KR101057605B1 - Photosensitive resin composition and pattern formation method - Google Patents

Abstract

Photosensitive resin containing the base resin (A) which the solubility to aqueous alkali solution increases by the action of an acid, the acid generator (B) which generate | occur | produces an acid in response to electromagnetic waves, and the quencher (C) which collects the said acid. As a composition, the said base resin (A) contains a silicon-containing high molecular compound, and the said quencher (C) contains the basic compound which has a coumarin skeleton. The pattern formation method which uses the said photosensitive resin composition is provided simultaneously.

Description

Photosensitive resin composition and pattern formation method {PHOTOSENSITIVE RESIN COMPOSITION AND METHOD OF FORMING PATTERN}

The present invention relates to a photosensitive resin composition containing a basic compound having a coumarin skeleton as a quencher and a pattern forming method using the resin composition. More specifically, the present invention relates to a photosensitive resin composition having good resist characteristics over time and capable of long-term storage, and a pattern forming method using the composition.

In order to form a fine pattern with the demand for high integration and miniaturization in recent years, the multilayer resist method which has high dimensional precision and is easy to obtain a gorespect ratio is examined. In the resist material used for this multilayer resist method, the thing of the two-layered structure which made the upper layer into the positive resist layer and the lower layer into the organic resin layer is examined, and the silicon layer with high oxygen plasma resistance is high in this positive resist layer of this upper layer. The use of the containing high molecular compound is examined.

As such a composition for positive resists, For example, the base resin which the solubility to aqueous alkali solution increases by the action of an acid, the acid generator which generate | occur | produces an acid in response to electromagnetic waves, and the acid from an acid generator A chemically amplified composition containing an organic basic compound (quencher) capable of controlling the diffusion of is used (see Patent Document 1).

Patent Document 1: Japanese Unexamined Patent Publication No. 2004-334107 (corresponding US application 2004/0229161 A1)

DISCLOSURE OF INVENTION

Problems to be Solved by the Invention

However, the resist composition which uses the base resin which has silicon-containing high molecular compounds, such as a siloxane type or a silsesquioxane type as a main component, tends to deteriorate resin, and, in some cases, changes in sensitivity by the problem of gelation and storage. Problems (such as poor sensitivity over time) have occurred.

This invention is made | formed in view of the above subjects, and while having a quencher function, the composition has good stability with time-lapse, especially the gelation which causes the improvement of the molecular weight by the change over time during storage. It is an object of the present invention to provide a photosensitive resin composition and a pattern forming method using the composition, which can be prevented and can improve sensitivity over time.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors earnestly researched about the quencher which exhibits the quencher function and does not produce the molecular weight change of a base resin, and has a favorable sensitivity with time. As a result, it discovered that the said subject can be solved by mix | blending the basic compound which has a coumarin skeleton with the photosensitive resin composition, and came to complete this invention.

More specifically, this invention collects the base resin (A) which the solubility to aqueous alkali solution increases by the action of an acid, the acid generator (B) which generate | generates an acid in response to electromagnetic waves, and collects the said acid. A photosensitive resin composition containing a quencher (C), wherein the base resin (A) is a silicon-containing polymer compound, and the quencher (C) is a photosensitive resin composition which is a basic compound having a coumarin skeleton.

In more detail, the basic compound which has the said coumarin skeleton is a photosensitive resin composition which is a compound represented by following General formula (1).

[Formula 1]

(Wherein,

R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 1 to 5 carbon atoms.)

Effects of the Invention

According to the photosensitive resin composition of this invention, compared with the case of using the quencher which is a conventional amine compound, the stability with time-lapse of the composition at the time of storage can be improved, and especially the change over time during storage The gelation caused by the improvement of the molecular weight can be prevented. At the same time, changes in sensitivity and foreign matter increase during storage can be prevented. For this reason, according to the photosensitive resin composition of this invention, stability over time can be improved, demonstrating the quencher function which was conventionally traded off.

Moreover, since the upper layer film which consists of the photosensitive resin composition of this invention exhibits favorable alkali solubility even when it thins, high resolution is obtained and generation of edge roughness can be reduced.

Moreover, the shape of the resist pattern obtained from the photosensitive resin composition of this invention is a high aspect ratio, there is no pattern collapse and it is a favorable thing with high verticality.

1A is a diagram showing a process of the pattern forming method by lithography.

1B is a diagram showing a step of the method of forming a pattern by lithography.

1C is a diagram showing a step of the method of forming a pattern by lithography.

1D is a diagram showing a process of the pattern forming method by lithography.

1E is a diagram showing a step of the method of forming a pattern by lithography.

1F is a diagram showing a process of the pattern forming method by lithography.

Explanation of the sign

1 Processed film 2 Underlayer film

3 upper layer 4 photomask

DETAILED DESCRIPTION OF THE INVENTION

<Photosensitive resin composition (resist composition)>

Hereinafter, the photosensitive resin composition of this invention is demonstrated. The photosensitive resin composition (hereinafter may be referred to as a "positive resist composition" or "resist composition") of the present invention is a base resin (A) in which alkali solubility increases by the action of an acid and an acid in response to electromagnetic waves. An acid generator (B) which produces | generates and the quencher (C) which collects the generated acid are contained.

[Base resin (A)]

The base resin (A) of this invention is resin containing a silicon containing high molecular compound. Although it does not specifically limit as a silicon containing high molecular compound, In this invention, For example, the siloxane type high molecular compound which has a Si-O bond in a principal chain, the silicon carbide type high molecular compound which has a Si-C bond in a main chain, The polysilane type polymer compound which has a Si-Si bond in a principal chain, The silazane type polymer compound which has a Si-N bond in a principal chain, etc. are mentioned. Moreover, these arbitrary mixtures can be used. As a silicon-containing high molecular compound, a compound can be selected suitably so that the selection ratio with the board | substrate used may become large.

Moreover, in this invention, as base resin (A), you may further contain well-known various resin other than a silicon containing high molecular compound.

As base resin (A) in this invention, a siloxane polymer compound is preferable and resin which has a silsesquioxane resin (A1) as a main component is especially preferable. By making the main component of the base resin (A) a silsesquioxane resin, it is possible to maintain high resistance to oxygen plasma and high heat resistance while avoiding a decrease in time-dependent characteristics that are representative of a decrease in sensitivity during storage. In this manner, a pattern excellent in the cross-sectional shape can be obtained even through the heating step. In addition, the ratio of the silsesquioxane resin (A1) in the base resin (A) is preferably 70% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass.

As preferable silsesquioxane resin (A1), HSiO3 / ₂ unit and RSiO3 / ₂ unit are contained, and R is silsesquioxane resin which is group which has acid dissociation property. "Group having acid dissociability" is known as an acid, especially a group which can be cleaved by a photoacid generator (PAG). As the group having an acid dissociation property, those known to those skilled in the art can be used, and those described in European Patent Application No. 1142928 or US Patent Application Publication No. 2002/0090572 can be used. Forms part of the specification). Especially as group which has acid dissociation property, group represented by the following general formula (2) can be employ | adopted.

[Formula 2]

(Wherein,

R ₄ are each independently a linking group,

R ₅ is the second connector,

L is a linear or branched alkylene group having 1 to 10 carbon atoms, a fluoroalkylene group having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group, a substituted or unsubstituted cycloalkylene group, and a substituted or unsubstituted alk a It is selected from the group consisting of a rylene group, R <_6> is a hydrogen atom or a linear or branched alkyl group or a fluoroalkyl group,

R ₇ is an alkyl group or a fluoroalkyl group,

Z is a group dissociated by acid,

g represents an integer of 0 or 1,

h represents an integer of 0 or 1,

k represents an integer of 0 or 1.)

Examples of R ₄ each independently include alkylene chains such as methylene chain and ethylene chain, but are not limited thereto.

R ₅ includes, but is not limited to, a cycloalkylene group, a fluoroalkylene group, and an aryl group, such as a linear or branched alkylene group, a norbornyl group, or a cyclohexylene group.

Examples of L include, but are not limited to, substituted and unsubstituted methylene chains, ethylene chains, norbornene chains, cycloalkylene chains, and alkarylene chains such as fluorine substitution.

As R _{6, a} hydrogen atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; and a carbon number such as a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a 3,3,3-trifluoropropyl group Although 1-6 fluoroalkyl groups are mentioned, It is not limited to these.

As R <_7> , C1-C6 alkyl groups, such as a methyl group and an ethyl group; And C1-C6, such as a trifluoromethyl group, a 2,2,2- trifluoroethyl group, and a 3,3,3- trifluoropropyl group Although the fluoroalkyl group of is mentioned, It is not limited to these.

Examples of Z include -OH, -COOH, an ester group represented by general formula -COOR ₁₆ , a carbonate group represented by general formula -OCOOR ₁₇ , and an ether group represented by general formula -OR ₁₈ , but are not limited thereto. Here, R <_16> , R <_17> and R <_18> are group chosen so that acid dissociation may be provided.

In the acid dissociation group -COOR ₁₆ , as R ₁₆ , a t-butyl group; adamantyl group, norbornyl group, isobornyl group, 2-methyl-2-adamantyl group, 2-methyl-2-isobornyl group, 2 -Butyl-2-adamantyl group, 2-propyl-2-isobornyl group, 2-methyl-2-tetracyclododecenyl group, 2-methyl-2-dihydrodicyclopentadienylcyclohexyl group, 1- Cyclic or acyclic substituents having a tertiary bonding point such as methylcyclopentyl group or 1-methylcyclohexyl group (usually 7 to 12 carbon atoms); or 2-trimethylsilylethyl group or 2-triethylsilyl 2-trialkylsilylethyl groups, such as ethyl, are mentioned.

Examples of carbonate acid-dissociable group represented by the formula -OCOOR _17, specifically, (R ₁₇ is t- butyl) -Ot--butoxycarbonyl group can be given. Specific examples of the ether acid dissociation group represented by general formula -OR ₁₈ include tetrahydropyranyl ether (R ₁₈ is tetrahydropyranyl group) and trialkylsilyl ether (R ₁₈ is trialkylsilyl such as trimethylsilyl group). Can be.

As group represented by Z, Preferably, the organic ester group which produces | generates a cleavage reaction in the presence of the acid generate | occur | produced by a photo-acid generator, and produces | generates a carboxylic acid group is mentioned.

Examples of the acid dissociating group R include 1,1-dimethylethyl group, isopropyl group, 2-methyladamantyl group, cyclohexyl group, and 2-hydroxy-3-pinanyl ester or t-butyl ester of norbornane. Although it is possible, it is not limited to these.

In the present invention, in order to enhance the performance of the silsesquioxane resin, the silsesquioxane resin, in addition to the HSiO _3/2 unit and the RSiO _3/2 unit, is further added to the HSi (OR ₁₄ ) O _2/2. The unit, Si (OR ₁₄ ) _x O _{(4-x) / 2} unit, R ₁₅ SiO _3/2 unit, or any combination of these units may be contained. In these units, R ₁₄ can be each independently selected from a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of R ₁₄ include a methyl group, ethyl group, pro writing, butyl group, and 1-butyl group, but are not limited thereto. Preferably, R ₁₄ is a hydrogen atom or a methyl group. R ₁₅ is selected from the group represented by the general formula -R ₂₁ R ₂₂ . Here, R ₂₂ is preferably -OH or -COOH or a base soluble group, R ₂₁ is substituted and / or unsubstituted, and is a linear, branched, or cyclic C1-C12 alkyl group. . R _{15 is} bicycl [2,2,1] hepta-5-ene-2-trifluoromethylpropan-2-ol; 2-trifluoromethylbicyclo [2,2,1] hepta-5-ene 2-ol, 3,3,3-trifluoropropan-2-ol; and 2-trifluoromethyl-3,3-difluorobicyclo [2,2,1] hepta-5-ene-2 -All may be mentioned, but it is not limited to these.

Silsesquioxane resin, room access on the total amount of units contained in the rake dioxane resin, preferably from 5 mol% to 60 mol% or less, more preferably OR (of less than 45 mol% of at least 5 mole% HSi ₁₄ ) May contain _2/2 units. Further, the silsesquioxane resin is preferably 5 mol% or more and 45 mol% or less, more preferably 10 mol% or more and 25 mol% or less, based on the total amount of units contained in the silsesquioxane resin. Or (OR ₁₄ ) _x O _{(4-x) / 2} units. The silsesquioxane resin is 0 mol% or more and 25 mol% or less, preferably 10 mol% or more and 15 mol% or less (R ₁₅ SiO _{3 /)} relative to the total amount of units contained in the silsesquioxane resin. ₂ ) may contain units.

Although the compound represented by the following general formula is mentioned as silsesquioxane resin, It is not limited to these.

_{(HSiO 3/2) a (} RSiO 3/2) b

[Wherein R is isopropyl group, 2-methyladamantyl group, cyclohexyl group, or 2-hydroxy-3-pinanyl ester or 2-butyl ester of norbornane, a is 0.4 or more and 0.9 or less, b is 0.1 or more and 0.6 or less.]

(HSiO _3/2 ) _a (RSiO _3/2 ) _b (R ₁₄ OSiO _3/2 ) _c (SiO _4/2 ) _d

[Where R is an isopropyl group, 2-methyladamantyl group, cyclohexyl group, 2-hydroxy-3-pinanyl group, or t-butylbicyclo [2,2,1] heptane-2-carboxylate R ₁₄ is a hydrogen atom, a is 0.5 or more and 0.7 or less, b is 0.2 or more and 0.45 or less, c is 0.05 or more and 0.2 or less and d is 0.01 or more and 0.1 or less.]

(HSiO _3/2 ) _a (RSiO _3/2 ) _b (HSi (OR ₁₄ ) O _2/2 ) _c (Si (OR ₁₄ ) _x O _{(4-x) / 2} ) _d (R ₁₅ SiO _{3/2 e}

[Where R is an isopropyl group, 2-methyladamantyl group, cyclohexyl group, 2-hydroxy-3-pinanyl group, or t-butylbicyclo [2,2,1] heptane-2-carboxylate R ¹⁴ is a hydrogen atom, R ¹⁵ is bicyclo [2,2,1] hepta-5-ene-2-trifluoromethylpropan-2-ol, 2-trifluoromethylbicyclo [2, 2,1] hepta-5-en-2-ol, 3,3,3-trifluoropropan-2-ol, 2-trifluoromethyl-3,3-difluorobicyclo [2,2,1 ] Hepta-5-en-2-ol, a is 0.4 or more and 0.6 or less, b is 0.2 or more and 0.45 or less, c is 0.05 or more and 0.20 or less, d is 0.01 or more and 0.15 or less, e is 0.01 or more and 0.25 or less And x is 0 or more and 3 or less.]

The silsesquioxane resin of the present invention

(A) Hydrogen silsesquioxane resin which has the following general formula,

(HSiO _3/2 ) _m (HSi (OR ₁₄ ) O _2/2 ) _n (Si (OR ₁₄ ) _x O _{(4-x) / 2} ) _q

[Wherein, R ₁₄ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, x is 0 or more and 3 or less, m is 0.7 or more and 1.0 or less, preferably 0.8 or more and 0.9 or less, n is 0 or more and 0.4 Or less, preferably 0.05 or more and 0.3 or less, q is 0 or more and 0.45 or less, 0.9 ≦ m + n + q ≦ 1.0, and preferably m + n + q is about 1.0.]

(B) by reacting with a precursor of a group having acid dissociation,

(C) It can adjust by refine | purifying silsesquioxane resin which has the following general formula.

_{(HSiO 3/2) m1 (} RSiO 3/2) m2 (Si (OR 14) x O (4-x) / 2) q

[Wherein, R ₁₄ , n, q, and x are as described above, R is an acid dissociable group, m 2 is 0.1 or more and 0.6 or less, preferably 0.2 or more and 0.4 or less, and m1 + m2 is substantially the same as m. Value.]

What is known to a person skilled in the art can be used for the preparation method of hydrogen silsesquioxane resin (A). As such a method, hydrolysis of trihalosilanes, such as trichlorosilane, or trialkoxysilanes, such as triethoxysilane, is mentioned. Methods for preparing hydrogen silsesquioxane resins include US Pat. No. 3,615,272 (Collins et al.), US Pat. No. 5,010,159 (Bank et al.), US Pat. No. 4,999,497 (Frye et al.), US Pat. 6,353,074 (Carpenter et al.), US Patent Application No. 10/060558 (filed Jan. 30, 2002), and Japanese Patent Application Publication No. 59-178749, Japanese Patent Application Publication No. 60-86017 And Japanese Patent Application Laid-Open No. 63-107122 can be used, but is not limited thereto.

Next, the hydrogen silsesquioxane resin is reacted with the precursor of the group having (B) acid dissociation property. One method for reacting a hydrogen silsesquioxane resin with a precursor of a group having acid dissociation may include a method of catalytic hydrosilylation of a precursor of a group having acid dissociation and a hydrogen silsesquioxane resin.

As a precursor of group which has acid dissociation, t-butyl ester of norbornene, t-butyl-2- trifluoromethylacrylate, bicyclo [2,2,1] hepta-5-ene-2-t- Butyl carboxylate, cis-5-norbornene-2, 3-dicarboxylic acid anhydride, etc. are mentioned, It is not limited to these. Precursor of a group having an acid dissociable, the real sesquioleate on the total amount of units contained in the siloxane resin, and 5 mol% or more and 60 mol% or less, preferably RSiO _3/2 units of at least 15 mol% 35 mol% It is added to silsesquioxane resin with the addition amount produced.

As a hydrosilylation catalyst, although a platinum containing compound, a nickel containing compound, or a rhodium containing compound is mentioned as a compound well known to those skilled in the art, it is not limited to these. Examples of the platinum-containing compound include H ₂ PtCl ₆ , di-μ-carbonyldi-π-cyclopentadienyldinickel, platinum-carbonyl complexes, platinum-divinyltetramethyldisiloxane complexes and platinum-cyclovinylmethylsiloxane complexes. And platinum acetylacetonate (acac). Rh (acac) ₂ (CO) ₂ is mentioned as a rhodium containing compound, Ni (acac) ₂ is mentioned as a nickel containing compound. The amount of the hydrosilylation catalyst to be used is preferably 10 ppm or more and 10,000 ppm or less, more preferably 100 ppm or more and 1,000 ppm or less with respect to the amount of the reactant (that is, the precursor having a hydrogen silsesquioxane resin and an acid dissociable group). .

The reaction between the hydrogen silsesquioxane resin and the precursor of the group having acid dissociation is preferably performed at room temperature and atmospheric pressure, but may be accelerated by applying heat and pressure.

It is preferable that reaction of hydrogen silsesquioxane and the precursor of the group which has acid dissociation is performed in presence of a solvent. Examples of the solvent include alcohols such as ethyl alcohol or isopropyl alcohol; aromatic hydrocarbons such as benzene or toluene; alkanes such as n-heptane, dodecane, or nonane; ketones such as methyl isobutyl ketone; esters; glycol ether Siloxanes such as cyclic dimethylpolysiloxanes and linear dimethylpolysiloxanes (for example, hexamethyldisiloxane, octamethyltrisiloxane, and mixtures thereof); 2-ethoxyethanol; propylene glycol methyl ether acetate (PGMEA); cyclohexanone; and 1,2-diethoxyethane, etc., but it is not limited to these. Among these solvents, it is preferable to use methyl isobutyl ketone. The solvent may be the same solvent used for producing the hydrogen silsesquioxane resin.

The reaction time of the hydrogen silsesquioxane resin and the acid dissociating group precursor is preferably carried out for a sufficient time after substantially all of the precursor of the group having acid dissociation is reacted with the hydrogen silsesquioxane resin. However, in order to increase the molecular weight of the silsesquioxane resin and / or to improve the storage stability of the silsesquioxane resin, the reaction may be carried out for a long time while heating at a temperature of 40 ° C or more to the reflux temperature of the solvent. ("Thickening process"). A thickening process may be performed as a process following a reaction process, and may be implemented as a part of reaction process. The thickening step is preferably performed for 30 minutes or more and 6 hours or less, more preferably 1 hour or more and 3 hours or less.

The silsesquioxane resin containing a R ¹⁵ SiO _3/2 unit is prepared by reacting a hydrogen silsesquioxane resin (A) or silsesquioxane resin (C) with a functional group precursor. It is preferable to make a functional group precursor react with a hydrogen silsesquioxane resin or a silsesquioxane resin by catalytic hydrosilylation of a functional group precursor and a hydrogen silsesquioxane resin or a silsesquioxane resin. The catalytic hydrosilylation reaction is carried out under the same or the same treatment conditions as those described above for the catalytic hydrosilylation reaction of the hydrogen silsesquioxane resin and the precursor of the group having acid dissociability.

As one method, hydrogen silsesquioxane resin (A) can be made to react with a functional group precursor, and resin shown by the following general formula can be produced.

_{(HSiO 3/2) m1 (} R 15 SiO 3/2) m3 (HSi (OR 14) O 2/2) n (Si (OR 14) x O (4-x) / 2) q

[Wherein, R ₁₄ , n, q, and x are as described above, R ₁₅ is a modified functional group, m 3 is 0.01 or more and 0.25 or less, preferably 0.05 or more and 0.15 or less, and m1 + m3 is substantially the same value as m to be.]

Next, the said resin is made to react with the precursor of group which has acid dissociation property, and resin represented by the following general formula is produced.

(HSiO _3/2 ) _m1 (RSiO _3/2 ) _m2 (R ₁₅ SiO _3/2 ) _m3 (HSi (OR ₁₄ ) O _2/2 ) _n (Si (OR ₁₄ ) _x O _{(4-x) / 2} ) _q

[Wherein, R, R ₁₄ , R ₁₅ , n, q, m1, m2, m3, and x are as described above, and m1 + m2 + m3 is substantially the same value as m.]

Alternatively, the silsesquioxane resin (C) can be reacted with a functional group precursor to produce a resin represented by the following general formula.

_{(HSiO 3/2) m1 (} RSiO 3/2) m2 (R 15 SiO 3/2) m3 (HSi (OR 14) O 2/2) n (Si (OR 14) x O (4-x) / 2 ) _q

[Wherein, R, R ₁₄ , R ₁₅ , n, q, m1, m2, m3, and x are as described above, and m1 + m2 + m3 is substantially the same value as m.]

Alternatively, the hydrogen silsesquioxane resin (A) can be reacted with a mixture containing both a functional group precursor and a precursor of a group having acid dissociation property, thereby producing a resin represented by the following general formula.

(HSiO _3/2 ) _m1 (RSiO _3/2 ) _m2 (R ₁₅ SiO _3/2 ) _m3 (HSi (OR ₁₄ ) O _2/2 ) _n (Si (OR ₁₄ ) xO _{(4-x) / 2} ) _q

[Wherein, R, R ₁₄ , R ₁₅ , n, q, m1, m2, m3, and x are as described above, and m1 + m2 + m3 is substantially the same as m.]

Preferably, the hydrogen silsesquioxane resin is made to react with the precursor of the group which has acid dissociation property, and the silsesquioxane resin is made to react with a functional group precursor.

The novel functionalized hydrogen silsesquioxane-based resin used in the present invention has a weight average molecular weight of about 500 or more and 100,000 or less, preferably about 1,500 or more and 50,000 or less, and more preferably about 2,000 or more and 30,000 or less.

The novel functionalized hydrogen silsesquioxane resins of the present invention have suitable thermal stability, and in particular, suitable glass transition temperatures (Tg), which are suitable for the treatment of photoresists such as prebaking (PAB) and post-exposure heating (PEB). ) Tg of the functionalized hydrogen silsesquioxane resin of this invention becomes like this. Preferably it is 50 degreeC or more and 250 degrees C or less, More preferably, they are 70 degreeC or more and 180 degrees C or less, Most preferably, they are 80 degreeC or more and 150 degrees C or less.

Acid Generator (B)

As the acid generator (B), any of those known as acid generators in conventional chemically amplified resists can be appropriately selected and used. Examples of the acid generator (B) include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and poly (bissulphate). Diazomethane-based acid generators such as fonyl) diazomethanes and diazomethane-nitrobenzyl sulfonates, iminosulfonate-based acid generators, disulfone-based acid generators, and the like. In addition, in this invention, an acid generator (B) may be used independently and may be used in combination of 2 or more type.

The compounding quantity of an acid generator (B) is 0.5 mass part or more and 30 mass parts or less with respect to 100 mass parts of base resins (A), More preferably, they are 1 mass part or more and 10 mass parts or less. By setting it as 0.5 mass part or more, pattern formation is fully performed, and by setting it as 30 mass parts or less, a uniform solution can be obtained and storage stability improves.

Specific examples of the onium salt-based acid generator include trifluoromethanesulfonate or nonafluorobutanesulfonate of diphenyl iodonium; trifluoromethanesulfonate or nonafluoro of bis (4-tert-butylphenyl) iodonium Butanesulfonate, trifluoromethanesulfonate of triphenylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; trifluoromethanesulfonate of tri (4-methylphenyl) sulfonium, hepta Fluoropropanesulfonate or its nonafluorobutanesulfonate; Trifluoromethanesulfonate of (4-methylphenyl) diphenylsulfonium, Heptafluoropropanesulfonate or its nonafluorobutanesulfonate; (4- Trifluoromethanesulfonate of methoxyphenyl) diphenylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate; Trifluoromethanesulfonate of methyl (4-hydroxynaphthyl) sulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; and trifluoromethanesulfonate of monophenyldimethylsulfonium, the Heptafluoro propane sulfonate or its nonafluoro butane sulfonate, etc. are mentioned. In these, onium salt which uses a fluorinated alkyl sulfonic acid ion as an anion can be used preferably.

Specific examples of the oxime sulfonate-based acid generator include α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile, and α- (trifluoro Methylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloximino) -p-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -p-methylphenylacetonitrile, α- (methylsulfonyloxyimino) -p-bromophenylacetonitrile, and bis-O- (n-butylsulfonyl) -α-dimethyl Glyoxime etc. are mentioned. Among these, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile and bis-O- (n-butylsulfonyl) -α-dimethylglyoxime can be preferably used.

Specific examples of diazomethane-based acid generators include bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane and bis (isopropylsulfonate). Bisalkylsulfonyl diazomethane which has a C1-C4 linear or branched alkyl group, such as fonyl) diazomethane and bis (tert- butylsulfonyl) diazomethane; bis (cyclopentylsulfonyl) dia; Bisalkylsulfonyldiazomethanes having a cyclic alkyl group having 5 to 6 carbon atoms such as crude methane and bis (cyclohexylsulfonyl) diazomethane; bis (p-toluenesulfonyl) diazomethane and bis (2,4 Bisaryl sulfonyl diazomethane etc. which have aryl groups, such as -dimethylphenyl sulfonyl) diazomethane, etc. are mentioned.

Moreover, 1,3-bis (phenylsulfonyl diazommethylsulfonyl) propane (A = 3) which has a structure represented by following General formula (3) as poly (bissulfonyl) diazomethanes, for example 1,4-bis (phenylsulfonyldiazomethylsulfonyl) butane (for A = 4), 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane (for A = 6) , 1,10-bis (phenylsulfonyldiazomethylsulfonyl) decane (for A = 10), 1,2-bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane (for B = 2), 1,3-bis (cyclohexylsulfonyldiazomethylsulfonyl) propane (for B = 3), 1,6-bis (cyclohexylsulfonyldiazomethylsulfonyl) hexane (for B = 6), And 1,10-bis (cyclohexylsulfonyldiazomethylsulfonyl) decane (in the case of B = 10).

(3)

In this invention, when using an onium salt as an acid generator (B), it is preferable at the point which is excellent in a depth of focus width and an exposure margin. Moreover, when using diazomethane, it is preferable at the point which can improve the circularity of a resist hole pattern, or can suppress the standing wave of a cross-sectional pattern.

In addition, in this invention, onium salt type acid generator which makes a C3 or 4 perfluoroalkylsulfonate anion as an acid generator (B) may be abbreviated as C3-C4 onium salt hereafter. ), The mask linearity becomes good, and even a pattern in which various sizes are mixed is preferable because the mask can be faithfully reproduced. Moreover, since the thing excellent also in proximity effect, DOF, exposure margin, etc. can be obtained, it is preferable. Although the alkyl group of a perfluoroalkylsulfonate may be linear or branched, a linear type is preferable.

When mix | blending C3-C4 onium salt as an acid generator (B), it is preferable that the compounding quantity of C3-C4 onium salt with respect to the whole acid generator (B) shall be 50 mass%-100 mass%.

In addition, when mix | blending C3-C4 onium salt as an acid generator (B), Onium salt type acid generator (Hereinafter, C1 onium salt) which makes a C1-perfluoroalkylsulfonate anion. It may be abbreviated as above).

Moreover, in view of the effect of this invention, it is preferable to use a sulfonium salt also in an onium salt.

In addition, in a sulfonium salt, the triphenyl sulfonium salt is used preferably. The compounding quantity at the time of mix | blending a triphenylsulfonium salt becomes like this. Preferably it is 30 mol%-100 mol%, More preferably, you may be 50 mol%-100 mol% with respect to the whole acid generator (B). In particular, when the onium salt and diazomethane are mixed, the circularity of the resist hole pattern can be improved and the standing wave of the cross-sectional pattern can be suppressed without damaging the depth of focus width or the exposure margin. It is preferable because there is. When using this mixture, Onium salt content in a mixture becomes like this. Preferably it is 20 mol%-90 mol%, More preferably, it is 30 mol%-70 mol%.

Moreover, the triphenyl sulfonium salt which makes a perfluoroalkyl sulfonic acid ion anion especially represented by following General formula (4) among triphenyl sulfonium salt is used preferably at the point which can make high sensitivity.

[Formula 4]

(Wherein,

R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, a lower alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, or a halogen atom such as chlorine, fluorine or bromine, and p is 1 to 12, preferably Preferably it is 1-8, More preferably, the integer of 1-4 is represented.)

[Quencher (C)]

In order to improve stability over time, the positive photosensitive resin composition of this invention contains the quencher (C) which collects the acid generate | occur | produced from the acid generator (B) in the photosensitive resin composition, In this invention, As the quencher (C), one containing a basic compound having a coumarin skeleton is used. By adding a basic compound having a coumarin skeleton as the quencher (C), the stability over time, in particular, the sensitivity, molecular weight change, and foreign matter over time can be stabilized, and the resist pattern shape can be improved.

As quencher (C) in this invention, the basic compound which has a coumarin skeleton may be used alone, or 1 or more types of compounds other than the basic compound which has a coumarin skeleton may be used in combination.

The content of the quencher (C) is preferably 0.01 part by mass or more and 5.0 parts by mass or less, more preferably 0.05 part by mass or more and 4.0 parts by mass or less, particularly preferably 100 parts by mass of the base resin (A). It is the range of 0.1 mass part or more and 3.0 mass parts or less.

As a basic compound which has a coumarin skeleton used as quencher (C) of this invention, the compound represented by following General formula (5) is preferable.

[Chemical Formula 5]

(In formula, R <_1> , R <_2> and R <_3> show a C1-C5 alkyl group each independently.)

In the basic compound which has a coumarin skeleton represented by the said General formula (5), the compound whose R <_1> , R <_2> and R <_3> are all methyl groups, or the compound whose R <_1> is a methyl group, R <_2> and R <_{3> an} ethyl group are especially preferable. Do.

In addition, in this invention, you may combine nitrogen-containing organic compounds other than the basic compound which has a coumarin skeleton as quencher (C). Preferable nitrogen-containing organic compounds include aliphatic amines, especially nitrogen-containing organic compounds such as secondary aliphatic amines and tertiary aliphatic amines.

Specific examples of the aliphatic amine include amines (alkylamines or alkylalcoholamines) in which at least one hydrogen atom of ammonia (NH ₃ ) is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms. More specifically, monoalkylamines, such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; diethylamine, di-n-propylamine, di-n Dialkylamines such as -heptylamine, di-n-octylamine, and dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, Trialkylamines such as tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, and tri-n-dodecylamine; And alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. In these, alkyl alcohol amine or trialkyl amine is preferable and alkyl alcohol amine is the most preferable. In particular, among the alkyl alcohol amines, triethanolamine or triisopropanolamine is most preferred.

In addition, in this invention, it is preferable to combine the compound represented by following General formula (6) other than the basic compound which has a coumarin skeleton as quencher (C).

[Formula 6]

(In formula, R <_8> , R <_9> and R <_10> respectively independently represents an alkyl group, the cycloalkyl group which may have a substituent, or the aryl group which may have a substituent.)

In the compound represented by the said General formula (6), it is preferable that R <_8> -R <_10> is an aryl group which may respectively independently have a substituent, It is more preferable that it is a phenyl group which may have a substituent, It is especially preferable that it is a phenyl group .

<Other components>

The photosensitive resin composition of this invention may further contain arbitrary components other than a base resin (A), an acid generator (B), and a quencher (C). As an optional component, organic acid (D), a dissolution inhibitor, other additives, etc. are mentioned, for example.

[Organic acid (D)]

The photosensitive resin composition of this invention is made to contain an organic acid (D) as an arbitrary component for the purpose of preventing the sensitivity deterioration by mix | blending of a quencher (C), and improving a resist pattern shape, stability with storage time progress, etc. Can be. The organic acid (D) to be used is not particularly limited, and examples thereof include organic carboxylic acids or oxo acids of phosphorus or derivatives thereof. In addition, an organic acid (D) may be used individually by 1 type, and may use 2 or more types together.

Content in the case of mix | blending an organic acid (D), Preferably it is 0.01 mass part or more and 5.0 mass parts or less, More preferably, 0.05 mass part or more and 4.0 mass parts or less, Especially preferably, with respect to 100 mass parts of base resins (A). Preferably it is the range of 0.1 mass part or more and 3.0 mass parts or less.

As organic carboxylic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. can be used preferably, for example.

Examples of phosphorus oxo acids or derivatives thereof include derivatives such as phosphoric acid or esters thereof such as phosphoric acid, phosphoric acid-di-n-butyl ester, and phosphoric acid-diphenyl ester; phosphonic acid, phosphonic acid-dimethyl ester, phosphonic acid-di-n Derivatives such as phosphonic acids and esters thereof, such as -butyl ester, phenylphosphonic acid, phosphonic acid-diphenyl ester, and phosphonic acid-dibenzyl ester; derivatives such as phosphinic acid and their esters such as phosphinic acid and phenylphosphinic acid Among them, phosphonic acid is particularly preferable.

[Other additives]

In the photosensitive resin composition of this invention, as needed, additive which is miscible with a composition, for example, additional resin for improving the performance of the resist film obtained, surfactant for improving applicability, dissolution inhibitor, A plasticizer, a stabilizer, a coloring agent, an antihalation agent, etc. can be contained.

[Dissolution inhibitor]

In the photosensitive resin composition of this invention, a dissolution inhibitor becomes arbitrary components. When the dissolution inhibitor is contained in the photosensitive resin composition, line edge roughness can be effectively improved.

Here, the line edge roughness is a nonuniform unevenness of the line sidewall, and 3σ, which is a measure of the line edge roughness of the line and space pattern, is usually obtained. 3σ measures the width of the resist pattern of a sample at 32 points by measuring SEM (Hitachi Corporation make, brand name: S-9220), for example, and measures the value of the standard deviation (σ) calculated from the result. It can obtain | require by making it three times (3σ). This 3σ means that the smaller the value, the smaller the roughness, and a resist pattern having a uniform width is obtained.

When mix | blending a dissolution inhibitor, 1 type may be sufficient and 2 or more types may be mixed and used for it. Moreover, when making the photosensitive resin composition of this invention contain a dissolution inhibitor, it is preferable to make the content into the range of 1 mass part or more and 40 mass parts or less with respect to 100 mass parts of base resins (A), and 10 mass parts It is more preferable to set it as the range below 30 mass parts or more. By making content of a dissolution inhibitor more than a lower limit, the addition effect can fully be acquired. On the other hand, by using below an upper limit, deterioration of a pattern shape and deterioration of a lithographic characteristic can be suppressed.

As the dissolution inhibitor, for example, a compound in which at least one hydrogen atom of a phenolic hydroxyl group or a carboxyl group is substituted with an acid dissociable dissolution inhibiting group may be mentioned, which is already used in a three-component chemically amplified positive resist composition. Dissolved inhibitors can be used. As a dissolution inhibitor, it is preferable that a mass mean molecular weight is 1000 or less.

As a compound which has a phenolic hydroxyl group which can comprise a dissolution inhibitor, the polyphenol compound which has 3-5 phenolic hydroxyl groups, for example, the triphenylmethane type compound and bis (phenyl which have a hydroxyyl group as a nuclear substituent) Methyl) diphenylmethane type compound, and 1, 1- diphenyl-2- biphenyl ethane type compound are mentioned. Moreover, the 2-6 nucleus body obtained by formalin condensation of at least 1 sort (s) of phenols chosen from a phenol, m-cresol, and 2, 5- xylenol can also be used.

Moreover, biphenyl carboxylic acid, naphthalene (di) carboxylic acid, benzoyl benzoic acid, anthracene carboxylic acid, etc. are mentioned as a carboxyl compound in which the carboxy group was protected by the acid dissociable, dissolution inhibiting group.

Especially, it is preferable to use the compound represented by following General formula (7) (henceforth "DR1").

[Formula 7]

(Wherein R represents a CH ₂ COO-tert butyl group.)

[Organic Solvent]

The photosensitive resin composition of this invention dissolves the above-mentioned arbitrary components in base resin (A), an acid generator (B), quencher (C), and a desired thing, Preferably it is manufactured by organic solvent.

As an organic solvent used for the photosensitive resin composition of this invention, what is necessary is just to melt | dissolve each component to be used and to be able to make a uniform solution. In the present invention, any known organic solvent conventionally used as a solvent for chemically amplified resists can be used. These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.

The usage-amount of the organic solvent is not specifically limited, It is a density | concentration which can be apply | coated to a to-be-processed film, etc., and can be set suitably according to a coating film thickness. Generally, it is used so that solid content concentration of the photosensitive resin composition (resist composition) may be in the range of 2 mass% or more and 20 mass% or less, Preferably it is 5 mass% or more and 15 mass% or less.

As an organic solvent, For example, lactones, such as (gamma) -butyrolactone; Ketones, such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; Ethylene glycol, ethylene glycol monoacetate Polyhydric alcohols such as diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, or dipropylene glycol monoacetate, and monomethyl ethers thereof, monoethyl ether, monopropyl ether, monobutyl Derivatives such as ether or monophenyl ether; cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethoxy Ester, such as ethyl propionate, etc. are mentioned.

In this invention, it is preferable to use the mixed solvent which mixed propylene glycol monomethyl ether acetate (PGMEA) and a polar solvent as an organic solvent. What is necessary is just to determine the compounding ratio (mass ratio) suitably in consideration of compatibility of PGMEA and a polar solvent, etc., Preferably it is 1: 9-9: 1, More preferably, it is the range of 2: 8-8: 2.

In the present invention, a mixed solvent of propylene glycol monomethyl ether (PGME) and a solvent having a higher boiling point than PGME can be preferably used. Thereby, resist pattern shapes, such as line edge roughness and line-wise roughness (nonuniformity of the width | variety of the right and left of a line), can be improved. At the same time, the depth of focus (DOF) in the contact hole can be widened.

As the solvent having a higher boiling point than PGME, for example, among the solvents exemplified above, the boiling point exceeds 120 ° C, which is the boiling point of PGME, preferably the boiling point is 20 ° C or higher, and more preferably 25 Use higher than ℃. Moreover, there is no restriction | limiting in particular as an upper limit of the boiling point, It is preferable that it is about 200 degrees C or less. As such a solvent, propylene glycol monomethyl ether acetate (boiling point of 146 degreeC), EL (boiling point of 155 degreeC), (gamma) -butyrolactone (boiling point of 204 degreeC), etc. are mentioned, for example. Among these, EL is most preferable. 10 mass% or more and 60 mass% or less are preferable with respect to the whole mixed solvent, and, as for the compounding quantity of PGME in a mixed solvent, 20 mass% or more and 40 mass% or less are more preferable. When the compounding quantity of PGME in a mixed solvent exists in this range, the said effect is excellent.

<2-layer resist system>

The photosensitive resin composition of this invention can be used suitably for the method of patterning a support body using a two-layer resist. When the resist composition of the present invention is used as an upper layer material of a two-layer resist system, it has high sensitivity and high resolution, has a good cross-sectional shape, and may be referred to as edge roughness of line edge or hole pattern (together, edge roughness). ) Can give a small pattern.

[Resist Laminates of Two-Layer Resist Systems]

The resist laminate of the two-layer resist system is composed of an underlayer film (2 in FIG. 1B) that is insoluble in an alkali developer and dry-etchable on the processed film (1 in FIG. 1B) and the photosensitive resin composition of the present invention. The upper layer film (3 in FIG. 1B) formed is laminated.

The thickness of the upper layer film 3 and the lower layer film 2 in the resist laminate of the two-layer resist system is a throughput considering the desired aspect ratio and the time required for dry etching of the lower layer film 2. Although it can select suitably from the balance of, In general, as sum total of the thickness of the upper layer film 3 and the lower layer film 2, Preferably it is 15 micrometers or less, More preferably, it is 5 micrometers or less. Although the lower limit of the sum total of thickness is not specifically limited, Preferably it is 0.1 micrometer or more, More preferably, it is 0.35 micrometer or more.

The thickness of the upper layer film 3 becomes like this. Preferably it is 50 nm or more and 1000 nm or less, More preferably, it is 50 nm or more and 800 nm or less, More preferably, it is 100 nm or more and 500 nm or less. By setting the thickness of the upper layer film 3 within this range, the resist pattern can be formed at high resolution, and sufficient resistance to dry etching is obtained.

The thickness of the underlayer film 2 becomes like this. Preferably it is 200 nm or more and 20000 nm or less, More preferably, it is 300 nm or more and 8000 nm or less, More preferably, it is 400 nm or more and 5000 nm or less. By setting the thickness of the lower layer film 2 within this range, a resist pattern having a high aspect ratio can be formed, and sufficient etching resistance can be ensured at the time of etching the processed film.

In the pattern formation method by the two-layer resist system of this invention, the thickness of the upper layer film 3 can be 50 nm or more and 1000 nm or less, and the thickness of the lower layer film 2 can be 200 nm or more and 20000 nm or less, for example. In this invention, even if it is such a thick film, a pattern width can be made small and the pattern of a Gore-spectrum ratio (pattern of the lower layer film 2) can be formed. Therefore, the pattern obtained using the photosensitive resin composition of this invention can be used suitably for the field | area which especially requires microprocessing, such as for the electron beam, the pattern formation of a magnetic film, and other micromachining uses.

As a resist laminated body in which a resist pattern was formed, it is desired to form the pattern with high aspect ratio, without generating pattern collapse etc. It is because fine pattern formation with respect to a to-be-processed film can be performed with a higher precision, so that the pattern which has a high aspect ratio.

The aspect ratio here is the ratio (y / x) of the height y of the underlayer film 2 to the pattern width x of the resist pattern. In addition, the pattern width x of the resist pattern is the same as the pattern width after transferring to the underlayer film 2.

The pattern width refers to the width of the convex (lines) when the resist pattern is a line-shaped pattern such as a line-and-space pattern or an isolated line pattern. When the resist pattern is a hole pattern, the pattern width refers to the inner diameter of the formed hole (hole). In addition, when a resist pattern is a columnar dot pattern, the diameter is said. In addition, these pattern widths are all widths of a pattern downward.

According to the positive resist composition of the present invention, the pattern of the gore aspect ratio can be easily provided. In the case of a dot pattern or an isolated line pattern, for example, about the lower layer film of 2.5 micrometers in thickness, the dot pattern or the isolated line pattern of aspect ratio 8 or more and 20 or less which cannot be achieved by the conventional resist composition can be manufactured. have. In the case of a trench pattern, for example, a trench pattern having an aspect ratio of 10 or more and 20 or less, which cannot be achieved in a typical resist composition, can be produced for an underlayer film having a film thickness of 2.5 µm. In all, in the conventional resist composition, around aspect ratio 5 is a limit.

<Pattern formation by a two-layer resist system>

1A to 1F show process diagrams of a method of forming a pattern on a film to be processed by lithography of the present invention. In this embodiment, an underlayer film forming process (FIG. 1A), an upper layer film forming process (FIG. 1B), a 1st baking process (not shown), an exposure process (FIG. 1C), a 2nd baking process (not shown), and image development There is a process (FIG. 1D) and an etching process (FIG. 1E and FIG. 1F). Hereinafter, each process is demonstrated.

[Underlayer Film Forming Step]

1A is a diagram illustrating an underlayer film forming step of the pattern forming method according to the present embodiment. In the underlayer film forming step, a material for forming the underlayer film 2 is applied to the processing film 1 to obtain the underlayer film 2.

The material of the to-be-processed film 1 used in this invention is not specifically limited, A conventionally well-known thing can be used and it can select suitably according to the subsequent use of the pattern obtained by this invention. In the present invention, for example, a processed film for an electronic component, a film having a predetermined wiring pattern formed thereon, and the like, and more specifically, a silicon wafer, copper, chromium, iron, aluminum, or the like can be cited. The metal processing film, glass processing film, etc. are mentioned. Moreover, as a material of a wiring pattern, copper, aluminum, nickel, gold, etc. can be used, for example.

The method for applying the material for forming the underlayer film 2 on the workpiece film 1 is not particularly limited, and may be, for example, a spray method or a roll, depending on the material for forming the underlayer film 2. The coating method, the rotation coating method, etc. can be selected suitably. When spin-coating using a spinner or the like, preferably, the temperature is 180 ° C. or more and 300 ° C. or less, preferably 30 seconds or more and 300 seconds or less, more preferably 60 seconds or more and 180 seconds or less, and firing treatment. It is preferable to carry out.

In addition, in this embodiment, the organic or inorganic anti-reflective film may be formed between the obtained lower layer film 2 and the upper layer film 3 mentioned later.

The material for forming the underlayer film 2 is not particularly limited, and may be a material which is insoluble in the alkali developer used at the time of development after exposure, and which can be etched by a conventional dry etching method. Moreover, the material which forms the lower layer film 2 does not necessarily require photosensitivity like the material which forms the upper layer film 3 (photosensitive resin composition of this invention). In this invention, the resist composition and resin solution generally used as a base material can be used in manufacture of a semiconductor element and a liquid crystal display element.

Among them, since it can cope with current environmental problems in that it can be etched by an oxygen-based plasma and / or reactive ions, it is preferable to use a resist composition or a resin solution of an organic polymer forming an organic polymer film.

As a material for forming such an underlayer film 2, what has as a main component the at least 1 sort (s) chosen from the group which consists of a novolak resin, an acrylic resin, and a soluble polyimide is used preferably. The material containing these resins as a main component is easy to etch by oxygen plasma and has a strong resistance to fluorinated carbon-based gas which is generally used at the time of etching a silicon processed film or the like in a later step.

In particular, novolak resins and acrylic resins having alicyclic moieties or aromatic rings in the side chains are particularly inexpensive and commonly used, and are particularly excellent in dry etching resistance due to fluorocarbon gas in a later step. It is preferably used.

As a novolak resin which is a preferable material for forming the underlayer film 2, what is generally used for a positive resist composition can be used, The positive resist for i line | wire or g line | wire containing a novolak resin as a main component is used. Can also be used.

Here, a novolak resin is resin obtained by addition condensation of the aromatic compound (henceforth simply "phenol") and aldehydes which have a phenolic hydroxyl group under an acidic catalyst, for example.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol and p-butylphenol , 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2 , 3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglycinol, hydroxydiphenyl, bisphenol A, Gallic acid, a gallic acid ester, (alpha)-naphthol, (beta) -naphthol, etc. are mentioned.

Moreover, as aldehydes, formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, etc. are mentioned, for example.

Although the catalyst at the time of addition condensation reaction is not specifically limited, For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. can be used for an acid catalyst.

Thus, the mass average molecular weight (Mw) of the novolak resin obtained is normally 3000 or more and 10000 or less, Preferably it is 6000 or more and 9000 or less, More preferably, it is preferable to exist in the range of 7000 or more and 8000 or less. When the mass average molecular weight is less than 3000, it may sublimate when baked at high temperature, which is not preferable. Moreover, when mass average molecular weight exceeds 10000, there exists a tendency for dry etching to become difficult and it is not preferable.

What is marketed can also be used for novolak resin, As a commercial resin, BLC-100 (brand name; Tokyo Oka Corporation make) is mentioned, for example. In particular, while the mass mean molecular weight (Mw) is 5000 or more and 50000 or less, Preferably it is 8000 or more and 30000 or less, The content of the low-nucleus body of molecular weight 500 or less, Preferably 200 or less, the gel permeation chromatography method (GPC method) It is preferable to use the novolak resin which is 1 mass% or less, Preferably it is 0.8 mass% or less. The content of the low nucleus body is so preferable that it is small, Preferably it is 0 mass%.

By setting Mw of novolak resin to 50000 or less, it is excellent in the embedding characteristic with respect to the to-be-processed film which has a fine unevenness, On the other hand, by setting Mw to 5000 or more, it is excellent in the etching resistance with respect to a fluorocarbon type gas.

Moreover, the embedding characteristic with respect to the to-be-processed film which has a fine unevenness | corrugation becomes favorable because content of the low nucleus body of molecular weight 500 or less is 1 mass% or less. The reason why the embedding characteristics are improved by reducing the content of the low nucleus body is not clear.

Here, "the low nucleus of molecular weight 500 or less" is detected as a low molecular weight fraction of molecular weight 500 or less when polystyrene is analyzed by GPC method as a standard. The "low nucleus with a molecular weight of 500 or less" includes monomers which are not polymerized and those having a low degree of polymerization, for example, different depending on molecular weight, in which 2 to 5 molecules of phenols are condensed with aldehydes and the like.

The content (mass%) of the low-nucleus content of the molecular weight 500 or less graphs the analysis result by this GPC method, holding the concentration number on the horizontal axis and the concentration on the vertical axis, and graphing the low molecular weight of the molecular weight 500 or less with respect to the total area under the curve. It is measured by obtaining the ratio (%) of the area under the curve of Sean.

As an acrylic resin which is a preferable material for forming the underlayer film 2, what is generally used for a positive resist composition can be used, For example, it has a structural unit and carboxyl group derived from the polymeric compound which has an ether bond. And acrylic resins containing structural units derived from polymerizable compounds.

As a polymeric compound which has an ether bond, 2-methoxyethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate And (meth) acrylic acid derivatives having ether bonds and ester bonds such as phenoxy polyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate, and the like. Can be. These compounds can be used individually or in combination of 2 or more types.

As a polymeric compound which has a carboxy group, Monocarboxylic acids, such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids, such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxy ethyl succinic acid, 2 Compounds having carboxyl groups and ester bonds such as -methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid, and the like can be exemplified. Are acrylic acid and methacrylic acid. These compounds can be used individually or in combination of 2 or more types.

Moreover, the soluble polyimide which is a preferable material for forming the underlayer film 2 should just be a polyimide which can be made into a liquid by the above-mentioned organic solvent.

[Layer film forming step]

1B is a diagram illustrating an upper layer film forming step of the pattern forming method according to the present embodiment. In the upper layer film formation process which concerns on this embodiment, the photosensitive resin composition of this invention is apply | coated on the lower layer film 2 obtained above, the upper layer film 3 of the photosensitive resin composition is formed, and it is for resist film formation Obtain a laminate.

As a method of apply | coating the photosensitive resin composition of this invention on the underlayer film 2, it does not specifically limit, For example, a spray method, a roll coat method, a rotation coating method, etc. are mentioned.

In the pattern formation method of the present embodiment, since the resist pattern is formed by a two-layer resist system in which the lower layer film and the upper layer film are laminated, the upper layer film can be thinned even when a pattern having a high aspect ratio is formed.

In general, when the upper layer film is thinned, resolution is improved, but edge roughness such as line edge roughness and edge roughness of a hole pattern tends to be remarkable. However, since the upper layer film which consists of the photosensitive resin composition of this invention exhibits favorable alkali solubility even when it thins, high resolution is obtained and generation of edge roughness can be reduced.

[First Firing Step]

In a 1st baking process, the upper layer film 3 which consists of the photosensitive resin composition formed in the lower layer film 2 by the upper layer film formation process is baked or semi-baked, and a cured film or a semi-hardened film is formed. The 1st baking process in this invention is arbitrary processes, and what is necessary is just to form, according to the kind of photosensitive resin composition.

The conditions of baking or semi-baking are not specifically limited. For example, under the temperature conditions of 70 degreeC or more and 130 degrees C or less, it is preferable to heat 40 second or more and 180 second or less, preferably 60 second or more and 90 second or less. In particular, in order to prevent generation of a white edge, it is effective to make the heating temperature in a 1st baking process into the grade of 70 degreeC or more and 90 degrees C or less.

Exposure process

1C is a diagram illustrating an exposure step of the pattern forming method according to the present embodiment. In an exposure process, exposure (shown by an arrow) is performed through the photomask 4 to the upper layer film 3 which consists of a photosensitive resin composition obtained by baking or semi-baking by a 1st baking process, and at least one part An exposure film which selectively serves as an exposure area is obtained.

The acid generator (B) contained in the photosensitive resin composition of this invention produces | generates an acid in response to exposure, and the base resin (A) which received the action of the generated acid increases solubility to aqueous alkali solution. For this reason, the difference in solubility with respect to a developing solution arises between an exposure range and an unexposed range, and an exposure range is melt | dissolved and removed by the developing process of the next process.

The exposure apparatus used is not specifically limited. Examples of the light source used for exposure include KrF excimer laser, ArF excimer laser, F ₂ excimer laser, electron beam, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), X-ray, soft X-ray, and the like. Can be mentioned.

In exposure of the coating layer which consists of the photosensitive resin composition of this invention, even when a fine resist pattern is formed, the line edge roughness of the pattern and the rectangularity of the cross-sectional shape are good, and the problem of pattern collapse does not occur. Etc., an electron beam can be used preferably at the point which can aim at high fine processing.

The exposure method in the exposure process of this invention will not be specifically limited if light and / or heat can be applied to the required area | region of an upper layer film. For example, selective irradiation using a photomask, drawing by an electron beam, etc. are mentioned. At the time of exposure, the exposure between the lens and the upper layer film on the processing film, which is conventionally filled with an inert gas such as air or nitrogen, is filled with a solvent (liquid immersion medium) having a refractive index greater than that of air. So-called immersion lithography (immersion lithography) for performing (immersion lithography) may also be employed.

The exposure conditions in the exposure process of this invention are not specifically limited. According to the light source and method used for exposure, exposure area, exposure time, exposure intensity, etc. can be selected suitably.

[2nd baking process]

In a 2nd baking process, the exposure film which made at least one part exposure area is baked further. In the pattern formation method of this invention, a 2nd baking process is arbitrary processes.

The baking conditions of a 2nd baking process are not specifically limited. For example, under the temperature conditions of 70 degreeC or more and 130 degrees C or less, it is preferable to heat from 40 second to 180 second, preferably 60 second to 90 second.

[Developing process]

1D is a diagram illustrating a developing step of the pattern forming method according to the present embodiment. In a developing process, the exposure area of the exposure film which performed the exposure process and the 2nd baking process as needed is selectively melt | dissolved according to a developing solution, and the resist film in which the pattern which consists of a photosensitive resin composition was formed is obtained.

1D is a state in which the exposure area of the exposure film is dissolved in response to the exposure of the exposure step. The exposure area of the upper layer film 3 is removed by dissolution to leave the unexposed area as a pattern.

The alkali developer used in the developing step is not particularly limited. For example, an aqueous solution of tetramethylammonium hydroxide of 0.05% by mass or more and 10% by mass or less, preferably 0.05% by mass or more and 3% by mass or less can be used. In this embodiment, the resist pattern which is faithful to a mask pattern can be formed in an upper layer film by the image development process.

The shape of the resist pattern obtained by this embodiment is a good aspect ratio, there is no pattern collapse, and it is a favorable thing with high verticality.

[Etching Process]

1E and 1F are diagrams showing an etching step. In the etching step, the laminate having the resist film on which the pattern is formed is irradiated with plasma and / or reactive ions (illustrated by an arrow) using the pattern as a mask to remove the underlayer film by etching.

The gas of the plasma and / or reactive ions used in the etching step is not particularly limited as long as it is a gas commonly used in the dry etching field. For example, oxygen, a halogen, sulfur dioxide, etc. are mentioned. Among these, it is preferable to use the plasma containing oxygen and / or reactive ion from the point that the resolution of the pattern obtained is high, and since it is used universally. In the case of using oxygen-containing plasma and / or reactive ions, when the silsesquioxane resin is selected as the base resin (A), high etching resistance can be realized.

The etching method is not particularly limited. For example, known methods such as chemical etching such as downflow etching and chemical dry etching; physical etching such as sputter etching and ion beam etching; chemical and physical etching such as RIE (reactive ion etching) can be used.

As the most common dry etching, a parallel plate type RIE can be mentioned. In this method, first, a laminate in which a resist pattern is formed is placed in a chamber of an RIE apparatus, and a necessary etching gas is introduced. In the chamber, when a high frequency voltage is applied to the holder of the resist stack placed in parallel with the upper electrode, the gas is plasmaified. In the plasma, charged particles such as positive and negative ions and electrons, neutral active species and the like exist as etching species. When these etch species are adsorbed to the lower organic layer, chemical reactions occur and the reaction product is released from the surface, exhausted to the outside, and etching proceeds.

Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to this.

<Synthesis example 1>

HSiO _3/2 silsesquioxane resin having the units and RSiO _3/2 units was prepared by the Dow Corning Corporation, according to the method disclosed in the pamphlet of International Publication No. 05/007747. The reaction was carried out in a PEGMEA solvent to obtain a solution having a content of silsesquioxane resin of 20% by mass (hereinafter, referred to as "ZL-1001").

<Example 1>

[Preparation of Photosensitive Resin Composition]

As 100 parts by mass of the resin (ZL-1001) obtained in Synthesis Example 1, as a acid generator, 4.5 parts by mass of a compound represented by the following General Formula (8) (manufactured by Wako Pure Chemical Industries, Ltd., product name: WPAG-469), and a quencher 0.753 parts by mass of 7-diethylamino-4-methylcoumarin and 0.339 parts by mass of malonic acid as an organic acid are dissolved in a mixed solvent of propylene glycol monomethyl ether acetate: propylene glycol monomethyl ether = 8: 2 (mass ratio) to give a solid content concentration. The positive photosensitive resin composition (resist composition) was obtained by preparing so that it may become 5 mass%. Table 1 shows the formulation of the photosensitive resin composition.

[Formula 8]

About the obtained photosensitive resin composition, two types of storage of 6 hours were implemented at (i) 0 degreeC and (ii) 60 degreeC.

[Formation of Underlayer Film]

BLC-720 (manufactured by Tokyo Oka Industries Co., Ltd.) was applied on the silicon processed film as a lower layer film material by using a spinner, and a lower layer film having a film thickness of 210 nm was formed by performing a firing treatment at 100 ° C and 180 ° C for 90 seconds. It was.

[Application of Photosensitive Resin Composition]

On the obtained underlayer film, the photosensitive resin composition (i) or (ii) obtained above was apply | coated using a spinner, and it pre-baked at 85 degreeC for 60 second, and then dried, and the coating film of 100 nm of film thicknesses, respectively, was dried. It formed and the laminated body for resist pattern formation was obtained.

[Exposure]

Next, ArF excimer laser (193 nm) was selectively irradiated with ArF exposure apparatus (The Nikon company make, brand name: NSR-S302A, NA (number of openings): 0.60, (sigma): 2/3 ring zone).

[phenomenon]

After irradiation, the post-exciposor bake (PEB) treatment was carried out at 95 ° C. for 60 seconds, and further development was carried out at 23 ° C. for 30 seconds with an alkaline developer (2.38 mol% tetramethylammonium hydroxide aqueous solution). Furthermore, the resist pattern was obtained by post-baking at 100 degreeC for 60 second. The obtained resist pattern was a 110 nm vertical line-and-space (L & S) pattern.

[evaluation]

[Sensitivity over time]

When evaluating the sensitivity over time, the line widths are plotted for each exposure amount for each of the photosensitive resin composition (i) stored at 0 ° C. and the photosensitive resin composition (ii) stored at 60 ° C. for 6 hours, and the sensitivity becomes a design dimension. The ratio ((ii) / (i)) of the exposure amount corresponding to (EOP) was obtained. The evaluation results are shown in Table 1.

[Molecular weight change, foreign matter over time]

When evaluating a molecular weight change and the foreign matter over time, the photosensitive resin composition obtained above was preserve | saved at 40 degreeC for 1 month, and the molecular weight change of the composition after storage, and the foreign material with time progress were evaluated, respectively. Molecular weight change converted the molecular weight of the resist composition preserve | saved at -20 degreeC as a reference value (100%). In addition, the foreign matter over time measured the number of foreign substances of 0.2 micrometer or more in 1 ml of resist compositions. The evaluation results are shown in Table 1.

Example 1 Comparative Example 1 Example 2 Example 3 Suzy Synthesis Example 1
100 parts by mass Synthesis Example 1
100 parts by mass Synthesis Example 1
100 parts by mass Synthesis Example 1
100 parts by mass Acid generator WPAG-469
4.5 parts by mass WPAG-469
4.5 parts by mass WPAG-469
4.5 parts by mass WPAG-469
4.5 parts by mass
Quencher 7-diethylamino-4-
Methylcoumarin
0.753 parts by mass Triisopropanolamine
0.6225 parts by mass 7-diethylamino-4-methylcoumarin
0.2 parts by mass 7-diethylamino-4-methylcoumarin
0.2 parts by mass TPS-OH
1.5 parts by mass TPS-OH
1.5 parts by mass Organic acid Malonic acid
0.339 parts by mass Malonic acid
0.339 parts by mass Salicylic acid
0.36 parts by mass - menstruum Propylene glycol monomethyl ether acetate: Propylene glycol monomethyl ether = 8: 2 Propylene glycol monomethyl ether acetate: Propylene glycol monomethyl ether = 8: 2 Propylene glycol monomethyl ether acetate: Propylene glycol monomethyl ether = 8: 2 Propylene glycol monomethyl ether acetate: Propylene glycol monomethyl ether = 8: 2 Sensitivity Over Time 101.46% 81.35% 100.13% 100.76% Molecular weight change 100% 140% - - Foreign object over time () 2.3 Multiple (Unmeasurable) - -

<Comparative Example 1>

[Preparation of Photosensitive Resin Composition]

In Example 1, instead of 7-diethylamino-4-methylcoumarin as a quencher, 0.6225 parts by mass of triisopropanolamine was used to obtain a positive photosensitive resin composition. Table 1 shows the formulation of the photosensitive resin composition.

After obtaining the laminated body for resist pattern formation by the operation similar to Example 1 using the obtained photosensitive resin composition, exposure process and image development were performed and the resist pattern was obtained. Moreover, using the obtained photosensitive resin composition, the sensitivity, the molecular weight change, and the foreign material with time progress were evaluated similarly to Example 1. The evaluation results are shown in Table 1.

As shown in Table 1, the sensitivity of the resist pattern obtained from the photosensitive resin composition of the comparative example 1 increased with time. Moreover, the molecular weight greatly increased, and many foreign substances existed so that measurement was impossible. On the other hand, while the photosensitive resin composition of Example 1 showed stable sensitivity also with time, there was no change of molecular weight and there existed almost no foreign substance.

<Example 2>

[Preparation of Photosensitive Resin Composition]

100 parts by mass of the resin (ZL-1001) obtained in Synthesis Example 1, 4.5 parts by mass of WPAG-469 (manufactured by Wako Pure Chemical Industries, Ltd.) as an acid generator, and 0.2 mass of 7-diethylamino-4-methylcoumarin as a quencher 1.5 mass parts of compound formula (TPS-OH) represented by the following general formula (9), and 0.36 mass parts of salicylic acid as an organic acid, The mixed solvent of propylene glycol monomethyl ether acetate: propylene glycol monomethyl ether = 8: 2 (mass ratio) It melt | dissolved in and prepared so that solid content concentration might be 5 mass%, and the positive photosensitive resin composition was obtained. Table 1 shows the formulation of the photosensitive resin composition.

[Formula 9]

<Example 3>

[Preparation of Photosensitive Resin Composition]

100 parts by mass of the resin (ZL-1001) obtained in Synthesis Example 1, 4.5 parts by mass of WPAG-469 (manufactured by Wako Pure Chemical Industries, Ltd.) as an acid generator, and 0.2 mass of 7-diethylamino-4-methylcoumarin as a quencher Part and 1.5 parts by mass of TPS-OH are dissolved in a mixed solvent of propylene glycol monomethyl ether acetate: propylene glycol monomethyl ether = 8: 2 (mass ratio) to prepare a solid content concentration of 5% by mass, and a positive photosensitive property. The resin composition was obtained. Table 1 shows the formulation of the photosensitive resin composition.

Using the photosensitive resin composition obtained in Examples 2 and 3, after obtaining the laminated body for resist pattern formation by the same operation as Example 1, exposure process and image development were performed and the resist pattern was obtained. Moreover, using the obtained photosensitive resin composition, the sensitivity over time was evaluated similarly to Example 1. The evaluation results are shown in Table 1.

<Example 4>

[Preparation of Photosensitive Resin Composition]

100 parts by mass of the resin ZL-1001 obtained in Synthesis Example 1, 3 parts by mass of WPAG-469 (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.2 part by mass of 7-diethylamino-4-methylcoumarin resin and TPS- as a quencher. Positive type photosensitive resin composition was obtained by dissolving 1 mass part of OH in the mixed solvent of propylene glycol monomethyl ether acetate: propylene glycol monomethyl ether = 8: 2 (mass ratio), and preparing so that solid content concentration might be 5 mass%. .

[Immersion exposure evaluation]

About the obtained photosensitive resin composition, liquid immersion exposure was evaluated. When evaluating, first, a BLC-720 (manufactured by Tokyo Oka Industries Co., Ltd.) was applied on a silicon processed film as a lower layer film material by using a spinner, and the lower layer film having a film thickness of 250 nm was subjected to baking treatment at 250 ° C. for 90 seconds. Formed.

Subsequently, on the obtained underlayer film, the photosensitive resin composition obtained above was apply | coated using a spinner, the prebaking process was performed for 90 second at 85 degreeC and 95 degreeC, and it is then dried to form a coating film with a film thickness of 60 nm. And the laminated body for resist pattern formation were obtained.

Next, cyclic purple which Daikin Kogyo Co., Ltd. make, brand name: Demumu S-20, Asahi Glass Co., Ltd. make, brand name: Cytop (ring-type perfluoroalkyl polyether) were mixed so that mixing weight ratio = 1: 5. A fluororesin containing fluoroalkyl polyether was prepared, and the fluororesin was dissolved in perfluorotributylamine to prepare a protective film material having a resin concentration of 2.5% by mass.

On the obtained resist pattern formation laminated body, the prepared protective film material was apply | coated rotationally, and it heated at 85 degreeC for 60 second, and formed the protective film of film thickness 32nm.

Subsequently, the liquid immersion two-beam interference exposure by the prism, water, and two-beam interference of 193 nm was performed using two-beam interference exposure machine LEIES193-1 (made by Nikon) as immersion exposure.

After the immersion lithography treatment, PEB treatment was carried out under the conditions of 120 ° C and 90 seconds, and paddle development was performed for 30 seconds with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23 ° C. Thereafter, water was rinsed using pure water for 30 seconds, followed by drying with water to form a resist pattern (hereinafter referred to as L / S pattern) of the line and space (1: 1).

As a result of observing the L / S pattern obtained by an electron microscope (SEM), a resist pattern in which 55 nm line and space became 1: 1 was confirmed. Moreover, the shape of the resist pattern did not have the curvature of a line, and also had few roughness, such as a pattern side wall.

Claims (15)

It contains base resin (A) which increases the solubility in aqueous alkali solution by the action of acid, an acid generator (B) which generates an acid in response to electromagnetic waves, and a quencher (C) which collects the acid. As a photosensitive resin composition to say, The base resin (A) contains a silicon-containing polymer compound, The quencher (C) contains a basic compound having a coumarin skeleton, The photosensitive resin composition containing organic acid (D) containing 0.01 mass part or more and 5 mass parts or less with respect to 100 mass parts of said base resins (A). The method of claim 1, The basic compound which has the said coumarin skeleton is a photosensitive resin composition represented by following General formula (1). [Formula 1]

(Wherein, R ₁ , R ₂ , and R ₃ each independently represent an alkyl group having 1 to 5 carbon atoms.) The method of claim 2, The basic compound which has the said coumarin skeleton is a photosensitive resin composition whose R <_1> , R <_2> and R <_3> are all methyl groups. The method of claim 2, The basic compound which has the said coumarin skeleton is a photosensitive resin composition whose R <_1> is a methyl group, R <_2> and R <_3> are ethyl groups. The method of claim 1, The base resin (A) contains HSiO _3/2 units and silsesquioxane resins containing RSiO _3/2 units, and R is a photosensitive resin composition which is a group having acid dissociation properties represented by the following General Formula (2). . [Formula 2]

(Wherein, R ₄ are each independently a linking group, R ₅ is the second connector, L is a linear or branched alkylene group having 1 to 10 carbon atoms, a fluoroalkylene group having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group, a substituted or unsubstituted cycloalkylene group, and a substituted or unsubstituted group. It is selected from the group which consists of an alxarylene group, R ₆ is a hydrogen atom or a linear or branched alkyl group or a fluoroalkyl group, R ₇ is an alkyl group or a fluoroalkyl group, Z is a group dissociated by acid, g represents an integer of 0 or 1, h represents an integer of 0 or 1, k represents an integer of 0 or 1.) The method of claim 1, Content of the said acid generator (B) is 0.5 mass part or more and 30 mass parts or less with respect to 100 mass parts of said base resins (A). The method of claim 1, Content of the said quencher (C) is 0.01 mass part or more and 5 mass parts or less with respect to 100 mass parts of said base resins (A). delete The method of claim 1, The said photosensitive resin composition is a photosensitive resin composition which is a composition for resists. The method of claim 1, The said photosensitive resin composition is a photosensitive resin composition which is a composition for upper layer resists of a two-layer resist system. The method of claim 1, The said photosensitive resin composition is a photosensitive resin composition which is a composition for upper layer resists of the two-layer resist system which makes a lower layer into an organic type polymer film. As a method of forming a pattern on a film to be processed by lithography, An underlayer film forming step of forming an underlayer film on the workpiece film; An upper layer film forming step of applying the photosensitive resin composition according to any one of claims 1 to 7 on the lower layer film to obtain an upper layer film, An exposure step of exposing the upper layer film to obtain an exposure film having at least part of the exposure area; And a developing step of treating the exposure film with a developing solution to selectively dissolve the exposure area of the upper layer film to obtain a resist film having a pattern formed of the photosensitive resin composition. 13. The method of claim 12, The underlayer film is an organic polymer film pattern forming method. 13. The method of claim 12, And a etching step of etching the underlayer film by plasma and / or reactive ions using the resist film as a mask after the developing step. The method of claim 14, Wherein said plasma and / or reactive ions contain oxygen.

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