlayer film forming composition of the present invention can achieve a dry etching rate close to that of the photoresist film by selecting a dry etching gas. The choice of speed is better than the choice of the dry etching rate of the semiconductor substrate. Further, the photoresist forming underlayer film forming composition of the present invention can simultaneously have an effect as an antireflection film for exposed light. Further, the photoresist underlayer film forming composition of the present invention can achieve good hard mask crack resistance. That is, the photoresist film formed by the composition of the present invention comprises a unit structure having an aromatic condensed ring, a unit structure having a protected carboxyl group and/or a protected hydroxyl group, and can be crosslinked by the same. The compound enhances solvent resistance or crack resistance by promoting the acid component formed by the crosslinking, thereby realizing a function as a hard mask. [Embodiment] The present invention relates to a lithographic photoresist underlayer film forming composition comprising -10-201001080 a polymer comprising a protected carboxyl group and/or a protected hydroxyl group, a crosslinking agent and a solvent, or containing A protected carboxyl group and/or a protected hydroxyl group polymer, a protected sulfhydryl group and/or a protected rhodium group compound, a crosslinking agent and a solvent, and optionally an additive such as a surfactant. The solid component from which the solvent is removed from the above composition contains 〇" to 70% by mass", preferably containing 1 to 60% by mass. /. . 1 to % by mass, or 10 to 90% by mass, or 20 to 90% by mass or 30 to 90% by mass of the polymer or polymer and the compound having a protected carboxyl group and/or a protected hydroxyl group in the solid content . The invention is described in detail below. The polymer used in the present invention is a polymer each having a unit structure represented by the formula (1) and the formula (2), [Chemical 3]

Formula (1)

In the above formula (1), X represents a hydrogen atom or an aromatic condensed ring, and Y represents an aromatic condensed ring. Further, X and Y may be bonded to each other to form a condensed ring. -11 - 201001080 The aromatic condensed ring is obtained by condensing two or more rings, preferably from 2 to 3 aromatic condensates. The above aromatic condensed ring is exemplified by, for example, a benzofuranyl group, an isobenzopyranyl group, a benzononenyl group, a salinyl group, a diaza naphthyl group, a porphyrin group, a porphyrin group, a naphthyl group. , thiol, carbazolyl and the like. It is preferably a naphthalene ring, an anthracene ring, a fluorene ring or the like based on a naphthyl group, a fluorenyl group or a sulfonyl group. Further, the naphthalene ring may be bonded not only to Y but also to X. The polymer having the unit structure of the above formula (1) is obtained by, for example, polymerizing vinyl naphthalene, vinyl naphthalene, vinyl anthracene, vinyl carbazole or the like. In the above formula (1), each of Ri and R2 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms. The halogen atom is exemplified by a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group having 1 to 3 carbon atoms is exemplified by a methyl group, an ethyl group, a propyl group and an isopropyl group. The unit structure of the above formula (1) is exemplified below. [Chemical 4]

In the above formula (2), the definitions of R3, R4 and R5 are the same as those of R1 and R2 in the above formula (1). Μ represents a direct bond or a divalent linking group (e.g., an aryl group, a hydroxyalkyl group). Examples of the extended aryl group are a stretching phenyl group, a stretching naphthyl group, an exfoliating group, and the like. The hydroxyalkylene group is exemplified by a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group or the like. -12- 201001080 When Μ is a direct bond, the above formula (2) is a unit based on acrylate. R6, R7 and R8 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R9 represents an alkyl group having 1 to 10 carbon atoms. The above alkyl group having 1 to 10 carbon atoms is exemplified by methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, t-butyl, t-butyl, cyclobutyl Base, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl , ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl - n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-positive Butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2 -trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl Cyclohexyl, 1-methyl -cyclopentyl, 2-methyl-cyclopentyl '3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2, 4-Dimethylcyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropane Base, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, -13-201001080 2,2,3- Trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl '2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl and the like. In the above formula (2), R7 and R8 may be bonded to each other to form a ring. In the above formula (2), the case where η is 〇 is a unit structure having a protected hydroxy group. A method for producing a polymer having the unit structure is a method of polymerizing a vinylphenol derivative having a protected hydroxyl group obtained by reacting a vinyl phenol with a vinyl ether, or a polymer of a vinyl phenol and a vinyl ether compound The method of reaction. Further, there is a method of polymerizing a vinyl derivative having a protected hydroxyl group obtained by reacting a hydroxyalkyl (meth) acrylate with a vinyl ether compound, or a polymer of a hydroxyalkyl (meth) acrylate with a vinyl group A method of reacting an ether compound. In the above formula (2), the case where η is 1 is a unit structure having a protected carboxyl group. A method for producing a polymer having the unit structure is a method of polymerizing a acrylate having a protected carboxyl group obtained by reacting (meth)acrylic acid with a vinyl ether compound, or a polymer of (meth)acrylic acid and a vinyl ether The method of compound reaction. Further, there is a method of polymerizing a (α-methyl)styrene derivative having a protected carboxyl group obtained by reacting (α-methyl)styrenecarboxylic acid with a vinyl ether compound, or (α-methyl)styrenecarboxylic acid A method of reacting a polymer with a vinyl ether compound. The vinyl ether compound used therein is represented by the following formula (4). -14- 201001080 [化5]

Formula (4) (wherein, Re, R7, R8, and Κ·9 are the same as defined in the above formula (2)). The reaction of the compound having a carboxyl group with the vinyl ether compound can be carried out, for example, as described in Japanese Unexamined Society, Vol. 34 (Vol. 34), pages 352 to 356, using phosphoric acid as a catalyst and stirring at room temperature. The vinyl ether compound represented by the above formula (4) is exemplified by, for example, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, An aliphatic vinyl ether compound such as a third butyl vinyl ether or a cyclohexyl vinyl ether; and 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, 2,3-dihydro-4? a cyclic vinyl ether compound such as pyran. The unit structure of the above formula (2) is exemplified below. -15- 201001080 1 CH /t 3 5CH3)-0H3I Η3-κ=οΗ-οιο(2 c—c'lc·—0 c ^CH3 3 H2 c )-OH IH3— 9 hcc(2 c-cIc—〇 :-k. Formula H3 2CH H c 0 9H3-1 H3} 9 h-cic(2 c—c·-c:-°·y12

H3 c 3 * H ) HICIC 6 rounds _ 9H32-3h o Hc-C ( H\T ^ I type c-cIcIο i12 CH 3 /TH "fO c 3 HI H c--cc } 9H3-5 £} 9h- Cc(2 CICIC-ot Γ type CH H3 4C h2)4 ^ ) 9h34 9h-c-ic(2-clcic-o12 type CH/T

-°H3 H3H-9H-C-ICetc——c—o 12 CH4V -ο

CH type 2 7 °H3H3l=oH-c-丨 c(2 c Jc'lc: l°

12 CH/T cl-o 8 ? 9H-C-C: 2 CICIC-〇 -0H3 -ο 9 -16- 201001080 [化7]

c=〇 c=〇 c:o

I Η I Η I H O-C-OCH2CH3 0-C-0(CH2)3CH3 O-C-OCH3 ch3 ch3 ch3 Formula (2-10) Formula (2-11) Formula (2-12)

c: 〇IH oco(ch2)4ch3 ch3 c:〇IH ?H3 〇-C-〇-C-CH3 ch3 ch3 c:〇I Η H OCOC-CH3 ch3 ch3 formula (2 - 1 5) formula (2 - 1 3) Equation (2—1 4)

201001080 [Chemical 8] ch3-fc-c-Vh2J, 0-C-OCH2CH3 ch3 (2- 1 9)

0-C-0(CH2)3CH3 ch3 Formula (2- 2 0)

O-c-och3 ch3 (2 - 2 1)

3 r H\T CIC

H3h-c-c. 12' CH

-2 CH 4V

CH9I Η Η ch3 oc-〇(ch2)4ch3 0-C-0-C-CH3 CH3 Formula (2 — 2 2) I CH3 ch3 Formula (2 - 2 3) HH 〇—C-〇—C—CH3 ch3 ch3 Equation (2 - 2 4) CH3 ch3 ch3is.

H 〇-c-〇-(^y ch3 type (2-2 5)

Ho-c-o I ch3 type (2-2 6) -o

Cl H O-C-O I ch3 type (2-2 7) -18- 201001080 [Chemistry 9]

Ch3c=o I o ch2chό HC~OCH2CH3 ch3 Formula (2-2 8) ch3c=o ch3c=o I9 ch2ch ό HC-〇(CH2)3CH3 ch3 Formula (2_2 9) ^rt>3 c=0 ch2ch hc-och3 Ch3 ^ (2-3 0) ch3ti ten c=oo ch2ch 0 HC-0(CH2)4〇H3 ch3 Formula (2-3 1) ch3c=o I o ch2chHC-O^O ch3 Formula (2-34) o Ch2ch ό ch3 HC-0-C-CH3 ch3 ch3 Formula (2 — 3 2) c=〇ch3oo o ch2ch ch3 Formula (2-3 5) o ch2ch ό H HC-OC-CH II ch3 ch3 Formula (2 - 3 3) CHZ I;?c = 〇I 9 ch2chH£f-°-〇ch3 Formula (2-3 6) The weight average molecular weight of the polymer used in the present invention is 1,000,000, preferably 1,000 to 200,000. These molecular weights are analyzed and converted into molecular weights obtained by polyethylation. The measurement conditions of the GPC can be, for example, a GPC apparatus (product 4 8 220 GPC 'made by Tosoh Corporation), a GPC column (Shodex KF803L, KF802, KF801, manufactured by Showa Denko), a temperature of 40 ° C, and a solution (dissolved solvent). For tetrahydrofuran, the flow rate of 100 to 'Λ GPC 1 HLC-product name' tube volume (flow -19-201001080 speed) was 1.0 ml/min, and the standard sample was made of polystyrene (manufactured by Showa Co., Ltd.). Further, the synthesis of a polymer each having a unit structure represented by the formulas (1) and (2) may be carried out by using another addition polymerizable monomer. Examples of the addition polymerizable monomer are an acrylate compound, a methacrylate compound, an acrylamide compound, a methacrylamide compound, a vinyl compound, a styrene compound, a maleimide compound, and maleic anhydride. And acrylonitrile and the like. The acrylate compound is exemplified by methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, decyl acrylate, decyl methacrylate, phenyl acrylate, 2-hydroxyethyl acrylate, acrylic acid 2- Hydroxypropyl ester, 2,2,2-trifluoroethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxy acrylate Ethyl ester, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate and 5-propenyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone. The methacrylate compound is exemplified by methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, naphthalene methacrylate. Ester, decyl methacrylate, decyl methyl methacrylate, phenyl methacrylate, 2-phenylethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, isobutyl methacrylate, 2-ethyl-20- 201001080 hexyl methacrylate, A Isodecyl acrylate, n-lauryl methacrylate, n-stearyl methacrylate, methoxy diethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, methacrylic acid Hydroquinone ester, isobornyl methacrylate, tert-butyl methacrylate, isostearyl methacrylate, n-butoxyethyl methacrylate, 3·chloro-2-hydroxypropyl methacrylate , 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate 5 - methyl-6-hydroxy-Bing Xixi norbornene-2-carboxylic acid 6-lactone and 2,2,3,3,4,4,4-heptafluoro-butyl methacrylate, and the like. Examples of the acrylamide compound are acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-benzyl acrylamide, N-phenyl acrylamide, and N, N-dimethyl propylene. Amidoxime and the like. The methacrylamide compound is exemplified by methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethyl Acrylamide, N,N-dimethylmethacrylamide, and the like. The vinyl compound is exemplified by vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether or the like. As the styrene compound, styrene, methyl styrene, chlorostyrene, bromostyrene and hydroxystyrene are exemplified. The maleidin compound is exemplified by maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. Each of the polymers having a unit structure represented by the formulas (1) and (2) may be an addition polymerizable monomer and a chain transfer agent (added to 1% by mass or less based on the mass of the monomer). After dissolving in an organic solvent, -21 - 201001080 was added to carry out a polymerization reaction by adding a polymerization initiator, and then it was produced by adding a polymerization terminator. The amount of the polymerization initiator added is 1 to 1% by mass based on the mass of the monomer, and the amount of the polymerization terminator is 0.01 to 0.2%. The organic solvent to be used is exemplified by propylene glycol monomethyl ether, propylene glycol monopropyl ether, ethyl lactate, cyclohexanone, methyl ethyl ketone and dimethylformamide. And 12 yards of thiol and the like. The polymerization initiator is exemplified by azobisisobutyronitrile and azobiscyclohexanecarbonitrile. The polymerization terminator is exemplified by 4-methoxyphenol or the like. The reaction temperature is between 30 and 1 〇 〇 ° C, and the reaction time is from 1 to 48 hours. The copolymerized polymer each having the unit structure represented by the above formula (1) and formula (2) is exemplified below. -22- 201001080 [化 10]

c:oIPo-c I CH3 (3 - 1) -0-C-CH3 ch3 ch3

Ch3

Formula (3 - 3) CO 〇_0-OCH2CH3 ch3

c:o I H 〇-C-0(CH2)3CH3

CH3H sub Π2 I c:o 0-CH3 Formula (3-4) ch3 -23- 201001080 [Chem. 11]

Ch3 ch3

〇-C-〇(CH2)3CH3 ch3

〇—C-OCH2CH3

Ch3

Equation (3-8) o-c-o(ch2)3ch3 ch3 -24- 201001080 [Chemistry 12]

(3 - 1 Ο)

Ch3 0-C-0(CH2)3CH3 Formula (3- 1 1)

o-C-OCH2CH3

Equation (3-12)

r H. CH3 c:o ‘Η2ό Equation (3—1 3) H 0-CH3 〇-C-〇(CH2)3CH3 ch3 -25- 201001080 [Chem. 13]

r Η -C-C , Η 2 C=00 CH2CH η ch3 Formula (3 — 1 4 ) Ο—C-0-C-CH3 I I ch3 ch3

Η One C-

C=0 Ο CH2CHh 0-C-0(CH2)3CH3 ch3 Formula (3- 1 5: oCH2CH H0-C~OCH2CH3 ch3 Formula (3 - 1 6)

η CH3 CH2CHh 0-CH3 Formula (3 - 1 7) oco(ch2)3ch3 ch3 The present invention is a polymer each having a unit structure of the above formula (1) and a unit structure having a protected carboxyl group of the above formula (2) ( 1) and a polymer (2) each having a unit structure of the above formula (1) and a unit structure having a protected hydroxyl group of the above formula (2), the polymer (1) and the polymer (2) may be used in combination. . In the case where the polymer of the present invention contains a polymer having a protected carboxyl group and a protected hydroxyl group, since the carboxyl group and the hydroxyl group can be formed by a trade bond of -26-201001080, the unit structure is located in the polymer. In the firing stage after coating, it is difficult to sublimate as a low molecular component, and since the unit structure of the polymer is not locally distributed and can be uniformly present in the film, the lower layer film does not generate a component in the entire film. Uneven. Therefore, by using the underlayer film, the dry etching rate in the lithography step or the pattern shape generated by the lithography is uniform in any portion of the film, and a good rectangular lithogram pattern and a numerator can be obtained. a compound (1) having at least two protected carboxyl groups represented by the following formula (3) or a compound (2) having at least two protected hydroxyl groups in the molecule, [Chem. 14] (C=〇) n I Re (3) OC——O-Rg CH—R8

Ry (wherein, Re, R7, Rs and R_9 are the same as defined in the above formula (3)). Thus, there is a combination of the above polymer (1) or the combination of the above polymer (2) and the above compound (2) or the above polymer (2) with the above compound or the above compound (2). The ratio of the above polymer to the above compound is such that the compound is contained in a ratio of 10 to 50 mol% based on the total amount of the monomer. a compound having at least two protected carboxy-27-201001080 groups represented by the above formula (3) or a compound having at least two protected hydroxyl groups in the molecule, which may have at least two carboxyl groups relative to the molecule Or a compound having at least two hydroxyl groups in the molecule, a mole, which is produced by reacting a vinyl ether compound represented by the above formula (4) with respect to the molar number reaction of the carboxyl group or the hydroxyl group. The compound having at least two carboxyl groups in the molecule which reacts with the vinyl ether compound represented by the above formula (4) is not particularly limited as long as it is a compound having a carboxyl group. Compounds having at least two, preferably two to four, carboxyl groups in the molecule are exemplified by, for example, isophthalic acid, terephthalic acid, pyromellitic acid, 1,2,4-trimellitic acid, 1,3. , 5-trimellitic acid, adipic acid, maleic acid, butane tetracarboxylic acid, ginseng (2-carboxyethyl) isocyanurate, naphthalene-2,6-dicarboxylic acid, methylene double Pamoic acid, 1,1'-bisnaphthalene-2,2'-dicarboxylic acid, hydrazine-9,10-dicarboxylic acid, maleic acid, itaconic acid, glutaric acid, 1,2 - cyclohexanedicarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, and the like. The compound having at least two, preferably two to four, hydroxyl groups in the molecule is exemplified by, for example, dihydroxybenzene, polynuclear phenol, dihydroxynaphthalene, dihydroxyindole, ethylene glycol, glycerin, bisphenol A, bisphenol S. Wait. The compound having at least two protected carboxyl groups represented by the above formula (3) or a compound having at least two protected hydroxyl groups in the molecule produced by the compounds has a molecular weight of 200 or more. When the molecular weight is less than the ruthenium, there is a problem that sublimation occurs when firing to form a photoresist underlayer film. The molecular weight is, for example, from 200 to 2,000, for example from 400 to 2,000. The photoresist-forming underlayer film forming composition for lithography of the present invention may further contain a crosslinking agent in the above polymerization -28-201001080 (1) or the above polymer (2). By using a crosslinking agent, when firing to form an underlayer film, a reaction occurs between the polymer and the crosslinking agent, and the underlayer film is formed to have a crosslinked structure. As a result, the underlayer film becomes strong and becomes a solubility lowering property to the organic solvent used for the solution of the hard mask or the photoresist applied to the upper layer. The crosslinking agent is a compound having two or more, for example two to six, or two to four substituents which are reactive with a protected carboxyl group or a protected hydroxyl group. The crosslinking agent is exemplified by a nitrogen-containing compound having a nitrogen atom substituted with an alkoxymethyl group such as a hydroxymethyl group or a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group or a hexyloxymethyl group. . Specific examples are hexamethoxymethyl melamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-fluorene (butoxymethyl) glycoluril (glycoluril), 1,3,4 ,6·肆(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-indole (butoxymethyl)urea, 1,1,3,3- Ruthenium (methoxymethyl) urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidone and 1,3-bis(methoxymethyl)-4,5- A nitrogen-containing compound such as dimethoxy-2-imidazolidinone. The crosslinking agent can be exemplified by a methoxymethyl melamine compound (trade name: CYMEL 300, CYMEL 301, CYMEL 303, CYMEL 3 50) manufactured by Mitsui CYTECH Co., Ltd., and a butoxymethyl melamine compound (product) MYCOTE 506, MYCOTE 508), glycoluril compound (trade name CYMEL 1170, POWERLINK 1174), methylated urea resin (trade name UFR 6 5 ), butylated urea resin (commodity -29-201001080 UFR3 00, U -VAN1 0S60, U-VAN 1 OR, U-VAN1 1 HV ), Urea/formaldehyde resin manufactured by Dainippon Ink Chemical Industry Co., Ltd. (high condensation type, trade name BECKAMINE J-3 00S 'BECKAMINE P-955, :BECKAMINE N ) and other commercially available compounds. Further, the crosslinking agent may be a compound obtained by condensing a hydrogen atom of an amine group with a hydroxymethyl group or an oxiranylmethyl group, such as the above-mentioned melamine compound, urea compound, glycosides compound, and a fox compound. . For example, a high molecular weight compound produced from a melamine compound (trade name: CYMEL 3 03) and a benzoguanamine compound (trade name: CYMEL 1 1 23) as described in U.S. Patent No. 63 23 3 1 0 can be used as crosslinkability. Compound. Further, as the crosslinking agent, N-hydroxymethylpropenylamine, N-methoxymethylmethacrylamide, N-ethoxymethylpropenylamine and N which are substituted with a hydroxymethyl group can be used. a polymer compound produced by butoxymethylmethacrylamide or the like, or a propylene oxime compound substituted with an alkoxymethyl group and a methacrylamide compound. The above polymer compound can be exemplified by, for example, poly(N-butoxymethylpropenylamine), a copolymer of N-butoxymethyl acrylamide and styrene, and N-hydroxymethylmethacrylamide. Copolymer of methyl methacrylate, copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and N-butoxymethyl acrylamide and benzyl methacrylate and methyl A copolymer of 2-hydroxypropyl acrylate or the like. The crosslinking agent may be used alone or in combination of two or more. The crosslinking agent may be contained in an amount of from 3 to 30% by mass, preferably from 5 to 20% by mass, based on the solid content of the solvent contained in the lithographic underlayer film forming composition of the present invention, -30 to 201001080. . Further, the retardation profile or the step coverage of the underlying substrate can be adjusted by changing the type or content of the crosslinking agent. The lithographic underlayer film forming composition for lithography of the present invention may contain the above polymer (1) or the above polymer (2), a crosslinking agent, and an acid which is a crosslinking catalyst. The crosslinking agent can be promoted by using a crosslinking catalyst. Further, by containing an acid which promotes the formation of cross-linking, the underlayer of the photoresist and the upper layer do not occur, and a good photoresist pattern can be formed. As the above acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, pyridine gun-p-toluenesulfonic acid, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, citric acid, benzoic acid and hydroxyl group can be used. An acid compound such as benzoic acid. The acid may be used alone or in combination of two or more. The acid may be contained in an amount of from 0.3 to 3.0% by mass, preferably from 0.5 to 2.0% by mass, based on the solid content of the solvent contained in the photoresist underlayer film forming composition of the present invention. The photoresist forming underlayer film forming composition for lithography of the present invention may further contain a photoacid generator. By using a photoacid generator, the acidity of the photoresist coated on the upper layer can be made uniform in the lithography step. Preferred photoacid generators are, for example, bis(4-tributylphenyl) iodine trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, and the like, iron salt-based photoacid generators, benzene Halogen-containing compounds such as bis-bis(trichloromethyl)-s-triazine are photoacid generators, benzoin tosylate, oxime-based leukotriene trifluoromethanesulfonate, etc. A sulfonic acid photoacid generator or the like. The photoacid generator may be contained in an amount of 0.2 to 10% by mass, preferably 〇. 4 to 5 by mass, in order to remove the solid content of the solvent contained in the lithographic underlayer film forming group of the present invention. %. Further, in addition to the above, the photoresist lower layer film forming composition for lithography of the present invention may further contain a light absorbing agent, a rheology adjusting agent, a bonding agent, and a surfactant, as needed. As the light absorbing agent, commercially available light absorbing agents such as those described in "Technology and Market for Industrial Pigments" (CMC Publishing) or "Dye Notes" (edited by the Society of Organic Synthetic Chemistry), such as CI Disperse Yellow 1, 3, 4, may be suitably used. 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; CI Disperse Orange 1, 5 , 13, 25, 29, 30, 31, 44, 57, 72 and 73; CI dispersion red 1' 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; CI Disperse Violet 43; CI Disperse Blue 96; c I · Fluorescent Brightener 1 1 2, 1 3 5 and 1 6 3 ; C. I. Solvent Orange 2 and 4 5 ; Cl Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CI Pigment Green 10; CI Pigment Brown 2, etc. The light absorbing agent may be contained in an amount of 10% by mass or less, preferably 5% by mass or less, based on the solid content of the solvent contained in the photoresist underlayer film forming composition of the lithography of the present invention. Group thick 塡 塡 成 成 充 充 充 充 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲The baking film of benzene, such as the drying layer of the film, is a lowering agent, and the high-density denaturing is adjusted to flow or adjust the flow, and the flow containing the fluid is uniform. Qualitative -32- 201001080 phthalic acid derivatives such as di-butyl phthalate, dihexyl phthalate, ester isodecyl ester, di-n-butyl diisobutyl adipate, Diisooctyl acid ester, octyl octyl adipate derivative, di-n-butyl maleate, diethyl maleate, maleic acid derivatives such as horse, oleic acid methyl ester, butyl oleate, oleic acid Oleic acid derivative, or n-butyl stearate, glyceryl stearate derivative. The rheology modifier may be contained in a proportion less than the solid content of the solvent contained in the photoresist for lithography of the present invention. The purpose of including the auxiliary agent is mainly to improve the adhesion of the substrate or the underlying film forming composition, especially for the purpose of stripping the photoresist. As the auxiliary agent, for example, trimethylchloroanthryl vinyl chlorodecane, methyl diphenyl chlorodecane, chloromethyl dichloro phthalane, trimethyl methoxy decane, dimethyl diethyl methyl group can be exemplified. Alkoxymercaptodioxane, hydrazine, Ν'-bis(trimethylnonane) such as dimethoxy decane, dimethylvinyl ethoxy decane methoxy decane, phenyl triethoxy decane Alkaloids such as urea methyl hydrazine alkylamine, trimethyl decyl imidazole, chloroalkane, r-chloropropyltrimethoxy decane, r-aminopropyl propyl sulfoxide, 7 _ glycidoxypropyl Dimethicone or the like triazole, benzimidazole, carbazole, 2-mercaptobenzimidazole, thiazole, 2-mercaptobenzoxazole, Urazole, butyl phthalate, A stearic acid layer film forming group of a diacid or the like of adipic acid, such as adipic acid, tetrahydrofurfuryl ester, etc., a 30% by mass of a photoresist and an optical aerogen, which does not cause an alkane or a dimethylmethylchloromethane. Oxygen sand yard, 'diphenyl monoalkane, hexamethyl, dimethyl tris, vinyl triyl triethoxy decane, benzene 2-mercaptobenzothiouracil ( -33- 201001 080

Thiouracil), a heterocyclic compound such as mercapto imidazole or mercaptopyrimidine, or urea or sulphur urine such as 1,1-dimethylurea or i,3-dimethylurea. Then, the auxiliary agent may contain less than %, preferably less than 2, based on the solid content of the solvent contained in the lower film of the photoresist for lithography of the present invention. /. Proportional allocation. The photoresist-forming underlayer film forming composition for lithography of the present invention contains pinholes or strains in the film, and further improves the application of the surfactant to the surface spot. The surfactant is exemplified by polyoxyethylene ethyl ethers such as polyoxyethylene ethyl lauryl ether, ethyl stearyl ether, polyoxyethyl methyl cetyl ether, polyoxyethylene ether, and the like; Polyoxyethylene ethyl allylic ethers such as ethyl octyl phenol ether and ethyl decyl phenol ether; ethyl polyoxyl propyl block oligomers; sorbitan Montan, sorbitan monopalmitate, sorbitan monostearate monostearate, sorbitan trioleate, sorbitol fatty acid ester, etc. Ester; polyoxyethylene ethyl hawthorn monolaurate, polyoxyethylene ethyl sorbitan monopalmitate, ethyl sorbitan monostearate, polyoxyethylene ethyl sorbate oleate Non-ionic surfactants such as polysorbate fatty acid esters such as polyoxyethylene sorbitan tristearate, EF301, EF303, EF3 5 2 (TOKEMU PRODUCTS) , Megafax F171, F173, R-30 (made by Dainippon), trade name), Fluorad FC430, FC431 (live)

The compound and the compound forming group 5 are manufactured for the optical property, the polyoxyalkylene group, the polyoxypolyoxylate, the sorbitan tristearyl alcohol, the polyoxyl anhydride trioxetene F Top Ink (:Made 3M -34- 201001080 (manufactured by the company), trade name), Asahigard AG710, Surflon S-382, SCI 01 > SC102 > SC103, SC104, SC105, SC106 (asahi Glass (manufacturing), trade name) It is a surfactant, organic siloxane polymer-KP 341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of the surfactant to be added is 2.0% by mass or less, preferably 1% by mass or less, based on the solid content of the solvent contained in the film forming composition for the lithographic photoresist of the present invention. The surfactants may be used singly or in combination of two or more. In the present invention, a solvent for dissolving the above polymer, a crosslinking agent component, a crosslinking catalyst or the like is exemplified by ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and methyl cellosolve acetate. , ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether Acid ester, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, Ethyl propoxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, and the like. These organic solvents may be used singly or in combination of two or more. Further, in the lithographic underlayer film forming composition for lithography of the present invention, a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate may be used in combination. Among these solvents, preferred are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, -35-201001080, cyclohexanone, and the like for improving the homogenization property. The so-called photoresist used in the present invention is a photoresist or an electron beam photoresist. The photoresist coated on the upper layer of the photoresist for the lithographic underlayer film formed by using the photoresist for forming a lower layer film for lithography of the present invention may be either a negative type or a positive type, for example, a novolac resin and a positive type photoresist composed of 1,2-naphthoquinonediazide sulfonate, a chemically amplified photoresist composed of a binder having a base for increasing the alkali dissolution rate due to acid decomposition, and a photoacid generator, and a base A chemically amplified photoresist composed of a low-molecular compound and a photo-acid generator which dissolves a soluble binder and an alkali-dissolving rate of a photoresist by acid decomposition, and an adhesive having a base which increases the alkali dissolution rate due to acid decomposition and A low-molecular compound which increases the alkali dissolution rate of the photoresist by acid decomposition, a chemically amplified photoresist composed of a photoacid generator, a photoresist having a Si atom in the skeleton, and the like. Specifically, the product name is APEX-E manufactured by Rohm and Haas Company. Further, the electron beam resist coated on the upper layer of the lithographic underlayer film formed using the photoresist underlayer film forming composition of the present invention is exemplified by, for example, an end containing a si_si bond in the main chain. a composition of an aromatic ring resin and an acid generator which generates an acid by irradiation with an electron beam or a poly(p-hydroxystyrene) substituted with an organic group containing an N-carboxyamine by a hydroxyl group and by an electron beam The irradiation produces a composition of an acid generator and the like. The latter electron beam resist composition is such that the acid generated by the electron beam irradiation of the acid generator reacts with the N-carboxyamino group of the polymer side chain to decompose the hydroxyl group of the polymer side chain to exhibit solubility and dissolution. In the test imaging liquid, a photoresist pattern is formed. -36- 201001080 The above acid generator is exemplified by ι, ι-bis[p-alkane, 1,1-bis[p-methoxyphenyl]-2,2,2_Ξchlorophenyl]-2,2-di Ethyl chloride, 2-chloro-6-(tri-ammonium compound, triphenylsulfonium salt, diphenylbenzyltosylate, dinitrobenzyltoluenesulfonate formed as light having lithography using the present invention The photo-resistance of the photoresist of the underlying film can be potassium, sodium carbonate, sodium citrate, sodium metasilicate, amine, n-propylamine and other primary amines, diethylamine, ditriethylamine, methyldiethyl The preferred imaging solution for a tertiary amine such as an amine such as an amine amine such as a diamine, a tetramethylammonium hydroxide or a hydroxy quaternary ammonium salt, or a cyclic amine such as pyrrole or piperidine is a quaternary ammonium salt. Further, in the aqueous solution of the above-mentioned alkali, a surfactant such as an alcohol or a nonionic surfactant may be used, and an appropriate coating method such as a photoresist pattern forming device of the present invention will be described. The base tape coating used for the production of the film-sealed circuit element, the glass substrate, the ruthenium substrate, and the like are bake-hardened to form a coating-type underlayer film. The film is directly or as needed. After layering to a plurality of layers of the underlayer film, the photoresist is coated and irradiated by electron beam or electron beam, and the image is formed by washing and blocking. Further, light or chlorophenyl group can be carried out as needed. 2,2,2-trichloroethane: a key salt such as a halogenated iodonium salt such as ethyl chloride or 1,1-bis[p-chloromethyl)pyridine, or a sulfonic acid ester of a nitro acid ester or the like. The underlayer film forming composition is an inorganic base such as sodium hydroxide or hydroxide aqueous ammonia, a secondary amine such as butyl butylamine, or an aqueous solution of a base such as methylethanolamine, triethylammonium triethylammonium or choline. The tetramethylammonium hydroxide and the guanidine method such as isopropyl alcohol are applied by spin coating or coating to form a composition (for example, a sand/dioxide substrate), followed by The coating type underlayer coating film is formed into a film which is light-dried after being coated with a predetermined mask, and is heated to obtain a good photoelectron beam, and then heated to -37-201001080 (PEB: post-exposure baking). Subsequently, the photoresist underlayer film removed by the above-described step removal is removed by dry etching to form a desired pattern on the substrate. The film thickness of the photoresist underlayer film is preferably from 0.01 to 3.0/zm. Further, the baking condition after coating may be suitably selected from a temperature of 80 to 35 (TC, time and a range of time of 0.5 to 120 minutes. The light of the above photoresist is exposed to near ultraviolet rays and far ultraviolet rays. Or chemical lines such as extreme ultraviolet rays (such as EUV), such as 248nm (KrF laser light), 193nm (ArF laser light), 157nm (F2 laser light), etc. Light irradiation can produce acid from photoacid generator The method can be used without any particular limitation, and the electron beam irradiation of the electron beam resist can be irradiated by, for example, an electron beam irradiation device with an exposure amount of 1 to 2000 mJ/cm 2 , 10 to 1500 mJ/cm 2 or 50 to 1 000 mJ/cm 2 ° . The present invention comprises the steps of forming a film on a semiconductor substrate by photoresist formation by a photolithography underlayer film formation by lithography, forming a photoresist film thereon, and irradiating and developing the light or electron beam The step of forming a photoresist pattern, and the step of etching the photoresist underlayer film according to the formed photoresist pattern, and the step of processing the semiconductor substrate according to the patterned photoresist underlayer film can be used to fabricate a semiconductor device. Can be After the photoresist underlayer film is formed on the substrate by the lithographic underlayer film forming composition of the present invention, after one or several layers of the coating film material are directly formed on the photoresist underlayer film as needed, The photoresist is coated, whereby the substrate can be processed by selecting an appropriate etching gas even if the pattern width of the photoresist is narrow and the pattern is collapsed and the thin layer photoresist is prevented from being collapsed. That is, the step of forming a photoresist underlayer film on the semiconductor substrate by the photoresist lower layer film composition of the present invention, and forming a hard mask thereon by using a coating material containing a bismuth component or the like, and further a step of forming a photoresist film thereon and a step of irradiating and developing a photoresist pattern by light or electron beam, a step of etching the hard mask according to the formed photoresist pattern, and a hard light according to the pattern The step of etching the photoresist underlayer film and the step of processing the semiconductor substrate by the patterned photoresist underlayer film can be used to manufacture a semiconductor device. The lithographic photoresist underlayer film composition of the present invention is considered as an antireflection film. Effect When the light absorbing portion enters the skeleton, there is no diffusing material in the photoresist during heating and drying, and the light absorbing portion has a sufficiently large light absorbing property, so that the reflected light preventing effect is high. Further, the lithographic resist for use in the present invention. The underlayer film forming composition has high thermal stability, and can prevent the upper layer film from being contaminated by the decomposition product at the time of firing, and has a sufficient temperature margin at the time of firing. The lithographic underlayer film forming composition of the present invention According to the process conditions, it can be used as a function of preventing light reflection, thereby preventing the substrate from interacting with the photoresist, or having a material which is prevented from being used in the photoresist or the photoresist is exposed to the substrate. In order to prevent the photoresist pattern associated with the miniaturization of the photoresist pattern from collapsing after development, the photoresist film is thinned. The thin film photoresist has a process of transferring the photoresist pattern onto the underlying film by an etching process, and processing the substrate by using the underlying film as a mask, or converting the photoresist pattern into an etching process-39 - 201001080 printed on the underlying film, using a different gas composition, transferring the pattern transferred onto the underlying film to the transfer step of the underlying film, and finally using the underlying film of the transfer pattern A process for processing a substrate on a reticle. The lithographic underlayer film forming composition for lithography of the present invention and the lithographic underlayer film formed using the composition are effective for the process, and are formed by forming a composition using the lithographic underlayer film of the present invention. The lithography underlayer film has a sufficient etching resistance for processing a substrate (for example, a thermal ruthenium film on a substrate, a tantalum nitride film, a polyimide film, etc.). Further, in order to obtain a fine photoresist pattern, it is also used in a dry etching of a photoresist underlayer film to make the photoresist pattern and the photoresist underlayer film have a finer pattern width than when the photoresist is developed. The underlayer film forming composition for photoresist for lithography of the present invention and the photoresist underlayer film for lithography formed using the composition are effective for the process, and have a selectivity close to the dry etching speed of the photoresist film. Therefore, the lithographic underlayer film formed by using the lithographic underlayer film forming composition of the present invention can be used as a planarization film, a photoresist underlayer film, a photoresist layer anti-contamination film, and has dry etching selectivity. The film. According to this, it is possible to easily and accurately form the photoresist pattern in the lithography process for semiconductor fabrication. EXAMPLES (Synthesis Example 1) 20-Og (0.1 mol) N-vinylcarbazole, 5.0 g (〇·〇26 mol) p-ethoxyethoxystyrene, -40 were placed in a 200 ml flask. - 201001080 6 1 · 0 g of tetrahydrofuran as a solvent. 1 gram of AIBN (azobisisobutyronitrile) as a polymerization initiator was added to the reaction vessel, and the temperature was raised to 8 (rC, and the reaction was carried out for 24 hours. The reaction solution was precipitated in 300 g of methanol, and filtered. The white solid obtained was dried under reduced pressure at 40 ° C to obtain 21 g of a white polymer. The analysis of the obtained polymer by GPC was as follows. Mass average molecular weight (Mw) = 9000, molecular weight distribution (Mw/Mn = 2.00, the polymer is called polymer (resin) A. (Synthesis Example 2) 5.0 g (0.026 mol) of N-vinylcarbazole and 14.4 g (0.095 mol) of ethylene were added to a 200 ml flask. Naphthalene, 9.9 g (0.052 mol) of p-ethoxyethoxystyrene, 71.0 g of tetrahydrofuran as solvent. Add 3.3 g of AIB N ' as polymerization initiator to the reaction vessel to raise to 80 °C After the reaction, the reaction solution was precipitated in 300 g of methanol, and the obtained white solid was filtered, and then dried under reduced pressure at 40 ° C to obtain 1 g of a white polymer. The obtained polymer was determined by GPC. The results of the analysis are as follows. Mass average molecular weight (Mw) = 11000 Molecular weight distribution (Mw/Mn) = 2.30, the polymer is called polymer (resin) B. (Comparative Synthesis Example 1) 2 〇.〇克(0.1 mol) N-vinyl azole was added to a 200 ml flask. 50.0 g of tetrahydrofuran as a solvent. The reactor was cooled to -7 Torr under a nitrogen atmosphere, and the gas was purged under reduced pressure into nitrogen and repeated three times. After heating to room temperature, '1.0 g was added as a solvent. AIBN of the polymerization initiator. After the temperature was raised to 80 ° C, the reaction was carried out for 24 hours. The reaction solution was precipitated in 250 g of methanol, and the obtained white solid was filtered, and dried under reduced pressure at 40 ° C to obtain 1 8 . White polymer poly-N-vinyl azole. The analysis results of the obtained polymer by GPC are as follows. Mass average molecular weight (Mw) = 12000, molecular weight distribution (Mw / Mn) two 1.55 'The polymer is called polymer (Resin) C. (Comparative Synthesis Example 2) 5.0 g (0.026 mol) of N-vinylcarbazole, 15.0 g (0.078 mol) of p-ethoxyethoxystyrene, 5 was added to a 200 ml flask. 〇. gram as a solvent for tetrahydrofuran. Add 1.0 gram to the reaction vessel. The AIBN of the polymerization initiator was reacted for 24 hours after the temperature was raised to 8 ° C. The reaction solution was precipitated in 300 g of methanol, and the obtained white solid was filtered, and dried under reduced pressure at 40 ° C to obtain 1 6 g of a white polymer. The analysis results of the obtained polymer by GP C were as follows: Mass average molecular weight (Mw) = 12,000, molecular weight distribution (Mw/Mn) = 1.98, and the polymer was called polymer (resin) D. (Comparative Synthesis Example 3) 20.0 g of (N-vinyl oxazole) N-vinylcarbazole, 0.6 g (0.003 mol) of p-ethoxyethoxystyrene, 5 〇.〇 were added to a 200 ml flask. Glucan as a solvent. To the reaction vessel, 1.1 g of -42 to 20100,1080 of AIBN as a polymerization initiator was added, and the mixture was heated to 80 ° C and reacted for 24 hours. The reaction solution was quenched in 300 g of methanol. The obtained white solid was filtered, and then dried under reduced pressure at 401 to yield 17 g of white polymer. The analysis results of the obtained polymer by G P C were as follows. The mass average molecular weight (Mw) is 2 2000' molecular weight distribution (Mw/Mn) = 1.8, and the polymer is referred to as polymer (resin) E. The resin represented by the above polymers (resins) A to E, the acid generator represented by the following AG 1 (pyridyl p-toluene), and the crosslinker represented by the following CR1 in the ratios shown in Table 1 (tetramethoxymethyl glycoluril) dissolved in a fluorine-containing surfactant (Daily Ink Chemical Industry Co., Ltd. 'trade name Megafax R-30) 13 parts by mass of organic solvent (1 000 parts by mass of ring In the mixed solvent of hexanone and 3 parts by mass of propylene glycol monomethyl ether acetate, the lithographic underlayer film forming composition (Examples 1 to 2 and Comparative Examples 1 to 4) was separately prepared. Here, the surfactant is added so that each composition becomes 〇. 3 mass%. [化15]

AG1 OMe

MeO—y j-- N^N0=^(丁)=〇 N-

MeO ” ^—OMe CR1

-43- 201001080 Table 1 Resin (parts by mass) Crosslinking agent (parts by mass) Acid generator (parts by mass) Example 1 Resin A (100) CR1 (15) AG1 (1.5) Example 2 Resin B (100) CR1 (15) AG1 (1.5) Comparative Example 1 Resin C (100) Comparative Example 2 Resin A (100) CR1 (1) AG1 (1.5) Comparative Example 3 Resin D (100) CR1 (15) AG1 (1.5) Comparative Example 4 Resin E (100) CR1 ( 15 ) AG1 (1.5) The thus prepared lithography solution of the photoresist underlayer film forming composition (Examples 1 to 2 and Comparative Examples 1 to 4) was applied onto a ruthenium substrate, Baking at 240 °C for 60 seconds, respectively forming a film under the photoresist with a film thickness of 500 nm. [Measurement of Refractive Index and Extinction Coefficient] After forming the above-mentioned photoresist underlayer film, the refractive index of 193 nm was obtained by using ellipsometers (VASE) with variable incident angle of JA WOOLLAM. And the extinction coefficient (k), the results are shown in Table 2. [Crack Test] A solution of the above-mentioned prepared lithography underlying photoresist film forming composition (Examples 1 to 2 and Comparative Examples 1 to 4) was applied onto a ruthenium substrate disk at 240 Å. (: baking for 60 seconds) forming a photoresist film having a film thickness of 7 〇〇 nm. The composition is formed by a hard mask on the upper layer (the composition of the underlayer film containing the yttrium photoresist for ArF, the S i content rate is 3 9 %, solid content 3 %) baked at 250 ° C for 60 seconds, filming a film thickness of 160 ηηη to form a hard mask. Then 'bake at 270 ° C -44-201001080 for 180 seconds 'Check for cracks (cuts) on the hard mask (underlying film containing ruthenium). The confirmation method was performed with an optical microscope BX 5 1 制造 manufactured by 〇iympus Co., Ltd. The results are shown in Table 2. Table 2] Table 2 η k hard mask without cracks Example 1 1.55 0.40 Μ JW\ Example 2 1.50 0.30 Μ Comparative Example 1 1.52 0.31 Comparative Example 2 1.55 0.40 Comparative Example 3 1.59 0.80 /fm·- Thief Comparative Example 4 1.52 0.32 As shown in Table 2 above, the refractive index η 値 of the photoresist underlayer film obtained in Examples 1 to 2 and Comparative Examples 1, 2 and 4 was 1 · 50 to 1.59, and the extinction coefficient k 値 was 0, .30 to 0.40. Especially, the film thickness of 200 nm or more shows an optimum refractive index (η) which exhibits sufficient antireflection effect. And extinction coefficient (k). When the composition was formed using the photoresist underlayer films of Examples 1 to 2 and Comparative Example 3, good hard mask crack resistance was exhibited, but the light of Comparative Examples 1, 2, and 4 was used. When the underlayer film is formed to form a composition, the hard mask is cracked. [Observation of pattern shape] (1) Formation of photoresist pattern The above-mentioned modulated photoresist film is formed into a composition (Examples 1 and 2 and Comparative Example) The solution of 1 to 4) was applied onto a substrate having a thickness of 300 nm of Si〇2 - 45 to 201001080, and baked at 240 ° C for 60 seconds to form a photoresist underlayer film having a film thickness of 200 nm. A thin mask is formed on the photoresist underlayer film to form a composition (a film forming composition of a photoresist containing germanium), and baked at 240 ° C for 60 seconds to form a hard mask having a film thickness of 80 nm (a photoresist containing germanium) Next, an ArF photoresist (trade name: TArF-P6239, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was baked on the laminate film at 120 ° C for 60 seconds to form an ArF light having a film thickness of 150 nm. Next, an ArF exposure apparatus (manufactured by Nikon Corporation, trade name NSR-S307E, NA0.85, outer σ = 0.85, inner σ = 0.81) 4, double pole illumination, HT mask) exposure, baking at 110 ° C for 60 seconds (PEB), and imaging in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, obtaining 0.08 // Positive pattern of mL/S (line and space). (2) Observing the cross-sectional shape of the underlying film of the photoresist after CF4/Ar dry etching, followed by the L (line) / S (space) photoresist of 〇.〇8 " m obtained by exposure and development of the above ArF The pattern was used as a mask, and dry etching was performed using CF4 gas as a main body, and the pattern was transferred onto a hard mask (a film material containing a germanium-containing photoresist for ArF). The etching conditions are as follows. The chamber pressure was 15.0 Pa, the RF power was 200 W, the CF4 gas flow rate was 50 sccm, the Ar gas flow rate was 200 sccm, and the time was 52 seconds. (3) Observing the cross-sectional shape of the underlying film of the photoresist after etching of the 〇2/N2 gas -46 - 201001080 followed by dry etching with the above CF4 gas to form a pattern of hard mask (including light) The underlayer film material is subjected to uranium engraving in a 〇2/N2-based gas as a photomask. The pattern is transferred onto a photoresist underlayer film formed by using the lithographic photoresist underlayer film forming composition of the present invention. The etching conditions are as follows. The chamber pressure was 1 · 0P a , the RF power was 280 W ’ 〇 2 gas flow rate was lOsccm, the N2 gas flow rate was lOsccm, and the time was 125 seconds. (4) Observing a SiO 2 substrate etched with a C4F8/Ar/02 gas, followed by dry etching using the above-mentioned 02/N 2 gas as a main component, and forming a pattern of the lithographic underlayer film using the lithography of the present invention. The underlayer film of the photoresist formed by the formation of the composition was used as a photomask, and was etched by a C4F8/Ar/02-based gas to process the SiO 2 substrate. The etching conditions are as follows. The chamber pressure was 6. OP a, RF power was 280 W, C4F8 gas flow was 30 sccm, Ar gas flow was lOOsccm, 〇2 gas flow was 3 s c c m, and time was 3 15 seconds. As a result, when the composition was formed using the photoresist underlayer film for lithography of Examples 1 and 2, the cross-sectional shape of the underlayer film of the photoresist after the substrate processing and etching was a vertical shape, and it was confirmed to be good. [Dry etching resistance test] The dry etching resistance test was carried out by applying a solution of the above-mentioned prepared photoresist underlayer film forming composition (Examples 1 and 2 and Comparative Examples 1 to 4) onto a ruthenium substrate at 240 ° C. Bake for 60 seconds to form a photoresist underlayer film having a film thickness of 500 nm. The evaluation was carried out under the following conditions. -47 - 201001080 (Erosion resistance test of CF4/Ar gas) The film thickness difference of the photoresist film before and after etching was measured using the dry etching apparatus ES4〇 1 ' manufactured by SCIENTIFIC Co., Ltd., Japan as the etching speed. The etching conditions are as described above. The results are shown in Table 3. [Table 3] Table 3 Etching speed (nm/min) of the film underlying film CF^Ar-based gas Example 1 140 Example 2 115 Comparative Example 1 126 Comparative Example 2 138 Comparative Example 3 160 Comparative Example 4 130 As shown, the CF4/Ar gas etching rate is independent of the crack resistance generated on the hard mask, and the polymer having a high ratio of the aromatic condensation ring has a slow etching rate and exhibits high etching resistance. Further, the hungry speed was preferably 1 to 40 n m / m i η or less, and the etching rate of Comparative Example 3 was 160 nm/min, which was extremely fast. Therefore, when the pattern is transferred, a good shape cannot be obtained. [Industrial Applicability] A photoresist pattern forming method for forming a photoresist for use in a lithography process, and a photoresist pattern forming method for forming a composition using the photoresist underlayer film, and a semiconductor device In the manufacturing method. -48-

Claims (1)

201001080 VII. Patent Application Range: 1. A photoresist underlayer film forming composition used in a lithography process for manufacturing a semiconductor device, characterized in that the composition contains each of the formulas (1) and (2) Unit structure of polymer: Ch-r8 H7 (In the above formula, X represents a hydrogen atom or an aromatic condensed ring, Y represents an aromatic condensed ring, and further, X and Y may be bonded to each other to form a condensed ring, and R, R2, R3, R4 and R5 respectively And a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, and R6, R7 and R8 each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R9 represents an alkyl group having 1 to 1 carbon atom. Further, and R8 may also be bonded to each other to form a ring, Μ represents a direct bond or a linking group, and η represents 0 or 1), and when the total number of structures constituting all the units of the polymer is 1.0, the above formula (1) a polymer having a ratio of a unit structure number (a) to a unit structure number (b) expressed by the above formula (2) of 0.3 SaS 0.95 and 0.05 SbS 0.7, respectively, and the composition further And a crosslinking agent and a solvent, wherein the composition contains 3 to 30% by mass of the crosslinking agent based on the solid content of the solvent to remove the solvent - 49 - Formula (3) 201001080 2. Manufacturing of a semiconductor device In the lithography process, the layer film is formed into a composition, which is characterized in that the composition includes J) and formula (2) In addition to the polymer of the unit structure, there are at least two compounds represented by the following formula (3) or protected hydroxyl groups: [Chemical 2] (c=0) η I Re 〇~C—〇-Rg ch -r8 r7 (In the above formula, R6, R7 and R8 each represent a hydrogen atom or an alkyl group of 10, R9 represents a carbon atom number of 1 to 10 and R8 may be bonded to each other to form a ring, and η represents 0 or I) When the total number of unit structures of the polymer and the number of the compound are 5, the unit structure number represented by the formula (2) represented by the formula (1) and the formula (3) The total amount of (b) is 〇.3SaS0.95, the above polymer and the above compound, and the composition further contains a solvent, and the composition contains 3 to 30 based on the removal of the above component from the composition. % by mass of the above crosslinking agent. 3- The photoresist of the first or second aspect of the patent application, wherein the unit represented by the above formula (1) is under the photoresist of naphthalene, Acenaphthylene, and acetaminophen ( The above formula (1 further comprises a group having a protected carboxyl group having 1 atomic group, and further, R7 is a composition of a total of 1.0 and a combination of 0.05 and b^0.7, and a crosslinking agent is formed by a solid film of a solvent. The group is selected from the group consisting of a vinyl group, an N-vinyl-50-201001080 carbazole or a derivative of the above-mentioned derivatives. The photoresist underlayer film forming composition according to any one of claims 1 to 3, Further, it further contains an acid or an acid generator. The light-receiving underlayer film is characterized in that the photoresist underlayer film forming composition according to any one of claims 1 to 4 is coated on a semiconductor substrate. A method for forming a photoresist pattern, which is characterized in that the photoresist underlayer film forming composition according to any one of claims 1 to 4 is coated on a semiconductor substrate. 7. The semiconductor manufacturing process in which the lower layer film is formed by firing. A method of manufacturing a semiconductor device, comprising the steps of forming a lower film by a photoresist underlayer film forming composition according to any one of claims 1 to 4 on a semiconductor substrate, and forming a photoresist thereon a step of forming a film and a step of forming a photoresist pattern by light or electron beam irradiation and development and a step of etching the underlayer film according to the formed photoresist pattern, and a layer-by-layer film-to-semiconductor according to the patterning The step of processing the substrate. The method for manufacturing a semiconductor device, comprising the step of forming a lower film by forming a photoresist underlayer film forming composition according to any one of claims 1 to 4 on a semiconductor substrate. And the step of forming a hard mask thereon and the step of forming a photoresist film thereon, and the step of forming a photoresist pattern by light or electron beam irradiation and development, and by forming the light The step of obstructing the uranium engraved hard mask, and the step of etching the underlying film according to the patterned hard mask, and the step of processing the semiconductor substrate according to the patterned underlying film. -51 - 201001080 Representative diagram: (1) The representative representative of the case is: No. (2) The symbolic symbol of the representative figure is simple: If there are no five cases, if there is a chemical formula, please disclose the chemical formula that best shows the characteristics of the invention: Chemical 1 R1 R2 R3 R4 (C=〇)n I «6 〇*C—0-R〇 ch-r8 Rr