Compound and Composition for Forming Organic Film

Abstract

To provide a compound which is cured even under film deposition conditions in an inert gas, does not generate by-products, and can form an organic underlayer film not only excellent in heat resistance and properties of filling and planarizing a pattern formed on a substrate but also good in dry etching resistance during substrate processing, and to provide an organic film-forming composition containing the compound.SOLUTION: The compound has two or more structures represented by the following formula (1-1) in the molecule. (Ar represents a substituted / unsubstituted aromatic ring or an aromatic ring containing one or more of N and S; two Ar's may be linked together to form a ring structure; a broken line represents a bond with Y; Y represents a C6-30 divalent or trivalent organic group which has a substituted / unsubstituted aromatic ring or heteroaromatic ring and of which bonds are located in an aromatic ring structure or a heteroaromatic ring structure; and R represents H or a C1-68 monovalent group.)SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a compound, a method for producing the compound, and a composition for forming an organic film containing the compound, which are used, for example, in an inert gas in a semiconductor device manufacturing process.

Background Art

[0002] Conventionally, the high integration and high speed of semiconductor devices have been achieved by miniaturization of pattern dimensions due to shortening of the wavelength of the light source in lithography technology (photo-lithography) using optical exposure as a general-purpose technology. In order to form such a fine circuit pattern on a semiconductor device substrate (substrate to be processed), a method of processing the substrate to be processed by dry etching using a photoresist film having a pattern formed thereon as an etching mask is usually used. However, in reality, since there is no dry etching method capable of achieving complete etching selectivity between the photoresist film and the substrate to be processed, in recent years, substrate processing by a multilayer resist method has become widespread. This method involves interposing an intermediate film having different etching selectivity from the photoresist film (hereinafter referred to as the upper resist film) between the upper resist film and the substrate to be processed. After obtaining a pattern on the upper resist film, the upper resist film pattern is used as a dry etching mask to transfer the pattern to the intermediate film by dry etching, and further, the intermediate film is used as a dry etching mask to transfer the pattern to the substrate to be processed by dry etching.

[0003] One of the multilayer resist methods is a three-layer resist method that can be performed using a general resist composition used in the single-layer resist method. In this method, an organic lower layer film (hereinafter referred to as an organic film) is formed by coating and baking an organic lower layer film material composed of an organic resin-containing composition on a substrate to be processed, and a resist intermediate film material composed of a silicon-containing resin-containing composition is coated thereon and baked to form a silicon-containing film (hereinafter referred to as a silicon intermediate film), and a general resist upper layer film is formed thereon. After patterning the resist upper layer film, when dry etching is performed using a fluorine-based gas plasma, the organic resist upper layer film can have a good etching selectivity with respect to the silicon intermediate film, so that the resist upper layer film pattern can be transferred to the silicon intermediate film. According to this method, even when using a resist upper layer film that does not have a sufficient film thickness for directly processing the substrate to be processed or a resist upper layer film that does not have sufficient dry etching resistance for processing the substrate to be processed, usually, since the silicon intermediate film has a film thickness equal to or less than that of the resist upper layer film, the pattern can be easily transferred to the silicon intermediate film. Subsequently, if the pattern-transferred silicon intermediate film is used as a dry etching mask and pattern transfer is performed on the organic lower layer film by dry etching using an oxygen-based or hydrogen-based gas plasma, pattern transfer can be performed on the organic lower layer film having sufficient dry etching resistance for substrate processing. This pattern-transferred organic lower layer film pattern can be pattern-transferred to the substrate by dry etching using a fluorine-based gas, a chlorine-based gas, or the like.

[0004] On one hand, miniaturization in the manufacturing process of semiconductor devices is approaching the essential limit derived from the wavelength of the light source for photolithography. Therefore, in recent years, high integration of semiconductor devices that does not rely on miniaturization has been studied. As one of the methods, semiconductor devices having complex structures such as multi-gate structures and gate all around have been studied, and some have already been put into practical use. When forming such structures by the multilayer resist method, minute patterns such as holes, trenches, and fins formed on the substrate to be processed can be filled with an organic film material without gaps, or steps, pattern-dense portions, and regions without patterns can be filled with an organic film material, and an organic film material capable of planarization can be applied. By forming a flat surface of the organic underlayer film on the stepped substrate using such an organic film material, the film thickness variation of the silicon intermediate film and the resist upper layer film formed thereon can be suppressed, and the focus margin of photolithography and the reduction of the margin in the subsequent processing steps of the substrate to be processed can be suppressed. As a result, it becomes possible to manufacture semiconductor devices with good yield. On the other hand, in the single-layer resist method, in order to fill the substrate to be processed with steps and patterns, the film thickness of the upper-layer resist film becomes thick, resulting in pattern collapse after exposure and development, and deterioration of the pattern shape due to reflection from the substrate during exposure. The pattern formation margin during exposure becomes narrow, and it is difficult to manufacture semiconductor devices with good yield.

[0005] Furthermore, as a method for increasing the speed of next-generation semiconductor devices, for example, the application of new materials with high electron mobility using strained silicon, gallium arsenide, etc., and precision materials such as ultra-thin polysilicon controlled in angstrom units has also begun to be studied. However, in the substrate to be processed to which such new precision materials are applied, under the conditions for forming a planarization film using the above-mentioned organic underlayer film material, for example, in an atmosphere of oxygen at a film formation temperature of 300 °C or higher, the material is corroded by oxygen in the air, and the high speed of the semiconductor device cannot exhibit the performance as designed, and it may not be possible to achieve a yield that can be established as industrial production. Therefore, in order to avoid the reduction in yield caused by the corrosion of the substrate by air under such high-temperature conditions, an organic underlayer film material capable of film formation in an inert gas is expected.

[0006] Conventionally, condensation resins using carbonyl compounds such as ketones and aldehydes and aromatic alcohols as condensing agents for phenolic and naphthol compounds have been known as materials for forming organic films for the multilayer resist method. For example, the fluorene bisphenol novolak resin described in Patent Document 1, the bisphenol compound and this novolak resin described in Patent Document 2, the novolak resin of the adamantane phenol compound described in Patent Document 3, the bisnaphthol compound and this novolak resin described in Patent Document 4, etc. can be exemplified. Such materials are cured by crosslinking with a methylol compound as a crosslinking agent or by a crosslinking reaction due to oxidation at the α-position of the aromatic ring by the action of oxygen in the air and subsequent condensation, and are formed into a film having solvent resistance against the coating film material used in the next step.

[0007] Furthermore, as examples of materials applying a triple bond as an intermolecular crosslinking group of a curable resin, Patent Documents 5-10 etc. are known. However, in these materials, the curing conditions are not actually exemplified in an inert gas, and regarding the formation of a cured film in an inert gas in these materials and the film thickness variation due to thermal decomposition under high temperature conditions, etc., they are not known.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

[0009] The present invention has been made in view of the above problems, and cures not only in air but also under film-forming conditions in an inert gas, generates no volatile by-products, and has excellent heat resistance and embedding and planarization characteristics of patterns formed on a substrate. Another object of the present invention is to provide a compound capable of forming an organic underlayer film having good dry etching resistance during substrate processing, a method for producing the compound, and an organic film-forming composition using the compound. [Means for Solving the Problems

[0010] In order to solve the above problems, the present invention provides a compound having two or more structures represented by the following general formula (1-1) in the molecule. [Chemical Formula (In the formula, each Ar independently represents an aromatic ring which may have a substituent, or an aromatic ring which may have a substituent and contains at least one of a nitrogen atom and a sulfur atom, and two Ar's may be linked to form a ring structure. The broken line is a bond to Y, and Y has an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, and is a divalent or trivalent organic group having 6 to 30 carbon atoms in which the bond is in an aromatic ring structure or a heteroaromatic ring structure. R is a hydrogen atom or a monovalent group having 1 to 68 carbon atoms.)

[0011] For such a compound, it can be cured not only in air but also under film-forming conditions in an inert gas, without generating by-products, and is not only excellent in heat resistance, embedding and planarization characteristics of patterns formed on a substrate, but also can form an organic underlayer film with good dry etching resistance during substrate processing.

[0012] Also in this case, it is preferable that the compound is a compound having units represented by the following general formulas (2-1) and (2-2).

Chemical formula

Chemical formula

[0013] A compound having units represented by the above general formulas (2-1) and (2-2) is preferable because it can be more surely cured even under film-forming conditions in an inert gas and is further excellent in heat resistance, embedding and planarization characteristics of patterns formed on a substrate.

[0014] Also in the present invention, a method for producing a compound having two or more structures represented by the above general formula (1-1) in the molecule, a step of producing a diol or a triol by a reaction represented by the following formula (4-1),

Chemical formula

Chemical formula

Chemical formula

[0015] According to such a method for producing a compound, it is possible to produce a compound without using a transition metal, which is a cause of defects in the dry etching process during semiconductor device manufacturing, as a catalyst during the formation of the compound skeleton. Therefore, since defects derived from the transition metal during dry etching do not occur, it is possible to produce a semiconductor device with a high yield.

[0016] Further, in the present invention, a method for producing a compound having units represented by the above general formulas (2-1) and (2-2), A step of producing a diol or a triol by the reaction represented by the following formula (5-1),

Chemical formula

Chemical formula

Chemical formula

[0017] Further, the present invention is a method for producing a compound having units represented by the above general formulas (2-1) and (2-2), A step of producing a diol or triol by the reaction represented by the following formula (5-1),

Chemical formula

Chemical formula

Chemical formula

[0018] Examples of the method for producing the compound having the units represented by the above general formulas (2-1) and (2-2) include these methods.

[0019] Further, the present invention provides an organic film-forming composition characterized by containing (A) a compound having two or more structures represented by the following general formula (1-1) in the molecule and (B) an organic solvent for forming an organic film. [Chemical formula] (In the formula, each Ar independently represents an aromatic ring which may have a substituent, or an aromatic ring which may have a substituent and contains at least one of a nitrogen atom and a sulfur atom, and two Ar's may be linked to form a ring structure. The broken line is a bond to Y, and Y has an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, and is a divalent or trivalent organic group having 6 to 30 carbon atoms in which the bond is in an aromatic ring structure or a heteroaromatic ring structure. R is a hydrogen atom or a monovalent group having 1 to 68 carbon atoms.)

[0020] The organic film-forming composition of the present invention is an organic film-forming composition capable of forming an organic film having high heat resistance, high dry etching resistance, and high embedding / planarization characteristics.

[0021] In this case, it is preferable that the compound (A) is a compound having units represented by the following general formulas (2-1) and (2-2). [Chemical formula] (In the formula, AR1 and AR2 are a benzene ring, a pyridine ring or a naphthalene ring which may have an alkoxy group, an alkenyloxy group, an alkynyloxy group or an aryloxy group having 1 to 30 carbon atoms, m is 0 or 1, and when m = 0, a bridging structure is not formed between the aromatic rings of AR1 and AR2, and when m = 1, AR1 and AR2 form a bridging structure between the aromatic rings of AR1 and AR2 via X, and X is a single bond or any of the following formulas (3). n is 2 or 3, and Y is the same as described above. Z is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. a is bonded to b, and c is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms or is bonded to a.) [Chemical formula]

[0022] If it is a composition for forming an organic film containing the above compound, more surely, it can be cured even under film formation conditions in an inert gas, and an organic underlayer film excellent in heat resistance and in filling and planarization characteristics of a pattern formed on a substrate can be formed.

[0023] In this case, it is preferable that the component (A) has a weight average molecular weight of 500 to 20,000.

[0024] With such a molecular weight, the thermal fluidity of the compound becomes better, so that when blended in the composition, not only can the fine structure formed on the substrate be filled well, but also an organic film in which the entire substrate becomes flat can be formed.

[0025] In this case, it is preferable that the composition for forming an organic film further contains one or more of (C) an acid generator, (D) a surfactant, (E) a crosslinking agent, and (F) a plasticizer.

[0026] The composition for forming an organic film of the present invention can contain one or more of the above components (C) to (F) according to its purpose. [Effects of the Invention]

[0027] As described above, the compound of the present invention cures without generating volatile by-products in film formation in an inert gas in which corrosion of the substrate is prevented, and is useful for forming an organic underlayer film having both high embedding and planarization characteristics. Further, the composition for forming an organic film containing this compound has excellent embedding / planarization characteristics and is a material for forming an organic film having various characteristics such as heat resistance and etching resistance. Therefore, for example, it is extremely useful as an organic film material in a multilayer resist method such as a two-layer resist method, a three-layer resist method using a silicon intermediate film, or a four-layer resist method using a silicon intermediate film and an organic antireflection film, or as a planarization material for manufacturing semiconductor devices. Further, since the organic film formed from the composition for forming an organic film of the present invention is excellent in heat resistance, even when a CVD hard mask is formed on the organic underlayer film, there is no film thickness variation due to thermal decomposition, and it is suitably used for pattern formation. In addition, in the production method of the compound of the present invention, it becomes possible to form the polymer skeleton without using a transition metal catalyst.

Brief Description of Drawings

[0028]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0029] As described above, in order to prevent corrosion of the substrate, an organic underlayer film is required that has film-forming conditions in an inert gas, for example, does not generate volatile by-products even at 300 °C or higher, has excellent embedding and planarization characteristics of the pattern formed on the substrate, and also has good dry etching resistance during substrate processing. Furthermore, even when forming a CVD hard mask on the organic underlayer film, an organic film without film thickness variation due to decomposition is required, and the development of a compound for forming an organic film that realizes these characteristics has been demanded.

[0030] Generally, when forming an organic underlayer film, a compound for forming an organic film is dissolved in an organic solvent to form a composition, which is applied onto a substrate on which the structure and wiring of a semiconductor device are formed, and then baked to form the organic underlayer film. Immediately after the application of the composition, a coating film conforming to the shape of the step structure on the substrate is formed. However, when this coating film is baked, most of the organic solvent evaporates before hardening, and an organic film is formed by the compound for forming an organic film remaining on the substrate. The inventors of the present invention conceived that if the compound for forming an organic film remaining on the substrate at this time has sufficient thermal fluidity, it is possible to flatten the step shape immediately after application by thermal fluidity and form a flat film.

[0031] The inventors of the present invention further conducted intensive studies and, in order to provide a material that has high heat resistance and cures in an inert gas to prevent corrosion of the substrate by oxygen in the air, as a structure for achieving such a curing reaction, a structure represented by the general formula (1-1), that is, a structure having two or more quaternary carbons in the molecule having three aromatic substituents as intermolecular crosslinking groups and one triple-bonded carbon as a substituent, has thermosetting properties under film-forming conditions in air and in an inert gas, exhibits curing performance equivalent to that of conventional underlayer film materials even in an inert gas, does not generate volatile by-products during the curing reaction, and has high heat resistance due to effectively arranged aromatic rings. Also, because of its good thermal fluidity, it has advanced embedding / planarization characteristics, good dry etching resistance, and heat resistance without film thickness variation of the coating film due to thermal decomposition even when forming a CVD hard mask, and the present invention has been completed by finding that it provides an organic film-forming composition having these properties.

[0032] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0033] <Compound (1)> The compound of the present invention is a compound having two or more structures represented by the following general formula (1-1) in the molecule (hereinafter referred to as compound (1)). [Chemical formula] (In the formula, each Ar independently represents an aromatic ring which may have a substituent, or an aromatic ring which may have a substituent and contains at least one of a nitrogen atom and a sulfur atom, and two Ar's may be linked to form a ring structure. The broken line is a bond with Y, and Y has an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, and is a divalent or trivalent organic group having 6 to 30 carbon atoms in which the bond is in an aromatic ring structure or a heteroaromatic ring structure. R is a hydrogen atom or a monovalent group having 1 to 68 carbon atoms.)

[0034] Each Ar independently represents an aromatic ring which may have a substituent, or an aromatic ring which may have a substituent and contains at least one of a nitrogen atom and a sulfur atom, and two Ar's may be linked to form a ring structure. Examples of the aromatic ring in the above Ar include a benzene ring, a naphthalene ring, a pyridine ring, a thiophene ring and the like. Further, the substituent is not particularly limited, and examples thereof include an alkoxy group having 1 to 30 carbon atoms, an alkenyloxy group, an alkynyloxy group, an aryloxy group and the like.

[0035] Further, Y is a divalent or trivalent organic group having 6 to 30 carbon atoms, which has an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent in the organic group, and the bonding hand is a group in an aromatic ring structure or a heteroaromatic ring structure. Examples of the aromatic ring or heteroaromatic ring in Y include a benzene ring, a naphthalene ring, a pyridine ring, a furan ring, a thiophene ring and the like. Examples of the substituent include the same ones as those exemplified above as the substituent in Ar. In the present invention, the "organic group" means a group containing at least carbon, further contains hydrogen, and may also contain nitrogen, oxygen, sulfur, silicon and the like.

[0036] R is a hydrogen atom or a monovalent group having 1 to 68 carbon atoms, and a hydrogen atom or a group containing a carbon-carbon triple bond and an aromatic ring or a heteroaromatic ring is preferable.

[0037] More specifically, the compound of the present invention is a compound having units represented by the following general formulas (2-1) and (2-2) (hereinafter referred to as compound (2)).

Chemical formula

Chemical formula

[0038] As the compound (1) or (2) shown here, specifically, the following structures can be exemplified, but the present invention is not limited to these structures.

[0039] [Chemical formula]

[0040] [Chemical formula]

[0041] [Chemical formula]

[0042] [Chemical formula]

[0043] [Chemical formula]

[0044] [Chemical formula]

[0045] In the above formula, p represents the number of repeating units and is 1 to 50.

[0046] Also, the weight average molecular weight calculated from the compound (1) of the present invention is preferably 500 to 20,000, and more preferably 15,000 or less from the viewpoints of flatness and embedding properties. With such a molecular weight, the thermal fluidity of the compound becomes better, so when blended into a composition, not only can the fine structure formed on the substrate be well embedded, but also an organic film that makes the entire substrate flat can be formed.

[0047] [Method for producing a compound] As a method for producing the compound (1) of the present invention, a step of producing (iii), which is a diol or triol, by an addition reaction of an organometallic reagent (ii) to the following ketone compound (i) (the following formula (4-1)), a step of leading (iii) to a dihalide or trihalide (iv) (the following formula (4-2)), and further, a step of producing a compound (vi) by performing a substitution reaction of an organometallic reagent (v) with respect to (iv) (a method including the following formula (4-3) can be mentioned.

Chemical formula

Chemical formula

Chemical formula

[0048] In the above (4-1), it is preferable to use 0.2 / n to 40 / n mol, particularly 0.5 / n to 2 / n mol of the organometallic reagent (ii) with respect to 1 mol of the ketone compound of the formula (i). As the organometallic reagent (ii), a Grignard reagent, an organolithium reagent, etc. are particularly preferable. In addition, in order to obtain the compound of the present invention, an organometallic reagent other than the above (ii) can also be used as the organometallic reagent for the addition reaction with the ketone compound. Examples of these organometallic reagents include organozinc reagents and organotitanium reagents. The Grignard reagent and the organolithium reagent may be prepared by direct metalation of the corresponding halide with metallic magnesium or metallic lithium, or may be prepared by a metal-halogen exchange reaction with an aliphatic organometallic compound such as isopropylmagnesium halide, methyllithium, or butyllithium. Further, the organozinc reagent and the organotitanium reagent can be prepared by reacting the corresponding Grignard reagent or organolithium reagent with zinc halide, titanium(IV) halide, alkoxytitanium(IV), etc. When preparing these organometallic reagents (ii) and / or when reacting these organometallic reagents with the ketone compound (i), a metal salt compound may coexist. Examples of the metal salt compound include cyanides, halides, and perhalogenates. Particularly preferable examples of the metal salt compound include lithium salts such as lithium chloride, lithium bromide, lithium iodide, and lithium perchlorate, and copper salts such as copper(I) cyanide, copper(II) cyanide, copper(I) chloride, copper(II) chloride, and dilithium tetrachlorocuprate. By adding these metal salt compounds in an amount of 0.01 to 5.0 equivalents, preferably 0.2 to 2.0 equivalents, to the organometallic reagent, the solubility of the organometallic reagent can be increased to facilitate its preparation, and the nucleophilicity and Lewis acidity of the reagent can be adjusted. As the solvent used for the preparation of the organometallic reagent (ii) and the reaction with the ketone compound (i), ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, and t-butyl methyl ether, hydrocarbons such as benzene, toluene, xylene, mesitylene, hexane, heptane, octane, and isooctane, and aprotic polar solvents such as N,N,N',N'-tetramethylethylenediamine, hexamethylphosphoric triamide, and N,N-dimethylformamide are used alone or in combination.The reaction temperature depends on the types of the ketone compound (i) and the organometallic reagent (ii) and the reaction conditions, but is preferably -70 to 150 °C. For example, when the organolithium reagent is used as (ii), it is -70 to 10 °C, and when the Grignard reagent is used, it can be variously selected such as at room temperature to under reflux at the boiling point of the solvent. It is desirable to track the reaction by chromatography or the like until the reaction is completed for the reaction time, but it is usually carried out for 30 minutes to 48 hours.

[0049] As a method for leading from the above diol or triol (iii) of (4-2) to the dihalide or trihalide (iv), a reaction between the diol or triol (iii) and a halogen compound such as hydrogen chloride, hydrogen bromide, thionyl chloride, thionyl bromide, phosgene, acetyl chloride, acetyl bromide and other carboxylic acid halides can be used. Examples of the solvent used in this reaction include ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane; chlorinated solvents such as methylene chloride, chloroform, dichloroethane, trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, hexamethylphosphoric triamide. These can be used alone or in combination of two or more. The reaction temperature is preferably -50 °C to about the boiling point of the solvent, more preferably room temperature to 100 °C.

[0050] In the above (4-3), the compound (vi), i.e., the compound (1), is obtained by the substitution reaction of the organometallic reagent (v) with the dihalide or trihalide (iv). In this case, as the organometallic reagent (v), a Grignard reagent or an organolithium reagent is particularly preferred. In addition, in order to obtain the compound of the present invention, an organometallic reagent other than the above (v) can also be used as the organometallic reagent. For example, an organozinc reagent, an organotitanium reagent, etc. can be exemplified. Grignard reagents and organolithium reagents can be prepared by the reaction of the corresponding acetylene compound with a Grignard reagent such as alkylmagnesium halide, for example, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, or an aliphatic organometallic compound such as methyllithium, n-butyllithium. As the solvent used in the reaction of the dihalide or trihalide (iv) with the organometallic reagent (v), ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, t-butyl methyl ether, hydrocarbons such as benzene, toluene, xylene, mesitylene, hexane, heptane, octane, isooctane, and aprotic polar solvents such as N,N,N',N'-tetramethylethylenediamine, hexamethylphosphoric triamide, N,N-dimethylformamide are used alone or in combination. The reaction temperature depends on the types and reaction conditions of the dihalide or trihalide (iv) and the organometallic reagent (v), but is preferably -70 to 150 °C. For example, when (v) is a Grignard reagent, it is under reflux at room temperature to the boiling point of the solvent, and when it is an organolithium reagent, it is -70 to 10 °C, etc., and various selections can be made. The reaction time is desirably determined by tracking the reaction by chromatography or the like until the reaction is completed, but it is usually carried out for 30 minutes to 48 hours.

[0051] As a method for producing the compound (2) of the present invention, a step of producing (viii), which is a diol or triol, by an addition reaction of an organometallic reagent (ii) to the following ketone compound (vii) (the following formula (5-1)), a step of leading (viii) to a dihalide or trihalide (ix) (the following formula (5-2)), and further, a step of producing a polymer by performing a substitution reaction of an organometallic reagent (x) with respect to (ix) (a method including the following formula (5-3) can be mentioned). [Chemical formula] (In the formula, AR1, AR2, X, Y, m, and n are the same as above. M is Li or Mg-Hal, and Hal is Cl, Br, or I.) [Chemical formula] (In the formula, AR1, AR2, X, Y, m, n, and Hal are the same as above.) [Chemical formula] (In the formula, AR1, AR2, X, Y, Z, n, m, and Hal are the same as above. M1 is Li or Mg-Hal. a is bonded to b, and d is a hydrogen atom or is bonded to a.)

[0052] In the above (5-1), (viii), which is a diol or triol, can be obtained by the same method using (vii) instead of the ketone compound (i) of the above (4-1). In the above (5-2), a dihalide or trihalide (ix) can be obtained by the same method using (viii) instead of the diol or triol (iii) of the above (4-2). In the above (5-3), the compound (xi), that is, the compound (2), can be obtained by the same method using (ix) instead of the dihalide or trihalide (iv) of the above (4-3).

[0053] Here, after performing a substitution reaction of an organometallic reagent (x) with a dihalide or trihalide (ix) (the following formula (5-4)), a halide, acyl chloride, acid anhydride, mesylate, tosylate, or sulfate ester is reacted to introduce a monovalent organic group having 1 to 30 carbon atoms at the end of the compound to obtain compound (xiii) (the following formula (5-5)).

[0054] [Chemical Formula] (In the formula, AR1, AR2, X, Y, Z, m, n, and Hal are the same as above. M1 is Li or Mg-Hal. a is bonded to b, and e is either M1 or is bonded to a. f is either a monovalent organic group having 1 to 30 carbon atoms or is bonded to a.)

[0055] After performing the substitution reaction of (x) with (ix), the reaction may be continued in the same reaction vessel to introduce an organic group, or the compound (2) obtained by post-treating and isolating the reaction of the above (5-3) is reacted with an aliphatic organometallic compound to prepare an organometallic reagent, which is then reacted with a compound selected from a halide, mesylate, tosylate, or sulfate ester to introduce a monovalent organic group.

[0056] The design concept of the compound (1) of the present invention will be described. The compound (1) of the present invention undergoes a thermal crosslinking reaction even under an oxygen-free condition where an oxidative crosslinking reaction does not occur due to the arrangement of a triple bond on the outer side of the molecule. Although a propargyl group is known as a functional group capable of reacting under an oxygen-free condition, in the compound (1) of the present invention, a higher heat resistance is obtained by eliminating an ether structure between the triple bond and the quaternary carbon. Furthermore, a very high heat resistance is achieved by effectively arranging a plurality of aromatic rings in the main skeleton of the compound. Therefore, it is suitable as a compound for an organic underlayer film for lithography that requires curing and film formation in an inert gas and does not generate by-products during that time.

[0057] As described above, the compound of the present invention can be cured even in an inert gas, and provides a composition for forming an organic film having heat resistance of 400 °C or higher and high embedding / planarization characteristics.

[0058] In the present invention, the planarization property refers to the performance of planarizing the surface of a substrate. For a composition containing the compound of the present invention, for example, as shown in FIG. 1, by applying a composition 3' for forming an organic film on a substrate 1 and heating to form an organic film 3, it is possible to reduce a 100 nm step on the substrate 1 to 30 nm or less. The step shape shown in FIG. 1 shows a typical example of the step shape in a substrate for manufacturing a semiconductor device, and the step shape of the substrate that can be planarized by the composition containing the compound of the present invention is of course not limited to this.

[0059] <Composition for forming an organic film> Further, the present invention provides a composition for forming an organic film, which contains (A) the compound of the present invention having two or more structures represented by the above general formula (1-1) in the molecule, and (B) an organic solvent. In the composition for forming an organic film of the present invention, the above-described compound of the present invention can be used alone or in combination of two or more.

[0060] As the (B) organic solvent that can be used in the composition for forming an organic film of the present invention, there is no particular limitation as long as it can dissolve the compound of the present invention, an acid generator, a crosslinking agent, other additives, etc. Specifically, a solvent having a boiling point of less than 180 °C such as the solvents described in paragraphs (0091) to (0092) of JP-A-2007-199653 can be used. Among them, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and a mixture of two or more of these are preferably used.

[0061] Such a composition can be applied by spin coating, and since it contains the compound of the present invention as described above, it has good dry etching resistance and becomes a composition for forming an organic film having heat resistance of 400 °C or higher and high embedding / planarization characteristics.

[0062] Furthermore, in the composition for forming an organic film of the present invention, as the organic solvent, it is also possible to add a high-boiling solvent having a boiling point of 180°C or higher to the solvent having a boiling point of less than 180°C (it is possible to mix and use a solvent having a boiling point of less than 180°C and a solvent having a boiling point of 180°C or higher). As the high-boiling organic solvent, there are no particular restrictions as long as it can dissolve the compound of the present invention, and examples include hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc. Specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3 - hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol - n-butyl ether, triethylene glycol butyl methyl ether, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4 - butanediol diacetate, 1,3 - butylene glycol diacetate, 1,Examples thereof include 6 - hexanediol diacetate, triethylene glycol diacetate, γ - butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc., and these may be used alone or in combination.

[0063] Regarding the above - mentioned high - boiling - point solvent, the boiling point may be appropriately selected according to the temperature for heat - treating the organic film - forming composition. The boiling point of the added high - boiling - point solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. With such a boiling point, there is no risk that the solvent will volatilize instantaneously during baking (heat - treatment) due to the boiling point being too low, so sufficient thermal fluidity can be obtained. Also, with such a boiling point, it will not remain in the film without volatilizing after baking, so there is no risk of adversely affecting film physical properties such as etching resistance.

[0064] Also, when using the above - mentioned high - boiling - point solvent, the blending amount of the high - boiling - point solvent is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the solvent having a boiling point of less than 180°C. With such a blending amount, there is no risk that the blending amount is too small to obtain sufficient thermal fluidity during baking, or on the other hand, that the blending amount is too large and remains in the film, deteriorating film physical properties such as etching resistance.

[0065] With such an organic film - forming composition, by imparting thermal fluidity by adding a high - boiling - point solvent to the above - mentioned organic film - forming compound, it becomes an organic film - forming composition having advanced embedding / planarization characteristics.

[0066] In the organic film - forming composition of the present invention, a (C) acid generator can be added to further promote the curing reaction. Acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation, and any of them can be added. Specifically, the materials described in paragraphs (0061) to (0085) of JP - A - 2007 - 199653 can be added, but are not limited thereto.

[0067] The above acid generator can be used alone or in combination of two or more. When adding the acid generator, the addition amount is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the compound (A).

[0068] In the composition for forming an organic film of the present invention, (D) a surfactant can be added to improve the coatability in spin coating. As the surfactant, for example, those described in (0142) to (0147) of JP-A-2009-269953 can be used.

[0069] Further, in the composition for forming an organic film of the present invention, (E) a crosslinking agent can also be added to enhance the curability and further suppress the intermixing with the upper layer film. The crosslinking agent is not particularly limited, and various known types of crosslinking agents can be widely used. As an example, melamine-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, and epoxy-based crosslinking agents can be exemplified.

[0070] As melamine-based crosslinking agents, specifically, hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxy-substituted products, and their partial self-condensates can be exemplified. As glycoluril-based crosslinking agents, specifically, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, their alkoxy and / or hydroxy-substituted products, and their partial self-condensates can be exemplified. As benzoguanamine-based crosslinking agents, specifically, tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy-substituted products, and their partial self-condensates can be exemplified. As urea-based crosslinking agents, specifically, dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy-substituted products, and their partial self-condensates can be exemplified. As β-hydroxyalkylamide-based crosslinking agents, specifically, N,N,N’,N’-tetra(2-hydroxyethyl) adipic acid amide can be exemplified. As isocyanurate-based crosslinking agents, specifically, triglycidyl isocyanurate, triallyl isocyanurate can be exemplified. As aziridine-based crosslinking agents, specifically, 4,4’-bis(ethyleneiminocarbonylamino) diphenylmethane, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl) propionate] can be exemplified. As oxazoline-based crosslinking agents, specifically, 2,2’-isopropylidene bis(4-benzyl-2-oxazoline), 2,2’-isopropylidene bis(4-phenyl-2-oxazoline), 2,2’-methylene bis 4,5-diphenyl-2-oxazoline, 2,2’-methylene bis-4-phenyl-2-oxazoline, 2,2’-methylene bis-4-tert butyl-2-oxazoline, 2,2’-bis(2-oxazoline), 1,3-phenylene bis(2-oxazoline), 1,4-phenylene bis(2-oxazoline), 2-isopropenyl oxazoline copolymer can be exemplified.Specific examples of the epoxy crosslinking agent include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0071] In addition, in the composition for forming an organic film of the present invention, a (F) plasticizer can be added in order to further improve the planarization / embedding characteristics. The plasticizer is not particularly limited, and various known types of plasticizers can be widely used. As an example, low molecular compounds such as phthalic acid esters, adipic acid esters, phosphoric acid esters, trimellitic acid esters, and citric acid esters, and polymers such as polyether-based, polyester-based, and polyacetal-based polymers described in JP 2013-253227 can be exemplified.

[0072] In addition, in the composition for forming an organic film of the present invention, as an additive for imparting embedding / planarization characteristics in the same manner as the plasticizer, for example, polyethylene glycol, a liquid additive having a polypropylene glycol structure, or a thermal decomposable polymer having a weight loss rate of 40% by mass or more between 30°C and 250°C and a weight average molecular weight of 300 to 200,000 is preferably used. This thermal decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formulas (DP1) and (DP1a).

[0073]

Chemical formula

[0074]

Chemical formula

[0075] As described above, the composition for forming an organic film of the present invention has good dry etching resistance, and forms an organic film having heat resistance of 400 ° C or higher and excellent embedding / planarization characteristics. Therefore, it is extremely useful as a material for forming an organic underlayer film used in a multilayer resist method such as a two-layer resist method, a three-layer resist method using a silicon-containing resist intermediate film or a silicon-containing inorganic hard mask, or a four-layer resist method using a silicon-containing resist intermediate film or a silicon-containing inorganic hard mask and an organic antireflection film. In addition, since the composition for forming an organic film of the present invention has excellent embedding / planarization characteristics without generating by-products even in film formation in an inert gas, it can also be suitably used as a planarization material in a semiconductor device manufacturing process other than the multilayer resist method.

[0076] <Organic Film Forming Method> For the heat-assisted film formation process for forming an organic film, single-step baking, two-step baking, or multi-step baking of three or more steps can be applied, but single-step baking or two-step baking is economically preferable. Film formation by single-step baking is preferably carried out in the range of 5 to 3600 seconds at a temperature of 100°C or higher and 600°C or lower, preferably in the range of 10 to 7200 seconds at a temperature of 150°C or higher and 500°C or lower. By performing heat treatment under such conditions, flattening due to heat flow and cross-linking reactions can be promoted. In the multi-layer resist method, a coating-type silicon intermediate film or a CVD hard mask may be formed on the obtained film. When applying a coating-type silicon intermediate film, it is preferable to form the organic underlayer film at a temperature higher than the temperature at which the silicon intermediate film is formed. Usually, the silicon intermediate film is formed at 100°C or higher and 400°C or lower, preferably 150°C or higher and 350°C or lower. When forming the organic underlayer film at a temperature higher than this temperature, dissolution of the organic underlayer film by the composition for forming the silicon intermediate film can be prevented, and an organic film that does not mix with the composition can be formed. Also, there is no risk of thermal decomposition of the organic underlayer film and generation of by-products during the formation of the silicon intermediate film.

[0077] When applying a CVD hard mask, it is preferable to form the organic underlayer film at a temperature higher than the temperature at which the CVD hard mask is formed. Examples of the temperature for forming the CVD hard mask can be a temperature of 150°C or higher and 500°C or lower.

[0078] On the other hand, when performing the first step of baking in air in film formation by two-step baking, when corrosion of the substrate by oxygen may occur, the upper limit of the processing temperature in air is preferably 300°C or lower, preferably 250°C or lower, and is carried out in the range of 10 to 600 seconds. The temperature of the second step of baking in an inert gas is higher than the temperature of the first step of baking and is preferably carried out in the range of 10 to 7200 seconds at a temperature of 600°C or lower, preferably 500°C or lower.

[0079] Further, the composition for forming an organic film of the present invention is a method for forming an organic film that functions as an organic underlayer film used in the manufacturing process of semiconductor devices. In order to prevent corrosion of the substrate to be processed, it can be applied to an organic film forming method in which a cured film is formed by heat-treating the substrate to be processed in an atmosphere with an oxygen concentration of 1% or less.

[0080] In this organic film forming method, first, the composition for forming an organic film of the present invention described above is spin-coated on the substrate to be processed. After spin-coating, in the case of two-stage baking, first, it is baked in air at 300°C or lower, and then the second-stage baking is performed in an atmosphere with an oxygen concentration of 1% or less. In the case of one-stage baking, the first-stage baking in air at the beginning may be skipped. As the atmosphere during baking, inert gases such as nitrogen, argon, and helium can be exemplified. With the materials of the present invention, even when heated in such an inert gas atmosphere, an organic film that is sufficiently cured without generating sublimates can be formed.

[0081] Also, the above organic film forming method can be used for a substrate to be processed having a structure or step with a height of 30 nm or more. As described above, since the composition for forming an organic film of the present invention has excellent embedding / planarization characteristics, even if the substrate to be processed has a structure or step (concavo-convex) with a height of 30 nm or more, a flat cured film can be formed. That is, the above organic film forming method is particularly useful when forming a flat organic film on such a substrate to be processed.

[0082] Note that the thickness of the organic film to be formed is appropriately selected, but it is preferably 30 to 20,000 nm, and particularly preferably 50 to 15,000 nm.

[0083] Also, the above organic film forming method is applicable to both the case of forming an organic film as the underlayer film in the multilayer resist method and the case of forming an organic film for a planarization film using the composition for forming an organic film of the present invention.

[0084] The composition for forming an organic film of the present invention can be used for forming an organic film capable of planarizing the surface of a stepped substrate used in the manufacturing process of a semiconductor device. The composition for forming an organic film of the present invention is spin-coated on a substrate to be processed, and the substrate coated with the composition for forming an organic film is heat-treated in air at a temperature of 50°C or higher and 250°C or lower for 10 to 600 seconds, and then heat-treated in an inert gas at a temperature of 250°C or higher for 10 to 7200 seconds to form a cured film, which can be applied to an organic film forming method.

[0085] In this organic film forming method, first, the composition for forming an organic film of the present invention described above is spin-coated on a substrate to be processed. By using the spin-coating method, good embedding characteristics can be surely obtained. After spin-coating, baking (heat treatment) is performed to promote planarization and crosslinking reaction due to heat flow. In addition, since the solvent in the composition can be evaporated by this baking, mixing can be prevented even when a resist upper layer film or a silicon-containing resist intermediate film is formed on the organic film.

[0086] <Pattern Forming Method> [Three-Layer Resist Method Using Silicon-Containing Resist Intermediate Film] An organic film is formed on a substrate to be processed using the composition for forming an organic film of the present invention, a silicon-containing film is formed on the organic film using a film forming material containing silicon atoms, a resist upper layer film is formed on the silicon-containing film using a resist upper layer film material composed of a photoresist composition, a circuit pattern is formed on the resist upper layer film, the silicon-containing film is etched to transfer the pattern using the resist upper layer film on which the circuit pattern is formed as a mask, the organic film is etched to transfer the pattern using the silicon-containing film on which the pattern is transferred as a mask, and further, the substrate to be processed is etched to transfer the pattern using the organic film on which the pattern is transferred as a mask, and a pattern forming method is possible.

[0087] As the substrate to be processed, it is preferable to use a semiconductor device substrate or a substrate with any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxynitride film, and a metal oxynitride film formed thereon. More specifically, although not particularly limited, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., and those with the above-mentioned metal films or the like formed as the layer to be processed on the substrate are used.

[0088] As the layer to be processed, various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si and their stopper films are used, and they can usually be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming the layer to be processed, substrates and the layer to be processed are made of different materials.

[0089] The metal constituting the substrate to be processed is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof.

[0090] Also, as the substrate to be processed, it is preferable to use a substrate having a structure or step with a height of 30 nm or more.

[0091] When forming an organic film on the substrate to be processed using the composition for forming an organic film of the present invention, the above-mentioned organic film forming method may be applied.

[0092] Next, a resist intermediate film (silicon-containing resist intermediate film) is formed on the organic film using a resist intermediate film material containing silicon atoms. As the silicon-containing resist intermediate film material, a polysiloxane-based intermediate film material is preferred. By imparting an antireflection effect to the silicon-containing resist intermediate film, reflection can be suppressed. In particular, for 193 nm exposure, when a material containing a large amount of aromatics and having a high etching selectivity with respect to the substrate is used as the composition for forming the organic film, the k value increases and the substrate reflection increases. However, by providing absorption such that an appropriate k value is obtained for the silicon-containing resist intermediate film, it becomes possible to suppress reflection, and the substrate reflection can be reduced to 0.5% or less. As the silicon-containing resist intermediate film having an antireflection effect, anthracene is used for 248 nm and 157 nm exposure, and a polysiloxane having an absorbing group having a phenyl group or a silicon-silicon bond in a pendant structure or a polysiloxane structure and crosslinking with an acid or heat is preferably used for 193 nm exposure.

[0093] Next, a resist upper layer film is formed on the silicon-containing resist intermediate film using a resist upper layer film material composed of a photoresist composition. The resist upper layer film material can be either positive or negative, and the same photoresist composition as that usually used can be used. After spin-coating the resist upper layer film material, it is preferably prebaked at 60 to 180 °C for 10 to 300 seconds. Thereafter, exposure is performed according to a conventional method, and further, post-exposure bake (PEB) and development are performed to obtain a resist upper layer film pattern. The thickness of the resist upper layer film is not particularly limited, but is preferably 30 to 500 nm, and particularly preferably 50 to 400 nm.

[0094] Next, a circuit pattern (resist upper layer film pattern) is formed on the resist upper layer film. In forming the circuit pattern, it is preferable to form the circuit pattern by lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof.

[0095] Note that as the exposure light, high-energy rays with a wavelength of 300 nm or less can be mentioned, specifically extreme ultraviolet rays, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 laser light (157 nm), Kr2 laser light (146 nm), Ar2 laser light (126 nm), soft X-rays (EUV) of 3 to 20 nm, electron beam (EB), ion beam, X-rays, etc.

[0096] In addition, in the formation of the circuit pattern, it is preferable to develop the circuit pattern by alkali development or organic solvent development.

[0097] Next, using the resist upper layer film on which the circuit pattern is formed as a mask, the pattern is transferred to the silicon-containing resist intermediate film by etching. The etching of the silicon-containing resist intermediate film performed using the resist upper layer film pattern as a mask is preferably performed using a fluorocarbon-based gas. Thereby, a silicon-containing resist intermediate film pattern is formed.

[0098] Next, using the silicon-containing resist intermediate film on which the pattern is transferred as a mask, the pattern is transferred to the organic film by etching. Since the silicon-containing resist intermediate film exhibits higher etching resistance to oxygen gas or hydrogen gas compared to organic substances, the etching of the organic film performed using the silicon-containing resist intermediate film pattern as a mask is preferably performed using an etching gas mainly composed of oxygen gas or hydrogen gas. Thereby, an organic film pattern can be formed.

[0099] Next, using the organic film onto which the pattern has been transferred as a mask, the pattern is transferred onto the substrate to be processed by etching. The etching of the next substrate to be processed (layer to be processed) can be performed by a conventional method. For example, if the substrate to be processed is SiO2, SiN, or a silica-based low dielectric constant insulating film, etching mainly using a fluorocarbon gas is performed. If it is p-Si, Al, or W, etching mainly using a chlorine-based or bromine-based gas is performed. When substrate processing is performed by etching using a fluorocarbon gas, the silicon-containing resist intermediate film pattern is peeled off simultaneously with the substrate processing. On the other hand, when substrate processing is performed by etching using a chlorine-based or bromine-based gas, in order to peel off the silicon-containing resist intermediate film pattern, it is necessary to separately perform dry etching peeling using a fluorocarbon gas after the substrate processing.

[0100] The organic film obtained by using the composition for forming an organic film of the present invention is excellent in etching resistance during etching of the substrate to be processed as described above.

[0101] [Four-layer resist method using a silicon-containing resist intermediate film and an organic antireflection film] Also, an organic film is formed on the substrate to be processed using the composition for forming an organic film of the present invention, a silicon-containing resist intermediate film is formed on the organic film using a resist intermediate film material containing a silicon atom, an organic antireflection film is formed on the silicon-containing resist intermediate film, a resist upper layer film is formed on the organic antireflection film using a resist upper layer film material composed of a photoresist composition, a circuit pattern is formed on the resist upper layer film, the pattern is transferred onto the organic antireflection film and the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the circuit pattern is formed as a mask, the pattern is transferred onto the organic film by etching using the silicon-containing resist intermediate film onto which the pattern has been transferred as a mask, and further, a pattern forming method in which the pattern is transferred onto the substrate to be processed by etching using the organic film onto which the pattern has been transferred as a mask is also possible.

[0102] Note that this method can be performed in the same manner as the three-layer resist method using the above-described silicon-containing resist intermediate film, except that an organic antireflection film (BARC) is formed between the silicon-containing resist intermediate film and the resist upper layer film.

[0103] The organic antireflection film can be formed by spin coating using a known organic antireflection film material.

[0104] [Three - layer resist method using an inorganic hard mask] Further, as a pattern formation method by a three - layer resist method using the composition for forming an organic film of the present invention, an organic film is formed on a substrate to be processed using the composition for forming an organic film of the present invention described above. An inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a titanium oxide film, and a titanium nitride film is formed on the organic film. A resist upper layer film is formed on the inorganic hard mask using a resist upper layer film material composed of a photoresist composition. A circuit pattern is formed on the resist upper layer film. The pattern is transferred to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern is formed as a mask. The pattern is transferred to the organic film by etching using the inorganic hard mask on which the pattern is transferred as a mask. Furthermore, a pattern formation method in which the pattern is transferred to the substrate to be processed by etching using the organic film on which the pattern is transferred as a mask is also possible.

[0105] Note that this method can be carried out in the same manner as the three - layer resist method using the above - mentioned silicon - containing resist intermediate film, except that an inorganic hard mask is formed on the organic film instead of the silicon - containing resist intermediate film.

[0106] Inorganic hard masks selected from silicon oxide films, silicon nitride films, and silicon oxynitride films (SiON films) can be formed by methods such as CVD or ALD. As a method for forming a silicon nitride film, for example, it is described in JP-A-2002-334869, WO 2004 / 066377, etc. The film thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. As the inorganic hard mask, a SiON film having a high effect as an antireflection film is most preferably used. Since the substrate temperature when forming the SiON film is 300 to 500 °C, the lower layer film needs to withstand a temperature of 300 to 500 °C. The organic film formed using the composition for forming an organic film of the present invention has high heat resistance and can withstand a high temperature of 300 °C to 500 °C. Therefore, a combination of an inorganic hard mask formed by CVD or ALD and an organic film formed by spin coating is possible.

[0107] [Four-layer resist method using an inorganic hard mask and an organic antireflection film] Further, as a pattern formation method by a four-layer resist method using the composition for forming an organic film of the present invention, an organic film is formed on a substrate to be processed using the composition for forming an organic film of the present invention described above. An inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film, and an organic antireflection film is formed on the inorganic hard mask. A resist upper layer film is formed on the organic antireflection film using a resist upper layer film material composed of a photoresist composition. A circuit pattern is formed on the resist upper layer film, and the pattern is transferred by etching to the organic antireflection film and the inorganic hard mask using the resist upper layer film on which the circuit pattern is formed as a mask. The pattern is transferred by etching to the organic film using the inorganic hard mask on which the pattern is transferred as a mask. Furthermore, a pattern formation method in which the pattern is transferred by etching to the substrate to be processed using the organic film on which the pattern is transferred as a mask is also possible.

[0108] Note that this method can be carried out in the same manner as the three-layer resist method using the above inorganic hard mask, except that an organic antireflection film (BARC) is formed between the inorganic hard mask and the resist upper layer film.

[0109] In particular, when a SiON film is used as the inorganic hard mask, it is possible to suppress reflection even in immersion lithography with a high NA exceeding 1.0 by the two-layer antireflection films of the SiON film and the BARC. Another merit of forming the BARC is that it has the effect of reducing the footing of the resist upper layer film pattern directly on the SiON film.

[0110] Here, an example of a pattern formation method by the three-layer resist method is shown in FIGS. 2(A) to (F). In the case of the three-layer resist method, as shown in FIG. 2(A), after forming the organic film 3 using the composition for forming an organic film of the present invention on the processed layer 2 formed on the substrate 1, a silicon-containing resist intermediate film 4 is formed, and a resist upper layer film 5 is formed thereon. Next, as shown in FIG. 2(B), the exposed portion 6 of the resist upper layer film 5 is exposed, and PEB (post-exposure bake) is performed. Next, as shown in FIG. 2(C), development is performed to form a resist upper layer film pattern 5a. Next, as shown in FIG. 2(D), using the resist upper layer film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is dry-etched using a fluorocarbon gas to form a silicon-containing resist intermediate film pattern 4a. Next, as shown in FIG. 2(E), after removing the resist upper layer film pattern 5a, the organic film 3 is etched with oxygen plasma using the silicon-containing resist intermediate film pattern 4a as a mask to form an organic film pattern 3a. Further, as shown in FIG. 2(F), after removing the silicon-containing resist intermediate film pattern 4a, the processed layer 2 is etched using the organic film pattern 3a as a mask to form a pattern 2a.

[0111] When forming the inorganic hard mask, the silicon-containing resist intermediate film 4 may be changed to the inorganic hard mask. When forming the BARC, the BARC may be formed between the silicon-containing resist intermediate film 4 and the resist upper layer film 5. The etching of the BARC may be continuously performed prior to the etching of the silicon-containing resist intermediate film 4, or the etching of only the BARC may be performed and then the etching of the silicon-containing resist intermediate film 4 may be performed after changing the etching apparatus or the like.

[0112] As described above, in the pattern formation method of the present invention, a fine pattern can be formed on a substrate to be processed with high precision by the multilayer resist method.

Example

[0113] Hereinafter, synthesis examples, comparative synthesis examples, examples, and comparative examples will be shown to more specifically explain the present invention, but the present invention is not limited thereto. As for the molecular weight and dispersity, the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, and the dispersity (Mw / Mn) was determined.

[0114] Synthesis Example: Synthesis of High Heat-Resistant Organic Compounds

[0115] [Synthesis Example 1] Synthesis of Compound (A1) 200 g of diol (B1), 800 g of 1,2-dichloroethane, and 76 g of acetyl chloride were mixed and heated under reflux for 72 hours. After cooling to room temperature, 400 mL of diisopropyl ether was added, and the solid was collected by filtration and dried under reduced pressure to obtain 211 g of dichloride (B2). To a mixture of 10.2 g of ice-cooled ethynylbenzene and 80 g of toluene, 100 mL of a 1N tetrahydrofuran solution of ethylmagnesium bromide was added, and the temperature was gradually raised to room temperature. 13.2 g of dichloride (B2) was added, and the mixture was heated and stirred at 60 °C for 5 hours. After cooling, dilute hydrochloric acid was added to stop the reaction. After washing with water, concentration under reduced pressure was performed to obtain 16.3 g of the target product (A1). The IR and LC-MS analysis results of the synthesized compound (A1) are shown below.

Chemical formula

[0116] IR (D-ATR): ν = 3285, 3060, 1600, 1490, 1448, 815, 754, 744, 690 cm -1 LC-MS(MM-ES Positive / aq.AcONH4-MeCN): m / z = 683 (C 54 H 34 + H + ).

[0117] [Synthesis Example 2] Synthesis of Compound (A2) Compound (A2) was synthesized by a method similar to [Synthesis Example 1], except that 1-ethynyl-4-methoxybenzene was used instead of ethynylbenzene. The IR and LC-MS analysis results of the synthesized compound (A2) are shown below.

Chemical Structure

[0118] IR (D-ATR): ν = 3037, 2955, 2933, 2835, 1605, 1509, 1448, 1290, 1248, 1170, 1030, 831, 812, 765, 754, 736 cm -1 LC-MS (MM-ES Positive / aq.AcONH4-MeCN): m / z = 743 (C 56 H 38 O2 + H + ).

[0119] [Synthesis Example 3] Synthesis of Compound (A3) To a mixture of 6.9 g of dichloride (B2) and 50 g of toluene, 100 mL of a 0.5 N tetrahydrofuran solution of ethynylmagnesium bromide was added, and the mixture was heated under reflux for 200 minutes. After cooling, dilute hydrochloric acid was added to stop the reaction. After washing with water, concentration under reduced pressure was performed to obtain 6.6 g of compound (A3). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, Mw = 1100 and Mw / Mn = 1.74. The IR and 1 1H-NMR analysis results of the synthesized compound (A3) are shown below.

Chemical Structure

[0120] IR (D-ATR): ν = 3291, 3061, 3036, 1604, 1493, 1475, 1448, 1005, 920, 815, 753, 730, 650 cm -1 。 1 H-NMR (600 MHz, THF-d8): δ = 2.85 - 2.90 (2H, H C≡C-), 7.00 - 7.85 (49H, Ar- H )。

[0121] [Synthesis Example 4] Synthesis of Compound (A4) To a mixture of 11 g of ice-cooled 1,3-diethynylbenzene and 80 g of toluene, 100 mL of a 1N ethylmagnesium bromide solution in tetrahydrofuran was added, and the temperature was gradually raised to room temperature. 23 g of dichloride (B2) was added, and the mixture was heated and stirred at 60 °C for 2 hours. After cooling, dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, methanol was added, and the resulting solid was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 27 g of the target compound (A4). By GPC, the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined, and Mw = 2000 and Mw / Mn = 1.58 were obtained.

Chemical Structure

[0122] The IR analysis results of the synthesized compound (A4) are shown below. IR (D-ATR): ν = 3291, 3061, 3028, 1594, 1493, 1475, 1448, 813, 794, 753, 732 cm -1

[0123] [Synthesis Example 5] Synthesis of Compound (A5) A mixture of 219 g of bis(4-bromophenyl) ether cooled to -20 °C under an N₂ atmosphere and 1000 mL of t-butyl methyl ether was added with 500 mL of a 2.67 M hexane solution of n-butyllithium, and the mixture was stirred at -20 °C for 20 minutes. 229 g of 9-fluorenone (B4) was added, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 4 hours. Water was added to stop the reaction. After washing with water and concentrating under reduced pressure, hexane was added, the resulting solid was collected by filtration, washed with hexane, and dried under reduced pressure to obtain 293 g of diol (B5). 265 g of diol (B5), 1000 g of 1,2-dichloroethane, and 157 g of acetyl chloride were mixed and stirred at room temperature for 22 hours. 1000 mL of hexane was added, the solid was collected by filtration, and dried under reduced pressure to obtain 181 g of dichloride (B6). To a mixture of 10.1 g of ice-cooled 1,3-diethynylbenzene and 50 g of toluene was added 50 mL of a 1 N tetrahydrofuran solution of ethylmagnesium bromide, and the temperature was gradually raised to room temperature. 11.4 g of dichloride (B6) was added, the temperature was raised to 40 °C, and the mixture was stirred for 4 hours. Dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, methanol was added, the resulting solid was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 13.3 g of the target product (A5). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, Mw = 1000 and Mw / Mn = 1.17 were obtained.

[0124] [Chemical formula]

[0125] The IR analysis results of the synthesized compound (A5) are shown below. IR (D-ATR): ν = 3289, 3062, 1594, 1496, 1475, 1448, 1240, 825, 751, 733 cm -1

[0126] [Synthesis Example 6] Synthesis of compound (A6) To a mixture of 43.2 g of 2,8-dibromodibenzofuran cooled to -20 °C under a nitrogen atmosphere and 200 mL of t-butyl methyl ether, 100 mL of a 2.65 M hexane solution of n-butyllithium was added, and the mixture was stirred at -20 °C for 15 minutes. 45.4 g of 9-fluorenone (B4) was added, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 5 hours. Water was added to stop the reaction. After washing with water and concentrating under reduced pressure, heptane was added, the resulting solid was collected by filtration, washed with heptane, and dried under reduced pressure to obtain 60.2 g of diol (B7). 31.7 g of diol (B7), 150 g of 1,2-dichloroethane, and 18.8 g of acetyl chloride were mixed, the temperature was raised to 40 °C, and the mixture was stirred for 18 hours. After cooling to room temperature, 300 mL of hexane was added, the solid was collected by filtration, and dried under reduced pressure to obtain 24.9 g of dichloride (B8). To a mixture of 10.5 g of ice-cooled 1,3-diethynylbenzene and 140 g of toluene, 100 mL of a 1 N tetrahydrofuran solution of ethylmagnesium bromide was added, and the temperature was gradually raised to room temperature. 23.6 g of dichloride (B8) was added, the temperature was raised to 40 °C, and the mixture was stirred for 19 hours. After cooling to room temperature, dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, diisopropyl ether was added, the resulting solid was collected by filtration, washed with diisopropyl ether, and dried under reduced pressure to obtain 21.4 g of the target product (A6). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, Mw = 1600 and Mw / Mn = 1.44 were obtained.

[0127] [Chemical formula]

[0128] The IR analysis results of the synthesized compound (A6) are shown below. IR (D-ATR): ν = 3292, 3061, 1594, 1476, 1448, 1205, 812, 793, 746, 733 cm -1

[0129] [Synthesis Example 7] Synthesis of compound (A7) A mixture of 31.1 g of 3,6-dibromo-9-phenylcarbazole cooled to -20 °C under an N₂ atmosphere and 200 mL of t-butyl methyl ether was added with 100 mL of a 1.55 M hexane solution of n-butyllithium, and stirred at -10 °C for 30 minutes. 26.5 g of 9-fluorenone (B4) was added, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 6 hours. Water was added to stop the reaction. After washing with water and concentrating under reduced pressure, heptane was added, the resulting solid was collected by filtration, washed with heptane, and dried under reduced pressure to obtain 36.7 g of diol (B9). 18.1 g of diol (B9), 80 g of 1,2-dichloroethane, and 9.4 g of acetyl chloride were mixed, heated to 60 °C, and stirred for 21 hours. After cooling to room temperature, 45 mL of diisopropyl ether was added, the solid was collected by filtration, and dried under reduced pressure to obtain 12.7 g of dichloride (B10). To a mixture of 5.0 g of ice-cooled 1,3-diethynylbenzene and 60 g of toluene was added 48 mL of an ethylmagnesium bromide 1N tetrahydrofuran solution, and the temperature was gradually raised to room temperature. 12.8 g of dichloride (B10) was added, and the mixture was stirred at room temperature for 22 hours. Dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, diisopropyl ether was added, the resulting solid was collected by filtration, washed with diisopropyl ether, and dried under reduced pressure to obtain 15.7 g of the target product (A7). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, Mw = 1500 and Mw / Mn = 1.37.

[0130] [Chemical formula]

[0131] The IR analysis results of the synthesized compound (A7) are shown below. IR (D-ATR): ν = 3292, 3062, 1596, 1501, 1483, 1475, 1448, 1236, 809, 793, 746, 732 cm -1

[0132] [Synthesis Example 8] Synthesis of Compound (A8) To a mixed solution of 28.8 g of 3,3'-dibromo-4,4'-dimethoxybiphenyl cooled to -20°C under an N₂ atmosphere and 200 mL of t-butyl methyl ether, 100 mL of a 1.55 M hexane solution of n-butyllithium was added, and the mixture was stirred at -20°C for 10 minutes. 26.5 g of 9-fluorene (B4) was added, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 4 hours. Water was added to stop the reaction. After washing with water and concentrating under reduced pressure, heptane was added, the resulting solid was collected by filtration, washed with heptane, and dried under reduced pressure to obtain 36.0 g of diol (B11). 11.5 g of diol (B11), 50 g of 1,2-dichloroethane, and 6.3 g of acetyl chloride were mixed, the temperature was raised to 60°C, and the mixture was stirred for 22 hours. After cooling to room temperature, 30 mL of hexane was added, the solid was collected by filtration, and dried under reduced pressure to obtain 6.7 g of dichloride (B12). To a mixture of 2.1 g of ice-cooled 1,3-diethynylbenzene and 30 g of toluene, 20 mL of a 1 N tetrahydrofuran solution of ethylmagnesium bromide was added, and the temperature was gradually raised to room temperature. 5.1 g of dichloride (B12) was added, the temperature was raised to 60°C, and the mixture was stirred for 4 hours. After cooling to room temperature, dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, diisopropyl ether was added, the resulting solid was collected by filtration, washed with diisopropyl ether, and dried under reduced pressure to obtain 4.2 g of the target product (A8). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, Mw = 2100 and Mw / Mn = 1.64.

[0133]

Chemical formula

[0134] The IR analysis results of the synthesized compound (A8) are shown below. IR(D-ATR): ν = 3289, 3060, 2933, 2833, 1594, 1487, 1475, 1448, 1251, 1023, 811, 794, 750, 733 cm -1

[0135] [Synthesis Example 9] Synthesis of Compound (A9) A mixture of 42.9 g of 5,5'-dibromo-2,2'-bithiophene cooled to -20 °C under an N₂ atmosphere and 200 mL of t-butyl methyl ether was added with 100 mL of a 2.65 M hexane solution of n-butyllithium and stirred at -20 °C for 20 minutes. 45.4 g of 9-fluorene (B4) was added, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 5 hours. Water was added to stop the reaction. After washing with water and concentrating under reduced pressure, hexane was added, the resulting solid was collected by filtration, washed with hexane, and dried under reduced pressure to obtain 50.2 g of diol (B13). 21.1 g of diol (B13), 100 g of 1,2-dichloroethane, and 12.6 g of acetyl chloride were mixed, the temperature was raised to 60 °C, and the mixture was stirred for 4 hours. After cooling to room temperature, 150 mL of hexane was added, the solid was collected by filtration, and dried under reduced pressure to obtain 18.6 g of dichloride (B14). To a mixture of 5.0 g of ice-cooled 1,3-diethynylbenzene and 30 g of toluene was added 25 mL of a 1 N tetrahydrofuran solution of ethylmagnesium bromide, and the temperature was gradually raised to room temperature. 5.6 g of dichloride (B14) was added, and the mixture was stirred at room temperature for 7 hours. Dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, methanol was added, the resulting solid was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 5.5 g of the target product (A9). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, Mw = 5800 and Mw / Mn = 3.21.

[0136] [Chemical formula]

[0137] The IR analysis results of the synthesized compound (A9) are shown below. IR (D-ATR): ν = 3294, 3060, 1593, 1475, 1446, 1349, 895, 794, 740, 732 cm -1

[0138] [Synthesis Example 10] Synthesis of Compound (A10) 24.2 g of 4,4'-dibromobiphenyl cooled to -20 °C under a nitrogen atmosphere was added to a mixture of 100 mL of t-butyl methyl ether and 100 mL of cyclopentyl methyl ether. 100 mL of a 2.67 M hexane solution of n-butyllithium was added, and the mixture was stirred at -20 °C for 20 minutes. 35.67 g of 4,4'-dimethoxybenzophenone (B15) was added, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 4 hours. Water was added to stop the reaction. After washing with water and concentrating under reduced pressure, heptane was added, the resulting solid was collected by filtration, washed with heptane, and dried under reduced pressure to obtain 42.2 g of diol (B16). 19.2 g of diol (B16), 80 g of 1,2-dichloroethane, and 9.42 g of acetyl chloride were mixed, the temperature was raised to 40 °C, and the mixture was stirred for 23 hours. After cooling to room temperature, 80 mL of diisopropyl ether was added, the solid was collected by filtration, and dried under reduced pressure to obtain 18.4 g of dichloride (B17). To a mixture of 4.21 g of ice-cooled 1,3-diethynylbenzene and 80 g of toluene, 40 mL of a 1 N tetrahydrofuran solution of ethylmagnesium bromide was added, and the temperature was gradually raised to room temperature. 11.3 g of dichloride (B17) was added, and the mixture was stirred at room temperature for 22 hours. Dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, methanol was added, the resulting solid was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 11.3 g of the target product (A10). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, Mw = 2100 and Mw / Mn = 1.40.

[0139] [Chemical formula]

[0140] The IR analysis results of the synthesized compound (A10) are shown below. IR (D-ATR): ν = 3290, 3032, 2997, 2951, 2930, 2904, 2833, 1606, 1506, 1440, 1298, 1250, 1177, 1034, 824, 795, 731 cm -1

[0141] [Synthesis Example 11] Synthesis of Compound (A11) To a mixed solution of 43.5 g of bis(4-bromophenyl) ether cooled to -20 °C under a nitrogen atmosphere and 200 mL of t-butyl methyl ether, 100 mL of a 2.65 M hexane solution of n-butyllithium was added, and the mixture was stirred at -20 °C for 30 minutes. 49.4 g of xanthone (B18) was added, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 4 hours. Water was added to stop the reaction. After washing with water and concentrating under reduced pressure, heptane was added, the resulting solid was collected by filtration, washed with heptane, and dried under reduced pressure to obtain 63.4 g of diol (B19). 33.8 g of diol (B19), 150 g of 1,2-dichloroethane, and 18.8 g of acetyl chloride were mixed, the temperature was raised to 40 °C, and the mixture was stirred for 24 hours. After cooling to room temperature, 300 mL of heptane was added, the solid was collected by filtration, and dried under reduced pressure to obtain 18.5 g of dichloride (B20). To a mixture of 5.26 g of ice-cooled 1,3-diethynylbenzene and 80 g of toluene, 50 mL of a 1 N tetrahydrofuran solution of ethylmagnesium bromide was added, and the temperature was gradually raised to room temperature. 12.5 g of dichloride (B20) was added, and the mixture was stirred at room temperature for 24 hours. Dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, heptane was added, the resulting solid was collected by filtration, washed with heptane, and dried under reduced pressure to obtain 10.4 g of the target product (A11). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, Mw = 1700 and Mw / Mn = 1.67 were obtained.

[0142]

Chemical formula

[0143] The IR analysis results of the synthesized compound (A11) are shown below. IR(D-ATR): ν = 3291, 3036, 1598, 1495, 1445, 1242, 825, 752 cm -1

[0144] [Synthesis Example 12] Synthesis of Compound (A12) 9.3 g of diol (B21), 60 g of 1,2-dichloroethane, and 5.0 g of acetyl chloride were mixed, heated to 60 °C, and stirred for 20 hours. After cooling to room temperature, 100 mL of hexane was added, the solid was filtered off, and dried under reduced pressure to obtain 7.2 g of dichloride (B22). To a mixture of 1.6 g of ice-cooled 1,3-diethynylbenzene and 20 g of toluene, 15 mL of a 1 N ethylmagnesium bromide solution in tetrahydrofuran was added, and the temperature was gradually raised to room temperature. 3.4 g of dichloride (B22) was added, and the mixture was stirred at room temperature for 5 hours. Dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, methanol was added, the resulting solid was filtered off, washed with methanol, and dried under reduced pressure to obtain 3.7 g of the target product (A12). When the weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, Mw = 2500 and Mw / Mn = 2.38.

[0145]

Chemical formula

[0146] The IR analysis results of the synthesized compound (A12) are shown below. IR (D-ATR): ν = 3291, 3058, 3027, 1591, 1491, 1474, 1457, 1440, 1393, 1189, 816, 794, 752 cm -1

[0147] [Synthesis Example 13] Synthesis of Compound (A13) To a mixed solution of 42.6 g of tris(4-bromophenyl)amine and 300 mL of t-butyl methyl ether cooled to -20 °C under a nitrogen atmosphere, 100 mL of a 2.65 M n-butyllithium solution in hexane was added, and the mixture was stirred at -20 °C for 30 minutes. 45.4 g of 9-fluorene (B4) was added, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 5 hours. Water was added to stop the reaction. After washing with water and concentrating under reduced pressure, heptane was added, the resulting solid was filtered off, washed with heptane, and dried under reduced pressure to obtain 33.3 g of triol (B23). 23.6 g of triol (B23), 200 g of 1,2-dichloroethane, and 14.1 g of acetyl chloride were mixed and stirred at room temperature for 19 hours. 150 mL of hexane was added, the solid was collected by filtration, and dried under reduced pressure to obtain 22.0 g of trichloride (B24). To a mixture of 9.7 g of ice-cooled 1,3-diethynylbenzene and 40 g of toluene, 46 mL of a 1 N solution of ethylmagnesium bromide in tetrahydrofuran was added, and the temperature was gradually raised to room temperature. 10.0 g of trichloride (B24) was added, and the mixture was stirred at room temperature for 4 hours. Dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, methanol was added, the resulting solid was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 13.4 g of the target product (A13). When the weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, Mw = 2100 and Mw / Mn = 1.37 were obtained.

[0148]

Chemical formula

[0149] The IR analysis results of the synthesized compound (A13) are shown below. IR (D-ATR): ν = 3289, 3060, 3034, 1595, 1502, 1447, 1280, 823, 752, 732, 685 cm -1

[0150] [Synthesis Example 14] Synthesis of compound (A14) To a mixture of 2.0 g of ice-cooled ethynylbenzene and 20 g of toluene, 20 mL of a 1 N solution of ethylmagnesium bromide in tetrahydrofuran was added, and the temperature was gradually raised to room temperature. 4.4 g of trichloride (B24) was added, and the mixture was stirred at room temperature for 6 hours. Dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, hexane was added, the resulting solid was collected by filtration, washed with hexane, and dried under reduced pressure to obtain 4.9 g of the target product (A14).

[0151]

Chemical formula

[0152] The IR and LC-MS analysis results of the synthesized compound (A14) are shown below. IR (D-ATR): ν = 3058, 1599, 1503, 1447, 1280, 824, 754, 743, 690 cm -1 LC-MS (MM-ES Positive / aq.AcONH4-MeCN): m / z = 1038 (C 81 H 51 N + H + ).

[0153] [Synthesis Example 15] Synthesis of Compound (A15) 7.0 g of diol (B25), 50 g of 1,2-dichloroethane, and 3.0 g of acetyl chloride were mixed and stirred at room temperature for 22 hours. 45 mL of hexane was added, and the solid was collected by filtration and dried under reduced pressure to obtain 3.9 g of dichloride (B26). To a mixture of 1.3 g of ice-cooled 1,3-diethynylbenzene and 20 g of toluene, 12 mL of a 1N solution of ethylmagnesium bromide in tetrahydrofuran was added, and the temperature was gradually raised to room temperature. 3.8 g of dichloride (B26) was added, and the temperature was raised to 40 °C and stirred for 22 hours. Dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, methanol was added, and the resulting solid was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 3.4 g of the target product (A15). By GPC, the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined to be Mw = 2400 and Mw / Mn = 1.57.

[0154]

Chemical Structure

[0155] The IR analysis results of the synthesized compound (A15) are shown below. IR (D-ATR): ν = 3284, 3035, 2917, 2858, 2301, 2228, 1606, 1505, 1448, 1221, 1005, 821 cm -1

[0156] [Synthesis Example 16] Synthesis of Compound (A16) 47.9 g of 3,5-dibromoanisole (B27), 36.3 g of 2-methyl-3-butyn-2-ol, 1.71 g of copper iodide, 150 g of triethylamine, 75 g of tetrahydrofuran, and 6.32 g of dichlorobis(triphenylphosphine)palladium(II) were mixed, heated to 60 °C, and stirred for 7 hours. After cooling to room temperature, the mixture was filtered, the filtrate was concentrated under reduced pressure, hexane was added, the resulting solid was collected by filtration, washed with hexane, and dried under reduced pressure to obtain 41.4 g of diol (B28). 35.0 g of diol (B28), 2.06 g of sodium hydroxide, and 150 g of toluene were mixed, heated to 110 °C, and stirred for 2 hours. After cooling to room temperature, the mixture was washed with water and concentrated under reduced pressure, and the obtained solid was purified by column chromatography [silica gel N60 (350 g), hexane:ethyl acetate = 15:1] to obtain 4.71 g of diethynyl compound (B29).

[0157] [Chemical formula]

[0158] The IR and 1H NMR analysis results of the synthesized compound (B29) are shown below. IR (D-ATR): ν = 3276, 3075, 3000, 2960, 2940, 2838, 1580, 1448, 1323, 1294, 1157, 1060, 881, 858 cm -1 1H NMR (600 MHz, DMSO-d6) δ 7.11 (dd, J = 1.7, 1.7 Hz, 1H), 7.06 (d, J = 1.7 Hz, 2H), 4.26 (s, 2H), 3.77 (s, 3H).

[0159] To a mixture of 2.6 g of the cooled diethynyl compound (B29) and 30 g of toluene, 20 mL of a 1N ethylmagnesium bromide solution in tetrahydrofuran was added, and the temperature was gradually raised to room temperature. 4.7 g of dichloride (B6) was added, the temperature was raised to 40 °C, and the mixture was stirred for 5 hours. After cooling to room temperature, dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, diisopropyl ether was added, the resulting solid was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 4.5 g of the target product (A16). By GPC, the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined to be Mw = 2000 and Mw / Mn = 1.37.

[0160] [Chemical formula]

[0161] The IR analysis results of the synthesized compound (A16) are shown below. IR (D-ATR): ν = 3289, 3063, 2967, 2934, 2838, 1580, 1496, 1448, 1240, 1014, 849, 749, 728 cm -1

[0162] [Synthesis Example 17] Synthesis of compound (A17) 53.2 g of 2,4-dibromoanisole (B30), 40.4 g of 2-methyl-3-butyn-2-ol, 3.81 g of copper iodide, 150 g of triethylamine, 75 g of tetrahydrofuran, and 14.0 g of dichlorobis(triphenylphosphine)palladium(II) were mixed, the temperature was raised to 60 °C, and the mixture was stirred for 7 hours. After cooling to room temperature, it was filtered, the filtrate was concentrated under reduced pressure, and the resulting oily substance was purified by column chromatography [silica gel (600 g), hexane:ethyl acetate = 2:1] to obtain 50.9 g of diol (B31). 50.2 g of diol (B31), 29.4 g of sodium hydroxide, and 200 g of toluene were mixed, heated to 110 °C, and stirred for 5 hours. After cooling to room temperature, it was washed with water and concentrated under reduced pressure. The obtained solid was purified by column chromatography [silica gel N60 (500 g), hexane:ethyl acetate = 20:1] to obtain 10.1 g of diethynyl compound (B32).

[0163]

Chemical formula

[0164] The IR, 1H NMR, and LC-MS analysis results of the synthesized compound (B32) are shown below. IR (D-ATR): ν = 3304, 3271, 3009, 2974, 2948, 2896, 2843, 1598, 1496, 1290, 1259, 1118, 1020, 897, 821, 812 cm -1 1H NMR (600 MHz, DMSO-d6) δ 7.48 - 7.46 (m, 2H), 7.06 (d, J = 8.7 Hz, 1H), 4.29 (s, 1H), 4.07 (s, 1H), 3.83 (s, 3H). LC-MS (MM-ES Positive / aq.AcONH4-MeCN): m / z = 157 (C 11 H8O + H + ).

[0165] To a mixture of 2.6 g of ice-cooled diethynyl compound (B32) and 30 g of toluene, 20 mL of a 1N ethylmagnesium bromide solution in tetrahydrofuran was added, and the temperature was gradually raised to room temperature. 4.7 g of dichloride (B6) was added, the temperature was raised to 40 °C, and the mixture was stirred for 4 hours. After cooling to room temperature, dilute hydrochloric acid was added to stop the reaction. After washing with water and concentrating under reduced pressure, methanol was added. The resulting solid was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 6.0 g of the target product (A17). By GPC, the weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined to be Mw = 1800 and Mw / Mn = 1.55.

[0166] [Chemical formula]

[0167] The IR analysis results of the synthesized compound (A17) are shown below. IR (D-ATR): ν = 3288, 3062, 2940, 2840, 1597, 1495, 1448, 1243, 1016, 818, 744, 734 cm -1

[0168] [Synthesis Example 18] Synthesis of Compound (A18) 58.7 g of (B-33), 41.3 g of 9-fluorenone, 5 ml of 3-mercaptopropionic acid, and 300 ml of 1,2-dichloroethane were made into a homogeneous solution at an internal temperature of 70 °C under a nitrogen atmosphere. Then, 10 ml of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70 °C for 24 hours. After cooling to room temperature, 500 g of methyl isobutyl ketone was added. The organic layer was washed 5 times with 100 g of pure water, and then the organic layer was dried to dryness under reduced pressure. 200 g of THF was added to the residue to make a homogeneous solution, and then the polymer was reprecipitated with 1500 g of methanol. The precipitated polymer was separated by filtration and washed 2 times with 800 g of methanol and recovered. The recovered polymer was dried in vacuo at 70 °C to obtain (A18). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (A18): Mw = 3500, Mw / Mn = 2.94 [Chemical formula]

[0169] [Synthesis Example 19] Synthesis of Compound (A19) (B-33) (70.7 g), benzaldehyde (29.3 g), 3-mercaptopropionic acid (5 ml) and 1,2-dichloroethane (300 ml) were made into a homogeneous solution at an internal temperature of 70°C under a nitrogen atmosphere. Then, 10 ml of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70°C for 24 hours. After cooling to room temperature, 500 g of methyl isobutyl ketone was added. The organic layer was washed 5 times with 100 g of pure water, and then the organic layer was dried to dryness under reduced pressure. 200 g of THF was added to the residue to make a homogeneous solution, and then the polymer was reprecipitated with 1500 g of methanol. The precipitated polymer was separated by filtration and washed 2 times with 800 g of methanol and recovered. The recovered polymer was dried in vacuo at 70°C to obtain (A19). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (A19): Mw = 3700, Mw / Mn = 2.87

Chemical formula

[0170] Comparative Synthesis Example: Synthesis of Organic Compounds

[0171] [Comparative Synthesis Example 1] Synthesis of Compound (A20) In a 5 L four-necked flask, 26.4 g (1.09 mol) of magnesium was weighed. 168 g (0.54 mol) of 4,4'-dibromobiphenyl and 23.0 g (0.54 mol) of lithium chloride, which were previously dissolved in 1,000 ml of dehydrated THF (tetrahydrofuran), were added to such an extent that the magnesium was immersed. A small amount of dibromoethane was added to start the reaction, and then the remaining THF solution was added dropwise over 3 hours while maintaining the exothermic reaction. After the addition was complete, 500 ml of THF was added, and the mixture was aged under reflux for 8 hours to prepare a Grignard reagent. After cooling to an internal temperature of 55 °C, 150 g (0.83 mol) of 9-fluorenone, which was previously dissolved in 400 ml of dehydrated THF, was added dropwise over 2 hours. After the addition was complete, the mixture was aged under reflux for 5.5 hours, the flask was cooled in an ice bath, and the reaction was quenched with 1,000 ml of saturated aqueous ammonium chloride solution and 1,000 ml of pure water. At this time, a white precipitate formed in the solution, resulting in a suspension. 150 ml of MIBK (methyl isobutyl ketone) was added to the reaction solution, and the suspension was transferred to a separatory funnel as it was. The aqueous layer was extracted, and after further washing with 500 ml of pure water by liquid separation, the organic layer was concentrated under reduced pressure. Recrystallization was performed with diisopropyl ether, and the resulting white crystals were filtered off and dried to obtain 109 g of biphenyl derivative (B3) in a yield of 51.0%.

[0172]

Chemical formula

[0173] Biphenyl derivative (B3): IR (D-ATR): ν = 3539, 3064, 3039, 1605, 1495, 1447, 1164, 1030, 909, 820, 771, 754, 736 cm -1 。 1H-NMR (600 MHz in DMSO-d6): δ = 6.34 (2H, -OH, s), 7.24 (4H, t), 7.27 (8H, d), 7.36 (4H, t-t), 7.45 (4H, d), 7.81 (4H, d) ppm。 13C-NMR (150 MHz in DMSO-d6): δ = 82.44, 120.10, 124.66, 125.66, 126.28, 128.07, 128.51, 138.41, 139.14, 144.19, 151.23 ppm.

[0174] 40.3 g (78.4 mmol) of biphenyl derivative (B3), 23.73 g (164.6 mmol) of 2-naphthol, and 240 ml of 1,2-dichloroethane were weighed into a 1 L three-necked flask. While stirring in an oil bath at 30 °C, 7.3 ml of methanesulfonic acid was slowly added dropwise. After the addition was complete, the temperature of the oil bath was raised to 50 °C and the reaction was carried out for 6 hours. After allowing to cool to room temperature, it was diluted with 500 ml of MIBK, the insoluble matter was filtered off and transferred to a separatory funnel, and liquid-liquid washing with 300 ml of ultrapure water was repeated 9 times. The organic layer was concentrated under reduced pressure, 800 ml of THF was added to the residue and dissolved, and then crystallized with 2,500 ml of hexane. The crystals were filtered off and dried to obtain 51.6 g of biphenyl derivative compound (A20) in a yield of 85.8%.

[0175]

Chemical formula

[0176] Compound (A20): IR (KBr): ν = 3528, 3389, 3059, 3030, 1633, 1604, 1506, 1493, 1446, 1219, 1181, 750, 740 cm-1. 1H-NMR (600 MHz in DMSO-d6): δ = 6.98 (2H, d-d), 7.05 (2H, s-d), 7.17 (4H, d), 7.24 (2H, d-d), 7.29 (4H, t), 7.38 (4H, t), 7.40 (2H, s), 7.45 (4H, d), 7.50 (6H, d), 7.58 (2H, d), 7.93 (4H, d), 9.72 (2H, -OH, s) ppm. 13C-NMR (150 MHz in DMSO-d6): δ = 64.59, 108.35, 118.77, 120.58, 125.19, 126.11, 126.36, 126.62, 126.94, 127.16, 127.71, 127.88, 128.20, 129.35, 133.39, 138.14, 139.26, 139.59, 144.82, 150.56, 155.39 ppm.

[0177] [Comparative Synthesis Example 2] Synthesis of Compound (A21) 7.7 g of diol (A20), 3.0 g of potassium carbonate, and 40 g of N,N-dimethylformamide were mixed and heated to 55°C. 3.3 g of an 80% toluene solution of propargyl bromide was slowly added dropwise, and the mixture was heated and stirred at 55°C for 14 hours. After cooling to room temperature, 150 g of toluene was added, followed by washing with water and concentration under reduced pressure to obtain 8.4 g of the propargyl compound (A21). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (A21): Mw = 1000, Mw / Mn = 1.09

[0178] [Chemical formula]

[0179] [Comparative Synthesis Example 3] Synthesis of Compound (A22) 32.0 g of 2,7-dihydroxynaphthalene, 10.5 g of a 37% aqueous formalin solution, and 270 g of 2-methoxy-1-propanol were made into a homogeneous solution at an internal temperature of 80°C under a nitrogen atmosphere. Then, 18 g of a 20% p-toluenesulfonic acid 2-methoxy-1-propanol solution was slowly added, and the mixture was stirred at an internal temperature of 110°C for 8 hours. After cooling to room temperature, 600 g of methyl isobutyl ketone was added. The organic layer was washed 5 times with 200 g of pure water, and then the organic layer was dried to dryness under reduced pressure. 400 ml of THF was added to the residue, and the polymer was reprecipitated with 2,000 ml of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure. Subsequently, the obtained compound, 55.3 g of potassium carbonate, and 250 g of N,N-dimethylformamide were mixed and heated to 55°C. 59.5 g of an 80% toluene solution of propargyl bromide was slowly added dropwise, and the mixture was heated and stirred at 55°C for 22 hours. After cooling to room temperature, 150 g of toluene was added, followed by washing with water and concentration under reduced pressure to obtain the propargyl compound (A22). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (A22): Mw = 3500, Mw / Mn = 2.75

[0180]

Chemical formula

[0181] [Comparative Synthesis Example 4] Synthesis of Compound (A23) 90.1 g of 9,9-fluorenylidene-bisnaphthol, 10.5 g of a 37% aqueous formaldehyde solution, and 270 g of 2-methoxy-1-propanol were made into a homogeneous solution at an internal temperature of 80°C under a nitrogen atmosphere. Then, 18 g of a 20% p-toluenesulfonic acid 2-methoxy-1-propanol solution was slowly added, and the mixture was stirred at an internal temperature of 110°C for 8 hours. After cooling to room temperature, 600 g of methyl isobutyl ketone was added. The organic layer was washed 5 times with 200 g of pure water, and then the organic layer was dried under reduced pressure. 400 ml of THF was added to the residue, and the polymer was reprecipitated with 2,000 ml of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain compound (A23). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (A23): Mw = 3700, Mw / Mn = 2.82

[0182]

Chemical formula

[0183] Preparation of Organic Membrane Materials (UDL-1 to 19, Comparative UDL1 to 8) The above compounds (A3) to (A13), (A15) to (A16), (A18) to (A23), (B5), a crosslinking agent (CR1) as an additive, an acid generator (AG1), and as a high-boiling solvent (S1) 1,6-diacetoxyhexane: boiling point 260°C or (S2) tripropylene glycol monomethyl ether: boiling point 242°C were dissolved in propylene glycol monomethyl ether acetate (PGMEA) containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Limited) at the ratios shown in Table 1, and filtered through a 0.1-μm fluororesin filter to prepare organic film materials (UDL-1 to 19, Comparative UDL-1 to 8), respectively.

[0184]

Table 1

[0185] The following shows (CR1) as a crosslinking agent and an acid generator (AG1).

Chemical formula

[0186] Example 1: Solvent Resistance Measurement by Baking in Nitrogen Atmosphere (Examples 1-1 to 1-19, Comparative Examples 1-1 to 1-8) The organic film materials (UDL-1 to 19, Comparative UDL-1 to 8) prepared above were coated on a silicon substrate, baked at 450°C for 60 seconds under a nitrogen stream with the oxygen concentration controlled to 0.2% or less, then the film thickness was measured. PGMEA solvent was dispensed thereon, left for 30 seconds, spin-dried, baked at 100°C for 60 seconds to evaporate PGMEA, and the film thickness was measured again to determine the film thickness difference before and after PGMEA treatment.

[0187]

Table 2

[0188] As shown in Table 2, the organic film materials of the present invention (Examples 1-1 to 1-19) have a residual film ratio of 99% or more after PGMEA treatment, and it can be seen that a crosslinking reaction occurs even in a nitrogen atmosphere, exhibiting sufficient solvent resistance. On the other hand, in Comparative Examples 1-3 to 1-5 to which no crosslinking agent and thermal acid generator were added, the residual film ratio after PGMEA treatment was less than 50% for all, and sufficient solvent resistance was not exhibited. In order to exhibit sufficient solvent resistance, addition of a crosslinking agent and a thermal acid generator was necessary. From this result, it can be seen that a thermosetting reaction occurs due to the compound having a structure containing a triple bond of the present invention, and solvent resistance is exhibited to form a cured film.

[0189] Example 2: Solvent Resistance Measurement by Baking in Air (Examples 2-1 to 2-19, Comparative Examples 2-1 to 2-8) The above-prepared organic film-forming compositions (UDL-1 to 19, Comparative UDL-1 to 8) were applied onto a silicon substrate, baked at 350 °C for 60 seconds in air, then the film thickness was measured. PGMEA solvent was dispensed thereon, left standing for 30 seconds, spin-dried, baked at 100 °C for 60 seconds to evaporate PGMEA, the film thickness was measured, and the film thickness difference before and after PGMEA treatment was determined.

[0190]

Table 3

[0191] As shown in Table 3, the organic film-forming compositions of the present invention (Examples 2-1 to 2-19) have a residual film ratio of 99% or more after PGMEA treatment, and it can be seen that a crosslinking reaction occurs even in air, exhibiting sufficient solvent resistance. On the other hand, in Comparative Examples 2-4 and 2-5 to which no crosslinking agent and thermal acid generator were added, the residual film ratio after PGMEA treatment was less than 50%, and sufficient solvent resistance was not exhibited. In order to exhibit sufficient solvent resistance, addition of a crosslinking agent and a thermal acid generator was necessary. From this result, it can be seen that the compound having a structure containing a triple bond of the present invention causes a thermosetting reaction even in air, and solvent resistance is exhibited.

[0192] Example 3: Heat Resistance Property Evaluation (Examples 3-1 to 3-19, Comparative Examples 3-1 to 3-8) Each of the above-described organic film-forming compositions (UDL-1 to 19, Comparative UDL-1 to 8) was applied onto a silicon substrate, baked at 180°C in air to form a coating film with a thickness of 115 nm, and the film thickness was measured. Further, this substrate was baked at 450°C under a nitrogen stream in which the oxygen concentration was controlled to 0.2% or less, and the film thickness was measured (Examples 3-1 to 3-19, Comparative Examples 3-1 to 3-8). These results are shown in Table 4.

[0193]

Table 4

[0194] As shown in Table 4, for the organic film-forming compositions of the present invention (Examples 3-1 to 3-19), the film thickness reduction was less than 1% even after baking at 450°C, indicating that the organic films formed from the organic film-forming compositions of the present invention have high heat resistance. In contrast, in Comparative Examples 3-1 to 3-8, a large film thickness reduction occurred compared to the organic film materials of the present invention, and even in Comparative Examples 3-6 to 3-8 where a crosslinking agent was added and cured, a film thickness reduction of 10% or more occurred.

[0195] Example 4: Embedding Property Evaluation (Examples 4-1 to 4-19, Comparative Examples 4-1 to 4-8) As shown in Fig. 3, the above-described composition for forming an organic film (UDL-1 to 19, Comparative UDL-1 to 8) was respectively applied onto a SiO2 wafer substrate having a dense hole pattern (hole diameter 0.16 μm, hole depth 0.50 μm, distance between the centers of two adjacent holes 0.32 μm), and baked at 450 °C for 60 seconds under a nitrogen stream in which the oxygen concentration was controlled to 0.2% or less using a hot plate to form an organic film 8. The substrate used was a base substrate 7 (SiO2 wafer substrate) having a dense hole pattern as shown in Figs. 3(G) (plan view) and (H) (cross-sectional view). The cross-sectional shape of each obtained wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the organic film without voids (gaps) inside. The results are shown in Table 5. When using a composition for forming an organic film with poor embedding characteristics, voids are generated inside the holes in this evaluation. When using a composition for forming an organic film with good embedding characteristics, as shown in Fig. 3(I), the holes are filled with the organic film without voids in this evaluation.

[0196]

Table 5

[0197] As shown in Table 5, the composition for forming an organic film of the present invention (Examples 4-1 to 4-19) was confirmed to be capable of filling the hole pattern without generating voids and having good embedding characteristics. On the other hand, in Comparative Examples 4-1 to 4-8, it was confirmed that voids were generated and the embedding characteristics were poor. From this result, it can be seen that the composition for forming an organic film of the present invention has heat resistance ensured by the compound having a structure containing a triple bond of the present invention and the embedding characteristics are improved. On the other hand, in Comparative Examples 4-1 to 4-8, since the heat resistance was insufficient under a nitrogen atmosphere, voids were generated and good embedding characteristics could not be obtained.

[0198] Example 5: Planarization Property Evaluation (Examples 5-1 to 5-15, Comparative Examples 5-1 to 5-8) An organic film-forming composition (UDL-2 to 3, 5 to 13, 16 to 19, Comparative UDL-1 to 8) was respectively applied onto a lower base substrate 9 (SiO2 wafer substrate) having a giant isolated trench pattern (Fig. 4(J), trench width 10 μm, trench depth 0.10 μm) shown in Fig. 4, and baked at 450 °C for 60 seconds under a nitrogen stream in which the oxygen concentration was controlled to 0.2% or less. The step (delta10 in Fig. 4(K)) of the organic film 10 between the trench portion and the non-trench portion was observed using an NX10 atomic force microscope (AFM) manufactured by Park Systems. The results are shown in Table 6. In this evaluation, it can be said that the smaller the step, the better the planarization characteristics. Note that in this evaluation, a trench pattern with a depth of 0.10 μm was planarized using an organic film-forming composition with a normal film thickness of about 0.2 μm. Severe conditions were adopted to evaluate the superiority or inferiority of the planarization characteristics.

[0199]

Table 6

[0200] As shown in Table 6, the organic film-forming compositions of the present invention (Examples 5-1 to 5-15) were confirmed to have a smaller step between the organic films in the trench portion and the non-trench portion and to be excellent in planarization characteristics compared to Comparative Examples 5-1 to 5-8. Among the organic film-forming compositions of the comparative examples, those to which a cross-linking agent was added resulted in particularly poor flatness. The superiority of the structure containing a triple bond of the present invention was also shown in terms of planarization characteristics. Also, comparing Examples 5-12 to 5-13 to which a high-boiling solvent was added with Example 5-6 to which no high-boiling solvent was added, it can be seen that the addition of the high-boiling solvent further improved the flatness.

[0201] Example 6: Pattern Formation Test (Examples 6-1 to 6-15, Comparative Examples 6-1 to 6-8) The above-described composition for forming an organic film (UDL-2 to 3, 5 to 13, 16 to 19, Comparative UDL-1 to 8) was applied onto a silicon wafer substrate on which a 300-nm SiO2 film was formed, and baked at 450 °C for 60 seconds under a nitrogen stream in which the oxygen concentration was controlled to 0.2% or less to form an organic film (resist underlayer film). A CVD-SiON hard mask was formed thereon, and further, an organic antireflection film material (ARC-29A: manufactured by Nissan Chemical Industries, Ltd.) was applied and baked at 210 °C for 60 seconds to form an organic antireflection film with a film thickness of 80 nm. An ArF single-layer resist as a resist upper layer film material was applied thereon and baked at 105 °C for 60 seconds to form a photoresist film with a film thickness of 100 nm. A liquid immersion protective film material (TC-1) was applied onto the photoresist film and baked at 90 °C for 60 seconds to form a protective film with a film thickness of 50 nm.

[0202] As the resist upper layer film material (ArF single-layer resist), a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) were dissolved in a solvent containing 0.1 mass% of FC-4430 (manufactured by Sumitomo 3M Limited) at the ratios shown in Table 7, and filtered through a 0.1-μm fluororesin filter.

[0203]

Table 7

[0204] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) used are shown below.

Chemical formula

[0205] As the liquid immersion protective film material (TC-1), a protective film polymer (PP1) was dissolved in an organic solvent at the ratios shown in Table 8, and filtered through a 0.1-μm fluororesin filter.

[0206]

Table 8

[0207] The polymer (PP1) used is shown below.

Chemical formula

[0208] Subsequently, it was exposed using an ArF immersion exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA1.30, σ0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase shift mask), baked at 100 °C for 60 seconds (PEB), developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds, and a 55 nm 1:1 positive line and space pattern was obtained.

[0209] Subsequently, using the etching apparatus Telius manufactured by Tokyo Electron, the resist pattern was used as a mask to etch the organic antireflection film and the CVD-SiON hard mask by dry etching to form a hard mask pattern. The obtained hard mask pattern was used as a mask to etch the organic film to form an organic film pattern, and the obtained organic film pattern was used as a mask to etch the SiO2 film. The etching conditions are as shown below.

[0210] Transfer conditions of the resist pattern to the SiON hard mask. Chamber pressure 10.0 Pa RF power 1,500 W CF4 gas flow rate 75 sccm O2 gas flow rate 15 sccm Time 15 sec

[0211] Transfer conditions of the hard mask pattern to the organic film. Chamber pressure 2.0 Pa RF power 500 W Ar gas flow rate 75 sccm O2 gas flow rate 45 sccm Time 120 sec

[0212] Transfer conditions of the organic film pattern to the SiO2 film. Chamber pressure: 2.0 Pa RF power: 2,200 W C5F 12 Gas flow rate: 20 sccm C2F6 gas flow rate: 10 sccm Ar gas flow rate: 300 sccm O2 gas flow rate: 60 sccm Time: 90 sec

[0213] The results of observing the pattern cross-section with an electron microscope (S-4700) manufactured by Hitachi, Ltd. are shown in Table 9.

[0214] [Table 9]

[0215] As shown in Table 9, from the results of the composition for forming an organic film of the present invention (Examples 6-1 to 6-15), in all cases, the resist upper layer film pattern was finally successfully transferred to the substrate, and it was confirmed that the composition for forming an organic film of the present invention is suitably used for microfabrication by the multilayer resist method. On the other hand, in Comparative Examples 6-3 to 6-5, the heat resistance was insufficient under a nitrogen atmosphere and, as shown in Comparative Examples 1-3 to 1-5, they were not sufficiently cured, so pattern collapse occurred during pattern processing and good patterns could not be obtained. In Comparative Examples 6-1 to 6-2 and 6-6 to 6-8, patterns could be formed although the heat resistance was insufficient.

[0216] Example 7: Pattern Formation Test (Examples 7-1 to 7-15, Comparative Examples 7-1 to 7-8) On a SiO2 wafer substrate having a trench pattern (trench width: 10 μm, trench depth: 0.10 μm), the above-described composition for forming an organic film (UDL-2 to 3, 5 to 13, 16 to 19, Comparative UDL-1 to 8) was respectively applied, and a laminated film was formed in the same manner as in Example 6 except that it was baked at 450 °C for 60 seconds under a nitrogen stream in which the oxygen concentration was controlled to 0.2% or less, and patterning and dry etching were performed, and the shape of the resulting pattern was observed. [Table 10]

[0217] As shown in Table 10, from the results of the composition for forming an organic film (Examples 7-1 to 7-15) of the present invention, in any case, the resist upper layer film pattern was finally well transferred to the substrate, and it was confirmed that the composition for forming an organic film of the present invention was suitably used for microfabrication by the multilayer resist method. On the other hand, in Comparative Examples 7-3 to 7-5, the heat resistance was insufficient under a nitrogen atmosphere, and as shown in Comparative Examples 1-3 to 1-5, it was not sufficiently cured. Also, due to poor pattern filling, pattern collapse occurred during pattern processing and a good pattern could not be obtained. In Comparative Examples 7-1 to 7-2 and 7-6 to 7-8, solvent resistance was obtained and a cured film was formed, but due to poor pattern filling, pattern collapse occurred during pattern processing and a good pattern could not be finally obtained.

[0218] From the above, the composition for forming an organic film of the present invention containing the compound of the present invention has good dry etching resistance, and also has heat resistance of 450 ° C or higher and high embedding / planarization characteristics even under an oxygen-free inert gas. Therefore, it is extremely useful as a composition for forming an organic film used in the multilayer resist method. Also, it has become clear that in the pattern forming method using this, even if the substrate to be processed is a substrate having a pattern, a fine pattern can be formed with high precision.

[0219] Note that the present invention is not limited to the above embodiment. The above embodiment is an example, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Explanation of Signs

[0220] 1... Substrate, 2... Processed layer, 2a... Pattern formed on the processed layer 3... Organic film, 3’... Composition for forming an organic film, 3a... Organic film pattern 4…Silicon-containing resist intermediate film, 4a…Pattern of silicon-containing resist intermediate film, 5…Upper resist film, 5a…Pattern of upper resist film, 6…Exposed portion, 7…Lower substrate having a dense hole pattern, 8…Organic film, 9…Lower substrate having a large isolated trench pattern, 10…Organic film, delta10…Difference in film thickness of the organic film between the trench portion and the non-trench portion.

Claims

1. A compound characterized by being any of the compounds represented by the following formulas (T1) and (T2). 【Chemical 1】 (In the above formula (T1), p represents the number of repeating units and is 1 to 50.) [Chemical 2] (In the above formula (T2), the weight average molecular weight of the compound represented by (A3) is 1100, the weight average molecular weight of the compound represented by (A15) is 2400, and the parentheses in the formula indicate that it is a repeating unit.)

2. A composition for forming an organic film, comprising (A) any of the compounds represented by the following formulas (T3) and (T4), and (B) an organic solvent, and being a composition for forming an organic film characterized thereby. [Chemical Formula 3] 【Chemical Formula 4】 (The weight average molecular weight of the compound in the above formula (T4) is 1100, and the parentheses in the formula indicate that it is a repeating unit.)

3. The composition for forming an organic film according to claim 2, wherein the component (A) has a weight average molecular weight of 500 to 20,000.

4. The composition for forming an organic film according to claim 2 or claim 3, characterized in that the composition for forming an organic film further contains one or more of (C) an acid generator, (D) a surfactant, (E) a crosslinking agent, and (F) a plasticizer.

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