Sacrificial film-forming composition and method for producing sacrificial film pattern

Abstract

The purpose of the present invention is to provide a sacrificial film-forming composition that can form a resist pattern (sacrificial film pattern) exhibiting a high exposure sensitivity, excellent resolution, good pattern shape, and excellent dry etching resistance. A sacrificial film-forming composition according to the present invention contains a novolac resin (A), a quinonediazide compound (B), and a compound (C) that has an aromatic ring, a hydroxyl group bonded to the aromatic ring, and an alkoxymethyl group bonded to the aromatic ring.

Description

Sacrificial film forming composition and method for manufacturing sacrificial film pattern

[0001] The present invention relates to a composition for forming a sacrificial film that can form a resist pattern (sacrificial film pattern) that has high exposure sensitivity, excellent resolution, a good pattern shape, and excellent dry etching resistance.

[0002] Known methods for forming wiring and terminals on a substrate include etching a metal layer using a resist pattern as a mask pattern, and plating using a resist pattern as a mold pattern for plating.

[0003] A method for forming a resist pattern when forming wiring or terminals on a substrate includes forming a resist layer on the substrate using a negative resist composition, and then exposing and developing the resist layer. However, negative resist compositions have problems such as insufficient resolution and difficulty in removing the resist pattern (sacrificial film pattern) from the substrate after forming the wiring or terminals.

[0004] On the other hand, positive resist compositions have the advantage that they have good resolution and the resist pattern (sacrificial film pattern) can be easily removed from the substrate after the wiring and terminals have been formed.

[0005] As a positive resist composition for forming a sacrificial film, for example, Patent Document 1 proposes a positive resist composition containing an alkali-soluble phenolic resin and a quinone diazide sulfonic acid ester having a specific structure as a photosensitizer.

[0006] Japanese Patent Application Publication No. 3-48249

[0007] There is a demand for a positive resist composition for forming a sacrificial film that can form a resist pattern (sacrificial film pattern) that has high exposure sensitivity, excellent resolution, a good pattern shape (rectangular or trapezoidal cross-sectional shape), and excellent dry etching resistance. However, conventional positive resist compositions have not satisfied all of the above-mentioned properties.

[0008] The present invention has been made in view of the above problems, and aims to provide a composition for forming a sacrificial film that can form a resist pattern (sacrificial film pattern) that has high exposure sensitivity, excellent resolution, a good pattern shape, and excellent dry etching resistance.

[0009] The present inventors have conducted extensive research to solve the above-mentioned problems, and have found that the above-mentioned problems can be solved by further blending a compound having a specific functional group with a composition for forming a sacrificial film containing a novolac resin and a quinone diazide compound. The present invention was completed based on this finding and further research.

[0010] That is, the present invention provides the following aspects. <1> A composition for forming a sacrificial film, comprising a novolak resin (A), a quinone diazide compound (B), and a compound (C) having an aromatic ring, a hydroxyl group bonded to the aromatic ring, and an alkoxymethyl group bonded to the aromatic ring. <2> The composition for forming a sacrificial film according to <1>, wherein the total number of hydroxyl groups bonded to the aromatic ring is 2 to 8. <3> The composition for forming a sacrificial film according to <1> or <2>, wherein the total number of alkoxymethyl groups bonded to the aromatic ring is 2 to 8. <4> The composition for forming a sacrificial film according to any one of <1> to <3>, wherein the alkoxy group of the alkoxymethyl group bonded to the aromatic ring has 1 to 8 carbon atoms. <5> A method for producing a sacrificial film pattern, comprising: a coating film formation step of forming a coating film using the sacrificial film-forming composition according to any one of <1> to <4>, an exposure step of selectively exposing the coating film to light, and a development step of developing the coating film after the exposure step to form a pattern. <6> The method for producing a sacrificial film pattern according to <5>, further comprising a heating step of heating the pattern after the development step. <7> Use of a composition containing a novolak resin (A), a quinone diazide compound (B), and a compound (C) having an aromatic ring, a hydroxyl group bonded to the aromatic ring, and an alkoxymethyl group bonded to the aromatic ring, for producing a composition for forming a sacrificial film.

[0011] The sacrificial film-forming composition of the present invention contains, in addition to the novolac resin (A) and the quinone diazide compound (B), a compound (C) having an aromatic ring, a hydroxyl group bonded to the aromatic ring, and an alkoxymethyl group bonded to the aromatic ring, and thereby can form a resist pattern (sacrificial film pattern) that not only has high exposure sensitivity and excellent resolution but also has a good pattern shape and excellent dry etching resistance. Therefore, the sacrificial film-forming composition of the present invention is suitably used as a resist material (sacrificial film material) used when forming wiring or terminals on a substrate.

[0012] 1. Sacrificial Film-Forming Composition The sacrificial film-forming composition of the present invention is characterized by containing a novolac resin (A), a quinone diazide compound (B), and a compound (C) having an aromatic ring, a hydroxyl group bonded to the aromatic ring, and an alkoxymethyl group bonded to the aromatic ring. The sacrificial film-forming composition of the present invention will be described in detail below.

[0013] [Novolac Resin (A)] The composition for forming a sacrificial film of the present invention contains a novolac resin (A). As the novolac resin (A), any novolac resin used in a positive resist material can be used without particular limitation, and examples thereof include resins obtained by polymerizing a phenol and an aldehyde in the presence of an acid catalyst.

[0014] Examples of phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol. Examples of suitable phenols include alkylphenols such as t-butylphenol, trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol, polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol and phloroglucinol, alkyl polyhydric phenols (alkyl group carbon number: 1 to 4) such as alkylresorcinol, alkylcatechol and alkylhydroquinone, α-naphthol, β-naphthol, hydroxydiphenyl and bisphenol A. These phenols may be used alone or in combination of two or more.

[0015] Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, etc. These aldehydes may be used alone or in combination of two or more.

[0016] Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfate, and paratoluenesulfonic acid; and metal salts such as zinc acetate.

[0017] In the composition for forming a sacrificial film, the content of the novolac resin (A) is usually about 50 to 95 mass % based on the total solid content of the composition for forming a sacrificial film, and from the viewpoint of further improving the effects of the present invention, it is preferably 55 to 90 mass %, more preferably 60 to 90 mass %.

[0018] [Quinone Diazide Compound (B)] The sacrificial film-forming composition of the present invention contains a quinone diazide compound (B). The quinone diazide compound (B) interacts (e.g., hydrogen bonds) with the functional groups of the novolac resin (A) before exposure to light, rendering the novolac resin (A) insoluble in an alkaline aqueous solution. Furthermore, when irradiated with radiation such as ultraviolet light, gamma rays, or electron beams, the quinone diazide compound (B) generates an alkali-soluble carboxylic acid compound. The resulting alkali-soluble carboxylic acid compound in the irradiated region facilitates the dissolution of the novolac resin (A) in that region, along with the carboxylic acid compound, in an alkaline aqueous solution. This action increases the difference in alkali solubility between the unexposed and exposed regions of the novolac resin (A), thereby forming a resist pattern (sacrificial film pattern).

[0019] The quinone diazide compound (B) can be any quinone diazide compound used in positive resist materials without any particular limitation, and examples thereof include a quinone diazide sulfonic acid bonded to a polyhydroxy compound via an ester bond, a quinone diazide sulfonic acid bonded to a polyamino compound via a sulfonamide bond, a quinone diazide sulfonic acid bonded to a polyhydroxy polyamino compound via an ester bond and / or a sulfonamide bond, etc. These quinone diazide compounds may be used alone or in combination of two or more.

[0020] Of the quinone diazide compounds, naphthoquinone diazide compounds are preferred. Naphthoquinone diazide compounds can be obtained by esterification of a compound having a phenolic hydroxyl group with quinone diazide sulfonic acid.

[0021] Examples of naphthoquinone diazide compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, and BisRS- 26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-T PPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC -F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Yokuzai Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl Examples of such compounds include those obtained by introducing naphthoquinone diazide-4-sulfonic acid and / or naphthoquinone diazide-5-sulfonic acid via an ester bond into a compound such as 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, or BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

[0022] Naphthoquinone diazide sulfonic acid 4-ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. Furthermore, naphthoquinone diazide 5-sulfonic acid ester compounds have absorption extending to the g-line region of a mercury lamp and are suitable for g-line exposure. The sacrificial film-forming composition of the present invention may contain a naphthoquinone diazide 4-sulfonic acid ester compound and / or a naphthoquinone diazide 5-sulfonic acid ester compound, or may contain a naphthoquinone diazide sulfonic acid ester compound having a naphthoquinone diazide 4-sulfonyl group and a naphthoquinone diazide 5-sulfonyl group in the same molecule.

[0023] In the composition for forming a sacrificial film, the content of the quinone diazide compound (B) is usually about 1 to 40 mass % based on the total solid content of the composition for forming a sacrificial film, and from the viewpoint of further improving the effects of the present invention, it is preferably 3 to 30 mass %, more preferably 5 to 25 mass %.

[0024] In the composition for forming a sacrificial film, the content ratio of the novolak resin (A) to the quinone diazide compound (B) is not particularly limited, but the content of the quinone diazide compound (B) is usually about 2 to 80 parts by mass per 100 parts by mass of the novolak resin (A), and from the viewpoint of further improving the effects of the present invention, it is preferably 3 to 60 parts by mass, more preferably 5 to 40 parts by mass, even more preferably 7.5 to 30 parts by mass, and particularly preferably 7.5 to 25 parts by mass.

[0025] [Compound (C)] The sacrificial film-forming composition of the present invention contains a compound (C) having an aromatic ring, a hydroxyl group bonded to the aromatic ring, and an alkoxymethyl group bonded to the aromatic ring. The reason why the sacrificial film-forming composition of the present invention contains the compound (C) together with the novolac resin (A) and the quinone diazide compound (B) not only improves exposure sensitivity and resolution but also provides a resist pattern (sacrificial film pattern) having a good pattern shape and excellent dry etching resistance is thought to be as follows, without being bound by theory. As described above, the quinone diazide compound (B) interacts (e.g., hydrogen bonds) with the functional groups of the novolac resin (A) before exposure to light, making the novolac resin (A) insoluble in an alkaline aqueous solution. However, when the compound (C) coexists, the hydroxyl group bonded to the aromatic ring of the compound (C) interacts (e.g., hydrogen bonds) with the diazoketone moiety of the quinone diazide compound (B), which is thought to further reduce the solubility of the novolac resin (A) in an alkaline aqueous solution. This is thought to increase the difference in alkali solubility of the novolac resin (A) between the unexposed and exposed areas, thereby enabling the formation of a good pattern shape with high sensitivity and high resolution even with a small exposure dose. Furthermore, by heating the resist pattern after development, the alkoxymethyl group bonded to the aromatic ring of the compound (C) reacts with the phenolic hydroxyl group of the novolac resin (A), allowing the compound (C) to be introduced into the novolac resin (A), thereby enabling the formation of a resist pattern (sacrificial film pattern) with excellent dry etching resistance.

[0026] The aromatic ring of the compound (C) is not particularly limited, and examples thereof include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, biphenyl ring, anthracene ring, phenanthrene ring, pyrene ring, fluorene ring, acenaphthylene ring, and acenaphthene ring; heteroaromatic rings such as pyrrole ring, furan ring, thiophene ring, phosphole ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, and triazine ring; and condensed rings thereof, and preferably benzene ring. The aromatic ring may have a substituent such as an alkyl group, an alkenyl group, and a halogen group.

[0027] The total number of hydroxyl groups bonded to the aromatic ring is not particularly limited and is, for example, 1 to 10. From the viewpoint of further improving exposure sensitivity and resolution, and from the viewpoint of forming a resist pattern (sacrificial film pattern) having a better pattern shape, the total number is preferably 1 to 8, more preferably 2 to 8, even more preferably 2 to 6, and still more preferably 2 to 4.

[0028] The number of carbon atoms in the alkoxy group of the alkoxymethyl group bonded to the aromatic ring is not particularly limited and is, for example, 1 to 10. From the viewpoint of reactivity with the phenolic hydroxyl group of the novolak resin (A), the number is preferably 1 to 8, more preferably 1 to 6, even more preferably 1 to 4, and still more preferably 1 or 2.

[0029] The total number of alkoxymethyl groups bonded to the aromatic ring is not particularly limited and is, for example, 1 to 10, and from the viewpoint of forming a resist pattern (sacrificial film pattern) having superior dry etching resistance, it is preferably 2 to 8, and more preferably 2 to 6.

[0030] Examples of the compound (C) include compounds represented by the following general formula (1) or (2). (In the formula, R 1 is an alkoxymethyl group, and R 2 is a hydroxyl group, and R 3represents an alkyl group having 1 to 10 carbon atoms, X and Z each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a single bond, Y represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with an aryl group, an arylene group, or a single bond, a and b each independently represent 1 or 2, n represents an integer of 1 to 4, m represents 0, 1, or 2, and l represents 0, 1, or 2.

[0031] In the general formula (1), R 1 is bonded to the ortho position relative to the phenolic hydroxyl group, and it is preferred that n is 2, m is 0, and l is 0.

[0032] (In the formula, R 1 is an alkoxymethyl group, and R 2 is a hydroxyl group, and R 3 is an alkyl group having 1 to 10 carbon atoms, n is an integer of 1 to 4, m is 0, 1 or 2, and l is 0, 1 or 2.

[0033] In the general formula (2), R 1 is bonded to the ortho- and / or para-position relative to the phenolic hydroxyl group, and m is preferably 0 or 1, and l is preferably 0 or 1.

[0034] Specific examples of the compound represented by the general formula (1) include the following compounds.

[0035] Specific examples of the compound represented by the general formula (2) include the following compounds.

[0036] In the composition for forming a sacrificial film, the content of the compound (C) is usually about 1 to 30 mass % based on the total solid content of the composition for forming a sacrificial film, and from the viewpoint of further improving the effects of the present invention, it is preferably 2 to 25 mass %, more preferably 3 to 20 mass %, and even more preferably 4 to 15 mass %.

[0037] In the composition for forming a sacrificial film, the content ratio of the novolak resin (A) to the compound (C) is not particularly limited, but the content of the compound (C) is usually about 1 to 35 parts by mass per 100 parts by mass of the novolak resin (A), and from the viewpoint of further improving the effects of the present invention, it is preferably 2 to 30 parts by mass, more preferably 3 to 25 parts by mass, even more preferably 4 to 20 parts by mass, and particularly preferably 4 to 15 parts by mass.

[0038] In the composition for forming a sacrificial film, the content ratio of the quinone diazide compound (B) to the compound (C) is not particularly limited, but the content of the compound (C) is usually about 10 to 100 parts by mass per 100 parts by mass of the quinone diazide compound (B), and from the viewpoint of further improving the effects of the present invention, it is preferably 15 to 95 parts by mass, more preferably 20 to 90 parts by mass, and even more preferably 30 to 85 parts by mass.

[0039] [Other Components] The sacrificial film-forming composition of the present invention may contain other components commonly used in positive resist materials, such as a resin other than a novolac resin, a crosslinking agent, a crosslinking accelerator, an adhesion improver, a surfactant, a silane coupling agent, a plasticizer, a thermal acid generator, a sensitizer, a leveling agent, a colorant, fibers, fine particles, and a basic compound.

[0040] [Solvent] The sacrificial film-forming composition of the present invention can be prepared by dissolving the above-mentioned components in a solvent. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, cyclohexane, cyclopentanone, and cyclohexanol, alcohols such as n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol, ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane, alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, esters such as propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, and ethyl lactate, cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate. Examples of suitable solvents include cellosolve esters such as cellosolve acetate, propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether, diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether, halogenated hydrocarbons such as trichloroethylene, aromatic hydrocarbons such as toluene and xylene, and polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide. These solvents may be used alone or in combination of two or more. The content of the solvent may be appropriately adjusted taking into account the coatability.

[0041] 2. Method for Producing a Sacrificial Film Pattern The method for producing a sacrificial film pattern of the present invention includes a coating film forming step of forming a coating film using the sacrificial film-forming composition of the present invention, an exposure step of selectively exposing the coating film to light, and a development step of developing the coating film after the exposure step to form a pattern.

[0042] The coating film can be formed, for example, by applying the composition for forming a sacrificial film onto a substrate such as a semiconductor substrate, etc. Examples of the application method include spin coating, slit coating, dip coating, spray coating, and printing.

[0043] The substrate is not particularly limited, and examples thereof include substrates made of metals such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, aluminum, and gold, glass substrates or organic material substrates on which a metal thin film is laminated, and the like.

[0044] Next, if necessary, volatile components such as the solvent are removed to dry the coating film. The drying method is not particularly limited, and examples include methods of drying at 50 to 180°C for 1 minute to several hours using a hot plate, oven, infrared rays, etc. Before heating using a hot plate, etc., drying under reduced pressure at room temperature using a vacuum dryer (VCD) may be performed.

[0045] In the exposure step, the coating film is selectively exposed. The selective exposure can be performed, for example, through a desired mask pattern. The exposure can be performed using radiation such as i-line, h-line, g-line, KrF excimer laser, ArF excimer laser, F excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, or soft X-ray.

[0046] After the exposure, a PEB treatment (post-exposure bake) may be performed. The PEB treatment can be performed using, for example, an oven, a hot plate, infrared radiation, a flash annealing device, or a laser annealing device. The conditions for the PEB treatment vary depending on the types and blending ratios of the components in the composition, the coating film thickness, and the like, but the heating temperature is preferably 50 to 180°C, more preferably 60 to 150°C, and the heating time is preferably 10 seconds to several hours, more preferably 1 minute to 1 hour.

[0047] In the development step, the coating film after exposure is developed to form a pattern.

[0048] Examples of the developer include aqueous solutions of alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. Furthermore, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, may be added alone or in combination to these aqueous alkaline solutions.

[0049] Examples of the developing method include a puddle method, a dipping method, a puddle method, a spray method, etc. The developing time varies depending on the composition of the sacrificial film-forming composition, the thickness of the coating film, etc., but is usually about 1 to 30 minutes.

[0050] After development, the pattern is preferably rinsed with distilled water. Here, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may also be added to the distilled water for rinsing.

[0051] The method for producing a sacrificial film pattern of the present invention may include a heating step of heating the pattern after the development step. By heating the pattern, a sacrificial film pattern with excellent dry etching resistance can be obtained. The temperature during heating is not particularly limited, but is preferably 150°C or higher, more preferably 200°C or higher, and is preferably 350°C or lower, more preferably 300°C or lower. The heating time is usually about 30 seconds to 60 minutes, preferably 60 seconds to 30 minutes.

[0052] The sacrificial film pattern of the present invention has excellent resistance to dry etching and is therefore suitable for use as, for example, a hard mask.

[0053] The present invention will be described below with reference to examples, but the present invention is not limited to these examples in any way.

[0054] Examples 1 to 11 and Comparative Examples 1 to 5 Each component shown in Table 1 was mixed in the blending ratio (parts by mass) shown in Table 1 to prepare a composition for forming a sacrificial film. The components shown in Table 1 are as follows: Component (A-1): Novolac resin (TRM30B20G, manufactured by Asahi Organic Chemicals Co., Ltd.) Component (A-2): Novolac resin (TR4080G, manufactured by Asahi Organic Chemicals Co., Ltd.) Component (B-1): Naphthoquinone diazide compound represented by the following structural formula (TKF-528, manufactured by Sanbo Chemical Research Institute Co., Ltd.) Component (B-2): A naphthoquinone diazide compound represented by the following structural formula (DTRPA-300, manufactured by Daito Chemiks Co., Ltd.) Component (C-1): Compound represented by the following structural formula (TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) Component (C-2): Compound represented by the following structural formula (HMOM-TPPA, manufactured by Honshu Chemical Industry Co., Ltd.) Component (C-3): A compound represented by the following structural formula (4,6-DMXOC, manufactured by Asahi Organic Chemicals Co., Ltd.) Component (D-1): Crosslinking agent represented by the following structural formula (Nicalac MW-30, manufactured by Sanwa Chemical Co., Ltd.) Component (D-2): Crosslinking agent represented by the following structural formula (Nicalac MX-750, manufactured by Sanwa Chemical Co., Ltd.) Component (D-3): Crosslinking agent represented by the following structural formula (Celloxide 2021P, manufactured by Daicel Corporation) Component (D-4): Crosslinking agent represented by the following structural formula (4,6-DMOC, manufactured by Asahi Organic Chemicals Co., Ltd.) Surface conditioner: silicone-based surface conditioner (BYK Corporation, BYK-307) Solvent: propylene glycol monomethyl ether acetate (PMA)

[0055] Next, the exposure sensitivity, pattern shape, resolution, and dry etching resistance were measured or evaluated by the following methods using the compositions for forming sacrificial films prepared in Examples 1 to 11 and Comparative Examples 1 to 5. The results are shown in Table 1.

[0056] [Exposure Sensitivity] The sacrificial film-forming compositions prepared in Examples 1 to 11 and Comparative Examples 1 to 5 were applied to a glass substrate (10 cm x 10 cm) using a spin coater, allowed to stand at room temperature for 5 minutes, and then heated on a hot plate at 90°C for 2 minutes to completely remove the solvent, forming a coating film (film thickness: 1.5 μm). Thereafter, each of the resulting coating films was irradiated with light using a projection exposure machine (emission lines: g, h, i lines, illuminance at 365 nm: 20 mW / cm 2 The resist was then developed for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), and the minimum exposure dose at which no cured film remained in the exposed areas was measured and evaluated according to the following criteria. <Evaluation criteria> A: Minimum exposure dose was 30 mJ / cm 2 B: Minimum exposure amount is less than 30 mJ / cm 2 End

[0057] [Pattern Shape] Using the compositions for forming sacrificial films prepared in Examples 1 to 11 and Comparative Examples 1 to 5, coating films (film thickness: 1.5 μm) were formed in the same manner as in the formation of the coating films in the measurement of exposure sensitivity described above. Thereafter, each of the resulting coating films was irradiated with light through an L / S pattern mask using a projection exposure machine (emission lines: g, h, i lines, illuminance at 365 nm: 20 mW / cm 2). Then, the pattern was developed for 60 seconds using a 2.38% by mass aqueous solution of TMAH, and the resulting L / S pattern was observed and evaluated according to the following criteria. <Evaluation criteria> A: The value of 90% CD - 10% CD is less than 10% of the mask size. B: The value of 90% CD - 10% CD is 10% or more but less than 100% of the mask size. C: The value of 90% CD - 10% CD is 100% or more of the mask size.

[0058] [Resolution] Using the compositions for forming sacrificial films prepared in Examples 1 to 11 and Comparative Examples 1 to 5, coating films (film thickness: 1.5 μm) were formed in the same manner as in the formation of coating films in the measurement of exposure sensitivity described above. Subsequently, light irradiation and development were carried out in the same manner as in the evaluation of pattern shape described above, to obtain L / S patterns. The obtained L / S patterns were observed and evaluated according to the following criteria. <Evaluation criteria> A: Minimum resolution is L / S = 4 / 4 (μm) or less B: Minimum resolution is L / S = 5 / 5 (μm) or more, but less than L / S = 10 / 10 (μm) C: Minimum resolution is L / S = 10 / 10 (μm) or more, or a pattern cannot be produced

[0059] [Dry Etching Resistance] The sacrificial film-forming compositions prepared in Examples 1 to 11 and Comparative Examples 1 to 5 were applied to a silicon nitride (SiNx) substrate (10 cm x 10 cm) using a spin coater, allowed to stand at room temperature for 5 minutes, heated on a hot plate at 90°C for 2 minutes to completely remove the solvent, and then baked in a dryer at 120°C for 5 minutes to form a coating film (film thickness: 1.5 μm). Each of the resulting coating films was etched using an etching device (RIE-10N, manufactured by Samco) under the following conditions, and the etching rate (difference in film thickness of the coating film before and after etching (Å / min)) was measured and evaluated according to the following criteria. <Etching conditions> Chamber pressure: 300 mTorr RF power: 50 W CF4 gas flow rate: 40 sccm O2 flow rate: 12 sccm Time: 20 minutes <Evaluation criteria> A: Etching rate less than 500 (Å / min) B: Etching rate 500 (Å / min) or more but less than 700 (Å / min) C: Etching rate 700 (Å / min) or more

[0060]

[0061] As shown in Table 1, the sacrificial film-forming compositions of Examples 1 to 11 contained a compound (C) having an aromatic ring, a hydroxyl group bonded to the aromatic ring, and a methoxymethyl group bonded to the aromatic ring, and therefore were able to form resist patterns (sacrificial film patterns) that had high exposure sensitivity, excellent resolution, a good pattern shape, and excellent dry etching resistance. On the other hand, the sacrificial film-forming compositions of Comparative Examples 1 to 5 did not contain the compound (C), and therefore did not satisfy all of the above properties.

[0062] The composition for forming a sacrificial film of the present invention is suitably used as a resist material (sacrificial film material) used when forming wiring or terminals on a substrate.

Claims

1. A composition for forming a sacrificial film, comprising a novolac resin (A), a quinone diazide compound (B), and a compound (C) having an aromatic ring, a hydroxyl group bonded to the aromatic ring, and an alkoxymethyl group bonded to the aromatic ring.

2. The composition for forming a sacrificial film according to claim 1, wherein the total number of hydroxyl groups bonded to the aromatic ring is 2 to 8.

3. The composition for forming a sacrificial film according to claim 1 or 2, wherein the total number of alkoxymethyl groups bonded to the aromatic ring is 2 to 8.

4. The composition for forming a sacrificial film according to claim 1 or 2, wherein the alkoxy group of the alkoxymethyl group bonded to the aromatic ring has 1 to 8 carbon atoms.

5. A method for producing a sacrificial film pattern, comprising: a coating film formation step of forming a coating film using the sacrificial film-forming composition according to claim 1 or 2; an exposure step of selectively exposing the coating film; and a development step of developing the coating film after the exposure step to form a pattern.

6. The method for producing a sacrificial film pattern according to claim 5, further comprising a heating step of heating the pattern after the developing step.

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