Laminate, method for producing laminate, and pattern forming method

Abstract

To provide a laminate including a resist film obtained from a non-chemically amplified resist composition which is applicable to photolithography using high energy rays, particularly electron beam (EB) lithography and EUV lithography, and is excellent in sensitivity and limiting resolution, and an adhesive film under the resist film, and to provide a method for forming a pattern on an upper layer of the laminate.SOLUTION: A laminate includes a substrate, an adhesive film obtained from an adhesive film-forming composition containing a polymer containing a repeating unit represented by formula (1) or (2) and an organic solvent, and a resist film obtained from a resist composition containing a specific hypervalent iodine compound, a carboxy group-containing compound and a solvent, in this order.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate, a method for manufacturing a laminate, and a method for forming a pattern. [Background technology]

[0002] As the IoT market expands, there is a growing demand for higher integration, higher speeds, and lower power consumption in LSIs, leading to rapid progress in miniaturization of pattern rules. Logic devices, in particular, are driving this miniaturization. The most advanced miniaturization technology is ArF immersion lithography, with double patterning, triple patterning, and quadruple patterning being used to mass-produce 10nm-node devices. Furthermore, studies are underway to develop 7nm-node devices using next-generation extreme ultraviolet (EUV) lithography with a wavelength of 13.5nm.

[0003] As miniaturization progresses, image blurring due to acid diffusion has become a problem (Non-Patent Document 1). It has been suggested that in order to ensure resolution in fine patterns with processing dimensions of 45 nm and below, not only is it important to improve dissolution contrast, as has been proposed in the past, but also to control acid diffusion (Non-Patent Document 2). However, because chemically amplified resist compositions increase sensitivity and contrast through acid diffusion, attempts to minimize acid diffusion by lowering the post-exposure bake (PEB) temperature or shortening the PEB time result in significant decreases in sensitivity and contrast.

[0004] Adding an acid generator that generates bulky acid is effective in suppressing acid diffusion. Therefore, copolymerization of an onium salt acid generator with a polymerizable olefin into a polymer has been proposed. However, for resist film pattern formation with feature sizes of 16 nm or less, it is believed that chemically amplified resist compositions cannot be used to form patterns due to acid diffusion, and the development of non-chemically amplified resist compositions is desired.

[0005] One material for non-chemically amplified resist compositions is polymethyl methacrylate (PMMA), a positive resist material whose main chain is cleaved by EUV irradiation, resulting in a decrease in molecular weight, which improves its solubility in organic solvent developers.

[0006] Hydrogen silsesquioxane (HSQ) is a negative resist material that becomes insoluble in alkaline developers due to crosslinking caused by the condensation reaction of silanols generated by EUV irradiation. Chlorine-substituted calixarenes also function as negative resist materials. These negative resist materials have small molecular size before crosslinking and are free of blurring due to acid diffusion, resulting in low edge roughness and extremely high resolution, and are used as pattern transfer materials to indicate the resolution limit of exposure equipment. However, these materials have insufficient sensitivity, and further improvement is needed.

[0007] One of the challenges in developing materials for EUV lithography is the low photon count in EUV exposure. EUV energy is much higher than that of ArF excimer laser light, and the photon count in EUV exposure is one-fourteenth that of ArF exposure. Furthermore, the pattern dimensions formed with EUV exposure are less than half those of ArF exposure. This makes EUV exposure susceptible to variations in photon count. The variations in photon count in the extremely short wavelength radiation region are a physical phenomenon known as shot noise, and this effect cannot be eliminated. Therefore, so-called stochastics has attracted attention. While the effects of shot noise cannot be eliminated, methods for reducing this effect are being discussed. Shot noise not only increases dimensional uniformity (CDU) and line width roughness (LWR), but also causes hole blockage with a probability of one in several million. Blocked holes cause poor electrical conduction, preventing transistor operation and adversely affecting overall device performance. When considering practical sensitivity, resist compositions containing PMMA or HSQ as the main component are significantly affected by stochastics and are unable to achieve the desired resolution performance.

[0008] As a method for reducing the impact of shot noise on the resist side, the introduction of elements that have high absorption of EUV light has attracted attention. Patent Document 1 proposes a chemically amplified resist composition containing iodine atoms that have high absorption of EUV light. However, as mentioned above, chemically amplified resist compositions cannot achieve excellent resolution performance in EUV lithography, where processing dimensions will become increasingly finer in the future. In particular, in line and space patterns, as pattern dimensions become smaller, pattern collapse and line breakage increase significantly, and reducing these occurrences leads to an improvement in limiting resolution.

[0009] Patent Document 2 proposes a negative resist composition using a tin compound. Because this composition contains tin, which has high absorption of EUV light, as its main component, it has improved stochastics and can achieve high sensitivity and high resolution. However, so-called metal resists of this type have many issues, such as insufficient solubility in resist solvents, storage stability, and defects due to post-etching residues. Furthermore, since metal resists are negative resists in which the exposed areas become insoluble in developer solutions by primarily becoming metal oxides, applying them to contact hole patterning requires an additional reversal process, which raises cost concerns. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2018-5224 [Patent Document 2] Special Publication No. 2021-503482

[0011] [Non-Patent Document 1] SPIE Vol. 5039 p1 (2003) [Non-patent document 2] SPIE Vol. 6520 p65203L-1 (2007) Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made in view of the above circumstances, and aims to provide a laminate comprising a resist film obtained from a non-chemically amplified resist composition that is applicable to photolithography using high-energy rays, particularly electron beam (EB) lithography and EUV lithography, and that has excellent sensitivity and limiting resolution, and an adhesion film thereunder, and a method for forming a pattern on the upper layer of the laminate. [Means for solving the problem]

[0013] As a result of extensive research into achieving the above-mentioned object, the present inventors have discovered that by laying a desired adhesion film underneath a resist film obtained from a resist composition containing a predetermined hypervalent iodine compound and a carboxy group-containing compound as main components, a resist film exhibiting excellent resolution can be obtained, which is extremely effective for precise microfabrication, and have thus completed the present invention.

[0014] That is, the present invention provides the following laminate and pattern forming method. 1. A substrate; an adhesion film obtained from an adhesion film-forming composition containing a polymer containing a repeating unit represented by formula (1) or (2) and an organic solvent; a resist film obtained from a resist composition containing at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by the following formula (3), a hypervalent iodine compound represented by the following formula (4), and a hypervalent iodine compound represented by the following formula (5), a carboxy group-containing compound, and a solvent; A laminate comprising the above in this order. [ka] (In the formula, a is 0, 1, or 2. b is an integer that satisfies 0≦b≦4a+2. c is an integer that satisfies 1≦c≦4a+2, provided that 1≦b+c≦4a+2. d is 0, 1, 2, 3, 4, or 5. e is 0, 1, 2, 3, 4, or 5, provided that 1≦d+e≦5. R 1is a hydroxy group or a 2-propynyloxy group. R 2 is a carboxy group or a carboxymethoxy group. R 3 is a hydroxy group or a 2-propynyloxy group. R 4 is a carboxy group or a carboxymethoxy group. [ka] (In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5. , 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, provided that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, provided that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R 11 ~R 18 are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. 11 and R 12 , R 13 and R 14 , R 15 and R 16 , or R 17 and R 18 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. R 21 ~R 24 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 21 may be the same or different, and multiple R 21may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 22 may be the same or different, and multiple R 22 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 23 may be the same or different, and multiple R 23 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 24 may be the same or different, and multiple R 24 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. R 25 is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R 25 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and some of the -CH2- of the (n8)-valent hydrocarbon group may be substituted with a group containing a hetero atom, and R 24 and R 25 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. 2. The laminate of 1, which comprises a resist underlayer film and a silicon-containing intermediate film in this order from the substrate side between the substrate and the adhesive film. 3. The laminate of 1 or 2, wherein the weight average molecular weight of the polymer containing the repeating unit represented by formula (1) or (2) is 500 to 20,000. 4. The laminate of any one of 1 to 3, wherein the composition for an adhesion film further contains at least one selected from a surfactant, a crosslinking agent, and a thermal acid generator. 5. The laminate of any one of 1 to 4, wherein the adhesive film has a thickness of 2 to 50 nm. 6. The laminate of any one of 1 to 5, wherein the carboxy group-containing compound is a polymer containing a repeating unit represented by the following formula (6) or a compound represented by the following formula (7). [ka] (In the formula, R A is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 -X A1 is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring. * represents a bond to a carbon atom in the main chain. p is 1, 2, 3 or 4. R 31 is a p-valent hydrocarbon group having 1 to 40 carbon atoms or a p-valent heterocyclic group having 2 to 40 carbon atoms, and when p is 2, R 31 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Some or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- groups of the p-valent hydrocarbon group may be substituted with a group containing a heteroatom. R 32 is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a hetero atom, or some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a hetero atom. When p is 2, 3, or 4, each R 32 may be the same as or different from each other.) 7. A step of applying an adhesion film-forming composition containing a polymer containing a repeating unit represented by formula (1) or (2) and an organic solvent onto a substrate, followed by heat treatment to form an adhesion film; and a step of applying a resist composition containing at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by formula (3), a hypervalent iodine compound represented by formula (4), and a hypervalent iodine compound represented by formula (5), a carboxy group-containing compound, and a solvent onto the adhesion film, and then performing a heat treatment to form a resist film. A method for producing a laminate comprising the steps of: 8. A step of applying a resist underlayer film forming material onto a substrate and performing a heat treatment to form a resist underlayer film; forming a silicon-containing intermediate film on the resist underlayer film; a step of applying an adhesion film-forming composition containing a polymer containing a repeating unit represented by formula (1) or (2) and an organic solvent onto the silicon-containing interlayer film, and then heat-treating the composition to form an adhesion film; and a step of applying a resist composition containing at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by formula (3), a hypervalent iodine compound represented by formula (4), and a hypervalent iodine compound represented by formula (5), a carboxy group-containing compound, and a solvent onto the adhesion film, and then performing a heat treatment to form a resist film. A method for producing a laminate comprising the steps of: 9. The method for producing a laminate according to claim 8, wherein the silicon-containing intermediate film is formed by applying a silicon-containing resist intermediate film material onto the resist underlayer film and then heat treating the applied material. 10. The method for producing a laminate according to 8, wherein the silicon-containing intermediate film is an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film, formed by a CVD method or an ALD method. 11. The method for producing a laminate according to any one of 7 to 10, wherein the carboxy group-containing compound is a polymer containing a repeating unit represented by formula (6) or a compound represented by formula (7). 12. A pattern forming method comprising the steps of exposing a resist film of any one of the laminates 1 to 6 to i-line, KrF excimer laser light, ArF excimer laser light, electron beam or extreme ultraviolet light, and developing the exposed resist film using a developer. 13. The pattern formation method of 12, wherein the developer is an organic solvent. [Effects of the Invention]

[0015] The laminate of the present invention is extremely useful for forming fine patterns, achieving both high sensitivity and high resolution, particularly in i-line, KrF excimer laser light, ArF excimer laser light, EB lithography, and EUV lithography. DETAILED DESCRIPTION OF THE INVENTION

[0016] The laminate of the present invention is extremely useful as a laminate for multilayer resist processes such as a two-layer resist process or a four-layer resist process using a resist underlayer film and a silicon-containing intermediate film.

[0017] [Laminate] The laminate of the present invention comprises a substrate, an adhesive film, and a resist film in this order.

[0018] [substrate] The substrate is preferably a substrate for manufacturing an integrated circuit (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, etc.) or a substrate for manufacturing a mask circuit (Cr, CrO, CrON, MoSi2, SiO2, etc.).

[0019] [Adhesive film] The adhesion film is obtained from an adhesion film-forming composition containing a polymer containing a repeating unit represented by formula (1) or (2) and an organic solvent. [ka]

[0020] In formulas (1) and (2), a is 0, 1, or 2. b is an integer that satisfies 0≦b≦4a+2. c is an integer that satisfies 1≦c≦4a+2, provided that 1≦b+c≦4a+2. d is 0, 1, 2, 3, 4, or 5. e is 0, 1, 2, 3, 4, or 5, provided that 1≦d+e≦5.

[0021] In formulas (1) and (2), R1 is a hydroxy group or a 2-propynyloxy group. 2 is a carboxy group or a carboxymethoxy group. 3 is a hydroxy group or a 2-propynyloxy group. 4 is a carboxy group or a carboxymethoxy group.

[0022] Specific examples of the repeating unit represented by formula (1) include, but are not limited to, those shown below. [ka]

[0023] [ka]

[0024] Specific examples of the repeating unit represented by formula (2) include, but are not limited to, those shown below. [ka]

[0025] [ka]

[0026] [ka]

[0027] [ka]

[0028] Among polymers containing repeating units represented by formula (1) or (2), R 1is a hydroxy group (hereinafter also referred to as polymer A) can be obtained by a polycondensation reaction between a compound represented by the following formula (a) and a compound represented by the following formula (b) or (c): [ka] (Wherein, a to e and R 1 ~R 4 is the same as above.)

[0029] The polycondensation reaction can usually be carried out in the absence or presence of a solvent using an acid or a base as a catalyst at room temperature, or under cooling or heating as required. Examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; chlorine-based solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; lactones such as γ-butyrolactone; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide. The solvent is preferably used in an amount of 0 to 2000 parts by mass relative to 100 parts by mass of the total of the raw material compounds. The solvent may be used alone or in combination of two or more kinds.

[0030] Examples of the acid catalyst that can be used include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropolyacids; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide, and titanium(IV) oxide. Examples of the base catalyst that can be used include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, and calcium hydride; alkyl metals such as methyllithium, n-butyllithium, methylmagnesium chloride, and ethylmagnesium bromide; alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide; and organic bases such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, and 4-dimethylaminopyridine. The amount of the catalyst used is preferably 0.001 to 100 parts by mass, and more preferably 0.005 to 50 parts by mass, per 100 parts by mass of the raw material compound.

[0031] The reaction temperature of the polycondensation reaction is preferably from −50° C. to the boiling point of the solvent, and more preferably from room temperature to about 100° C. The reaction time of the polycondensation reaction is preferably from about 4 to 24 hours, and more preferably from about 4 to 10 hours.

[0032] Examples of methods for the polycondensation reaction include a method in which the raw material compounds and the catalyst are charged all at once, a method in which the raw material compounds are added dropwise to the catalyst, and a method in which the raw material compounds are mixed and then the catalyst is added dropwise thereto.

[0033] After the polycondensation reaction is complete, it is preferable to remove unreacted raw materials, catalysts, and the like remaining in the system. Examples of the removal method include raising the temperature of the reaction vessel to 130 to 230°C and removing volatiles at about 1 to 50 mmHg, fractionating the polymer by adding an appropriate solvent or water, and dissolving the polymer in a good solvent and then reprecipitating it in a poor solvent. These methods can be used depending on the properties of the resulting reaction product.

[0034] Among polymers containing repeating units represented by formula (1) or (2), R 1 The one in which is a 2-propynyloxy group can be produced, for example, by reacting polymer A with propargyl halide.

[0035] Specific examples of the propargyl halide include propargyl chloride, propargyl bromide, and propargyl iodide.

[0036] As a method for reacting polymer A with propargyl halide, for example, the method described in Japanese Patent Publication No. 01-503541 can be referred to.

[0037] The polystyrene-equivalent molecular weight of the polymer thus obtained is preferably a weight average molecular weight (Mw) of 500 to 500,000, more preferably 1,000 to 100,000. The polydispersity (Mw / Mn) is preferably 1.2 to 2.0. By eliminating monomer components, oligomer components, and low molecular weight components with Mw of 1,000 or less, volatile components during baking can be suppressed, preventing contamination around the bake cup and surface defects caused by deposited volatile components falling onto the wafer.

[0038] The organic solvent is not particularly limited as long as it dissolves the polymer and each optional component described later. Specific examples of the organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether. Examples of the alkyl ester include ethers such as pyrene glycol dimethyl ether and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono tert-butyl ether acetate; and lactones such as γ-butyrolactone.

[0039] In the adhesion film-forming composition, the content of the organic solvent is preferably 3,000 to 30,000 parts by mass, and more preferably 4,000 to 20,000 parts by mass, relative to 100 parts by mass of the polymer containing a repeating unit represented by formula (1) or (2). The organic solvent may be used alone or in combination of two or more.

[0040] The adhesion film-forming composition may contain an acid generator or a crosslinking agent to further accelerate the crosslinking reaction.

[0041] The acid generator may be one that generates an acid upon thermal decomposition (thermal acid generator) or one that generates an acid upon irradiation with light, and either may be used. Specific examples of the acid generator include onium salts, diazomethane derivatives, glyoxime derivatives, bissulfone derivatives, sulfonate esters of N-hydroxyimide compounds, β-ketosulfonic acid derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate salts, and sulfonate ester derivatives. More specific examples include those described in paragraphs

[0081] to

[0111] of JP 2008-65303 A. When the adhesion film-forming composition contains the acid generator, the content thereof is preferably 0.01 to 100 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the polymer containing a repeating unit represented by formula (1) or (2). The acid generators may be used alone or in combination of two or more.

[0042] Specific examples of the crosslinking agent include melamine compounds, guanamine compounds, glycoluril compounds, or urea compounds substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, as well as compounds containing double bonds such as epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, and alkenyl ether groups. More specific examples include those described in paragraphs

[0074] to

[0080] of JP 2008-65303 A. When the adhesion film-forming composition contains the crosslinking agent, the content thereof is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 30 parts by mass, per 100 parts by mass of the polymer containing a repeating unit represented by formula (1) or (2). The crosslinking agents may be used alone or in combination of two or more.

[0043] The adhesion film-forming composition may contain a surfactant to improve application properties in spin coating. Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, nonionic surfactants of polyoxyethylene sorbitan fatty acid esters, fluorine-containing surfactants, and surfactants based on partially fluorinated oxetane ring-opening polymers. More specific examples include those described in paragraphs

[0142] to

[0147] of JP 2009-269953 A. When the adhesion film-forming composition contains the surfactant, the content thereof is preferably 0.001 to 1 part by mass, more preferably 0.001 to 0.5 parts by mass, per 100 parts by mass of the polymer containing a repeating unit represented by formula (1) or (2). The surfactants may be used alone or in combination of two or more types.

[0044] The adhesion film-forming composition may contain a basic compound to improve storage stability. The basic compound acts as an acid quencher to prevent a small amount of acid generated by the acid generator from promoting a crosslinking reaction. Specific examples of the basic compound include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, and imide derivatives. Specific examples include those described in paragraphs

[0112] to

[0119] of JP 2008-65303 A. When the adhesion film-forming composition contains the basic compound, the content thereof is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the polymer containing a repeating unit represented by formula (1) or (2). The basic compounds may be used alone or in combination of two or more.

[0045] The thickness of the adhesive film is preferably 2 nm or more and less than 100 nm, and more preferably 2 nm or more and 50 nm or less.

[0046] In the fine patterning process using the multilayer resist method in the semiconductor device manufacturing process, the adhesion film has the effect of preventing the collapse of fine patterns in the formation of line and space patterns, and has the effect of enabling the formation of patterns with excellent CDU in the formation of contact hole patterns.

[0047] The high adhesion between the adhesion film and the resist film is due to the presence of carboxy groups in the adhesion film. By using the resist composition described below, the carboxy groups on the surface of the adhesion film and the carboxy groups of the carboxy group-containing compound contained in the resist composition are crosslinked by the hypervalent iodine compound upon baking after application of the resist composition. Because the resist composition described below is a positive resist composition, crosslinking occurs between the pattern in the unexposed areas and the surface of the adhesion film, making the resist composition resistant to stresses during development and preventing collapse of the line-and-space pattern, making it useful for producing resist patterns with high aspect ratios. Meanwhile, in contact hole patterns, the high adhesion between the resist film and the adhesion film prevents the developer from penetrating between the resist film and the resist underlayer film and causing swelling, thereby forming contact hole patterns with excellent CDU.

[0048] [Resist underlayer film and silicon-containing intermediate film] The laminate of the present invention may include a resist underlayer film and a silicon-containing intermediate film between the substrate and the adhesive film, in this order from the substrate side.

[0049] The resist underlayer film may be a known film used in a fine patterning process using a multilayer resist method. Specific examples of the resist underlayer film include spin-on carbon ODL-301 (carbon content: 88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd.

[0050] The resist underlayer film preferably has a thickness of 40 to 500 nm, more preferably 100 to 300 nm.

[0051] The silicon-containing intermediate film is preferably a silicon-containing resist intermediate film obtained using a solution-type composition for forming a silicon-containing resist intermediate film, or an inorganic hard mask intermediate film formed by a CVD method or an ALD method.

[0052] A polysilsesquioxane-based interlayer film is preferably used as the silicon-containing resist interlayer in the four-layer resist process. By imparting an anti-reflective effect to the silicon-containing resist interlayer, reflection can be suppressed. In particular, for exposure at a wavelength of 193 nm, using a material containing many aromatic groups and having high substrate etching resistance as the resist underlayer increases the k value and increases substrate reflection. However, by suppressing reflection with a silicon-containing resist interlayer, substrate reflection can be reduced to 0.5% or less. As a silicon-containing resist interlayer with anti-reflective effect, anthracene is preferably used for exposure at a wavelength of 248 nm or 157 nm, and polysilsesquioxane, which has pendant light-absorbing groups having phenyl groups or silicon-silicon bonds and is crosslinked by acid or heat, is preferably used for exposure at a wavelength of 193 nm.

[0053] The silicon-containing resist intermediate film preferably has a film thickness of 10 to 70 nm, more preferably 20 to 50 nm.

[0054] The inorganic hard mask intermediate film is preferably selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film, of which a SiON film is most preferred because of its high anti-reflection effect.

[0055] The inorganic hard mask intermediate film preferably has a thickness of 5 to 200 nm, more preferably 10 to 100 nm.

[0056] [Resist film] The resist film is obtained from a resist composition containing a predetermined hypervalent iodine compound, a carboxy group-containing compound, and a solvent.

[0057] The hypervalent iodine compound is a three-coordinate hypervalent iodine compound represented by the following formula (3), (4) or (5). [ka]

[0058] In formulas (3) to (5), m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, with the proviso that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, with the proviso that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4.

[0059] In formulas (3) to (5), R 11 ~R 18 are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. 11 and R 12 , R 13 and R 14 , R 15 and R 16 , or R 17 and R 18 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.

[0060] R 11 ~R 18 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.11 ~R 18 The hydrocarbyl group having 1 to 10 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, and tricyclo[5.2.1.0]. 2,6 ] cyclic saturated hydrocarbyl groups having 3 to 10 carbon atoms such as decanyl and adamantyl; alkenyl groups such as vinyl and allyl; aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl; and groups obtained by combining these. In addition, some or all of the hydrogen atoms in the hydrocarbyl groups may be substituted with groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and some of the -CH2- in the hydrocarbyl groups may be substituted with groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms, resulting in the hydrocarbyl groups containing hydroxy groups, cyano groups, halogen atoms, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate ester bonds, carbonate bonds, carbamate bonds, lactone rings, sultone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), etc. 11 ~R 18 is preferably a hydrocarbyl group having 1 to 4 carbon atoms.

[0061] In formulas (3) to (5), R 21 ~R 24 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a halogen atom or a heteroatom. When n2 is 2 or more, each R 21 may be the same or different, and multiple R 21may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n4 is 2 or more, each R 22 may be the same or different, and multiple R 22 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n6 is 2 or more, each R 23 may be the same or different, and multiple R 23 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. When n7 is 2 or more, each R 24 may be the same or different, and multiple R 24 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached.

[0062] R 21 ~R 24 Specific examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 21 ~R 24 The hydrocarbyl group having 1 to 40 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 40 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, and tricyclo[5.2.1.0]. 2,6cyclic saturated hydrocarbyl groups having 3 to 40 carbon atoms, such as a ]decanyl group, an adamantyl group, or an adamantylmethyl group; and aryl groups having 6 to 40 carbon atoms, such as a phenyl group, a naphthyl group, or an anthracenyl group. Some or all of the hydrogen atoms in the hydrocarbyl groups may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, or halogen atoms, and some of the -CH2- groups in the hydrocarbyl groups may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, or nitrogen atoms, so that the hydrocarbyl groups may contain hydroxy groups, cyano groups, halogen atoms, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate ester bonds, carbonate bonds, carbamate bonds, lactone rings, sultone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), or the like.

[0063] In formula (5), R 25 is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R 25 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and some of the -CH2- of the (n8)-valent hydrocarbon group may be substituted with a group containing a hetero atom, and R 24 and R 25 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.

[0064] R 25 The (n8)-valent hydrocarbon group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. The (n8)-valent hydrocarbon group is a group obtained by eliminating (n8) hydrogen atoms from a hydrocarbon. Examples of the hydrocarbon include alkanes having 1 to 40 carbon atoms, alkenes having 2 to 40 carbon atoms, alkynes having 2 to 40 carbon atoms, saturated cyclic hydrocarbons having 3 to 40 carbon atoms, unsaturated cyclic hydrocarbons having 3 to 40 carbon atoms, and aromatic hydrocarbons having 6 to 40 carbon atoms.

[0065] Specific examples of the alkanes having 1 to 40 carbon atoms include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and structural isomers thereof.

[0066] Specific examples of the alkenes having 1 to 40 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and structural isomers thereof.

[0067] Specific examples of the alkyne having 1 to 40 carbon atoms include acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, and structural isomers thereof.

[0068] Specific examples of the cyclic saturated hydrocarbon having 3 to 40 carbon atoms include cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, and norbornane.

[0069] Specific examples of the cyclic unsaturated hydrocarbon having 3 to 40 carbon atoms include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norbornene.

[0070] Specific examples of the aromatic hydrocarbon having 6 to 40 carbon atoms include benzene, naphthalene, and biphenyl.

[0071] R 25 The (n8)-valent heterocyclic group represented by the following formula is a group obtained by eliminating (n8) hydrogen atoms from a heterocyclic compound. Specific examples of the heterocyclic compound include furan, pyridine, pyrazole, and thiazolidine.

[0072] The (n8)-valent hydrocarbon group or (n8)-valent heterocyclic group may have some or all of its hydrogen atoms substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and as a result, may contain a hydroxy group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Furthermore, the (n8)-valent hydrocarbon group may have some of its -CH2- groups substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, may contain a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), etc.

[0073] Specific examples of the hypervalent iodine compound represented by formula (3) include, but are not limited to, the following: [ka]

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] Specific examples of the hypervalent iodine compound represented by formula (4) include, but are not limited to, the following: [ka]

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] Specific examples of the hypervalent iodine compound represented by formula (5) include, but are not limited to, the following: [ka]

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] The carboxy group-containing compound is preferably a polymer containing a repeating unit represented by the following formula (6) or a compound represented by the following formula (7). [ka]

[0096] In formula (6), R A is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. A is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX A1 -X A1is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring. * represents a bond to a carbon atom in the main chain.

[0097] In formula (7), p is 1, 2, 3 or 4.

[0098] In formula (7), R 31 is a p-valent hydrocarbon group having 1 to 40 carbon atoms or a p-valent heterocyclic group having 2 to 40 carbon atoms, and when p is 2, R 31 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. Some or all of the hydrogen atoms of the p-valent hydrocarbon group or p-valent heterocyclic group may be substituted with a group containing a heteroatom, and some of the -CH2- groups of the p-valent hydrocarbon group may be substituted with a group containing a heteroatom.

[0099] In formula (7), R 32 is a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a hetero atom, or some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a hetero atom. When p is 2, 3, or 4, each R 32 may be the same as or different from each other.

[0100] R 31 The p-valent hydrocarbon group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. The p-valent hydrocarbon group is a group obtained by eliminating p hydrogen atoms from a hydrocarbon. Examples of the hydrocarbon include alkanes having 1 to 40 carbon atoms, alkenes having 2 to 40 carbon atoms, alkynes having 2 to 40 carbon atoms, saturated cyclic hydrocarbons having 3 to 40 carbon atoms, unsaturated cyclic hydrocarbons having 3 to 40 carbon atoms, and aromatic hydrocarbons having 6 to 40 carbon atoms.

[0101] Examples of the alkanes having 1 to 40 carbon atoms include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, and structural isomers thereof.

[0102] Examples of the alkenes having 1 to 40 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and structural isomers thereof.

[0103] Examples of the alkyne having 1 to 40 carbon atoms include acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, and structural isomers thereof.

[0104] Examples of the cyclic saturated hydrocarbon having 3 to 40 carbon atoms include cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, adamantane, and norbornane.

[0105] Examples of the cyclic unsaturated hydrocarbon having 3 to 40 carbon atoms include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and norbornene.

[0106] Examples of the aromatic hydrocarbon having 6 to 40 carbon atoms include benzene, naphthalene, and biphenyl.

[0107] R 31 The p-valent heterocyclic group represented by the following formula is a group obtained by eliminating p hydrogen atoms from a heterocyclic compound. Examples of the heterocyclic compound include furan, pyridine, pyrazole, and thiazolidine.

[0108] The p-valent hydrocarbon group or p-valent heterocyclic group may have some or all of its hydrogen atoms substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and as a result, may contain a hydroxy group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Furthermore, the p-valent hydrocarbon group may have some of its -CH- groups substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, may contain a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), etc.

[0109] R 32The hydrocarbylene group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include a methanediyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,1 alkanediyl groups having 1 to 20 carbon atoms, such as a 2-diyl group; cyclic saturated hydrocarbylene groups having 3 to 20 carbon atoms, such as a cyclopentanediyl group, a cyclohexanediyl group, a norbornanediyl group, and an adamantanediyl group; unsaturated aliphatic hydrocarbylene groups having 2 to 20 carbon atoms, such as a vinylene group and a propene-1,3-diyl group; arylene groups having 6 to 20 carbon atoms, such as a phenylene group and a naphthylene group; and groups obtained by combining these. In addition, some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, or some of the -CH- constituting the hydrocarbylene group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbylene group may contain a hydroxy group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride or the like.

[0110] Among the carboxylic acid compounds represented by formula (7), those in which p is 2, 3, or 4 are preferred. In this case, when mixed with a hypervalent iodine compound, a strong resist film with a high molecular weight is easily formed, which is preferred from the viewpoints of etching resistance and developer resistance.

[0111] Specific examples of the carboxyl group-containing repeating unit represented by formula (6) include, but are not limited to, those shown below. A is the same as above. [ka]

[0112] [ka]

[0113] Examples of the carboxylic acid compound represented by formula (7) include, but are not limited to, the compounds shown below. [ka]

[0114] [ka]

[0115] [ka]

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] The carboxyl group-containing polymer containing the repeating unit represented by formula (6) may further contain a repeating unit other than the repeating unit represented by formula (6) (hereinafter also referred to as "other repeating units"). The other repeating units are not particularly limited, but are preferably those that can improve the solubility in a solvent of a polymer that is poorly soluble in the repeating unit having a carboxyl group alone. The other repeating units are preferably repeating units having a cyclic structure with a rigid skeleton that is expected to have high etching resistance, or repeating units containing a styrene skeleton.

[0120] Specific examples of the other repeating units include, but are not limited to, those shown below. A is the same as above, and X B are each independently —CH— or —O—. [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127]

change

[0128]

change

[0129]

change

[0130]

change

[0131]

change

[0132]

change

[0133]

change

[0134]

change

[0135]

change

[0136]

change

[0137]

change

[0138]

change

[0139]

change

[0140]

change

[0141]

change

[0142]

change

[0143]

change

[0144]

change

[0145]

change

[0146]

change

[0147]

change

[0148] [ka]

[0149] [ka]

[0150] In the resist composition, the molar ratio of the hypervalent iodine compound to the carboxy group-containing compound (when the carboxy group-containing compound is a carboxy group-containing polymer, the molar ratio of the hypervalent iodine compound to the carboxylic acid-containing repeating units in the polymer) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30. The hypervalent iodine compounds may be used alone or in combination of two or more. The carboxy group-containing polymers may be used alone or in combination of two or more having different composition ratios, Mw, and / or Mw / Mn.

[0151] In the carboxyl group-containing polymer, the molar ratio of the carboxyl group-containing repeating units to the other repeating units is preferably 10:90 to 90:10, more preferably 15:85 to 85:15, and even more preferably 20:80 to 80:20.

[0152] The weight average molecular weight (Mw) of the carboxy group-containing polymer is preferably 1,000 to 500,000, more preferably 3,000 to 100,000. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0153] Furthermore, if the carboxyl group-containing polymer has a broad molecular weight distribution (Mw / Mn), the presence of low-molecular-weight and high-molecular-weight polymers may result in the appearance of foreign matter on the pattern after exposure, or the pattern shape may be deteriorated. Therefore, since the effects of Mw and Mw / Mn tend to become greater as the pattern rule becomes finer, in order to obtain a resist composition that is suitable for use with fine pattern dimensions, it is preferable that the carboxyl group-containing polymer have a narrow Mw / Mn distribution of 1.0 to 2.0.

[0154] The carboxyl group-containing polymer can be synthesized, for example, by polymerizing a monomer that provides the repeating unit described above in an organic solvent with the addition of a radical polymerization initiator by heating.

[0155] Specific examples of organic solvents used in the polymerization reaction include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, cyclopentanone, cyclohexanone, methyl ethyl ketone (MEK), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). Specific examples of the polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The amount of the polymerization initiator added is preferably 0.01 to 25 mol% of the total amount of monomers to be polymerized. The reaction temperature is preferably 50 to 150° C., more preferably 60 to 100° C. The reaction time is preferably 2 to 24 hours, more preferably 2 to 12 hours from the viewpoint of production efficiency.

[0156] The polymerization initiator may be added to the monomer solution and then fed to the reaction vessel. Alternatively, an initiator solution may be prepared separately from the monomer solution, and each may be fed to the reaction vessel independently. From the perspective of quality control, it is preferable to prepare the monomer solution and the initiator solution independently and then add them dropwise, since radicals generated from the initiator during the waiting time may cause the polymerization reaction to proceed, resulting in the formation of ultra-high molecular weight polymers. Furthermore, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol may be used in combination to adjust the molecular weight. In this case, the amount of the chain transfer agent added is preferably 0.01 to 20 mol % of the total amount of monomers to be polymerized.

[0157] The amount of each monomer in the monomer solution may be appropriately set so as to achieve the preferred content ratio of the repeating units described above.

[0158] The resist composition contains a solvent. The solvent is not particularly limited as long as it can dissolve the hypervalent iodine compound, the carboxyl group-containing compound, and other components described below and can form a film. Organic solvents are preferred as such solvents, and specific examples thereof include ketones such as cyclohexanone, methyl-2-n-pentyl ketone, and methyl isoamyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, and 4-methyl-2-pentanol; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, and propylene glycol dimethyl ether. esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, methyl 2-hydroxyisobutyrate, propylene glycol mono tert-butyl ether acetate; carboxylic acids such as formic acid, acetic acid, and propionic acid; lactones such as γ-butyrolactone; and mixed solvents thereof.

[0159] The content of the solvent in the resist composition is preferably an amount such that the solids concentration in the resist composition is 0.1 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably 0.1 to 10 mass%. In the present invention, the solids refer collectively to all components of the resist composition other than the solvent. The solvents may be used alone or in combination of two or more.

[0160] The resist composition may further contain a surfactant. The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of such surfactants include those described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425. Furthermore, surfactants other than the fluorine-based and / or silicone-based surfactants described in paragraph

[0280] of U.S. Patent Application Publication No. 2008 / 0248425 may also be used.

[0161] When the resist composition contains the surfactant, the content thereof is preferably 0.0001 to 2 mass % of the total solid content. The surfactant may be used alone or in combination of two or more.

[0162] The resist composition may further contain a radical scavenger, which can control photoreactions during photolithography and adjust sensitivity.

[0163] Examples of the radical scavenger include hindered phenols, quinones, hindered amines, and thiol compounds. Specific examples of hindered phenols include dibutylhydroxytoluene (BHT) and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). Examples of quinones include 4-methoxyphenol (methoquinone) and hydroquinone. Examples of hindered amines include 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethylpiperidine-N-oxy radical. Examples of thiols include dodecanethiol and hexadecanethiol.

[0164] When the resist composition contains the radical scavenger, the content thereof is preferably 0.01 to 10 mass % of the total solid content. The radical scavenger may be used alone or in combination of two or more.

[0165] The resist composition may further contain a crosslinking agent, which promotes the crosslinking reaction during photolithography, improves the glass transition temperature of the pattern, and allows for the production of a pattern with excellent fine-line resolution.

[0166] Examples of the crosslinking agent include compounds having a carbon-carbon unsaturated bond as a functional group, such as a vinyl group, a (meth)acrylate group, an allyl group, an alkynyl group, or an aromatic ring. Specific examples of compounds having a vinyl group include linear alkenes, branched alkenes, and cyclic alkenes, which may have a substituent. Examples of compounds having a (meth)acrylate group include acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, which may have a substituent. Examples of compounds having an allyl group include allyl alcohols, allyl ethers, allyl esters, allyl amides, allyl amines, and allyl group-containing isocyanurates, which may have a substituent. Examples of compounds having an alkynyl group include linear alkynes, branched alkynes, cyclic alkynes, alkynyl alcohols, alkynyl ethers, alkynyl esters, alkynyl amides, alkynyl amines, and alkynyl group-containing isocyanurates, which may have a substituent. Examples of compounds having an aromatic ring include arenes, heteroarenes, styrene, stilbene, phenylacetylene, acenaphthylene, chalcone, and the like, which may have a substituent. The crosslinking agent may have only one of the above functional groups, or may have a plurality of functional groups. The number of the above functional groups contained in the crosslinking agent is preferably 1 to 10, and more preferably 2 to 8.

[0167] When the resist composition contains the crosslinking agent, the content thereof is preferably 0.01 to 50 mass % of the total solid content. The crosslinking agents may be used alone or in combination of two or more.

[0168] When the resist composition contains the crosslinking agent, it may further contain a photopolymerization initiator. The photopolymerization initiator generates radicals when irradiated with high-energy rays, and can promote crosslinking of the crosslinking agent.

[0169] Specific examples of the photopolymerization initiator include benzophenone, methyl O-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino acetophenone derivatives such as 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methylpropan-1-one and methyl phenylglyoxylate; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone and diethylthioxanthone; benzil, benzil dimethyl ketal ... Benzyl derivatives such as benzyl-β-methoxyethyl acetal; benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and other benzoin derivatives; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1, Oxime compounds such as 2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime-1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)]ethanone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime);α-Hydroxyketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropane; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl) Examples of suitable compounds include α-aminoalkylphenone compounds such as butan-1-one; phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

[0170] When the resist composition contains the photopolymerization initiator, its content is preferably 0.1 to 10 mass %, more preferably 0.1 to 5 mass %, and most preferably 0.1 to 1 mass %, based on the total solid content. When the content is 0.1 mass % or more, a sufficient blending effect can be obtained.

[0171] As described above, the resist composition contains a hypervalent iodine compound and a carboxyl group-containing compound as main components, but does not contain an acid-labile group-containing polymer or a photoacid generator, which are contained in conventional chemically amplified resist compositions. However, the resist composition of the present invention can form a positive-tone pattern, in which the exposed portion becomes soluble in a developer, particularly upon exposure to EB or EUV. The mechanism behind this is not completely clear, but is presumed to be as follows.

[0172] The hypervalent iodine compounds represented by formula (3), (4), or (5) are tricoordinate compounds having an aryl group and a carboxylate ligand. When such tricoordinate iodine compounds are mixed with a carboxyl group-containing compound, an exchange of the carboxylate ligand is thought to occur via an equilibrium reaction. If the original carboxylate ligand can be removed in some way, a hypervalent iodine compound with a new ligand is generated. For example, by mixing 1-iodonaphthylene diacetate as the hypervalent iodine compound with a carboxyl group-containing compound and removing the resulting low-boiling acetic acid, the ligand exchange is completed. The carboxyl group-containing compound then becomes a crosslinked polymer via the hypervalent iodine compound.

[0173] Polymers crosslinked with hypervalent iodine compounds are generated during film formation. This is because even if such crosslinked polymers are synthesized in advance, they are insoluble in most organic solvents, making it impossible to prepare a solution. This is presumably because hypervalent iodine compounds, which have low solvent solubility due to their inherent high polarization, become even less soluble when a carboxyl group-containing compound is used as a ligand. Therefore, it is desirable to complete the ligand exchange reaction and form a resist film by removing the original low-molecular-weight carboxylic acid component during film formation and the subsequent baking process.

[0174] The resist film obtained from the resist composition undergoes a change in polarity due to the decomposition of the hypervalent iodine compound, which is the main component, by light, and a pattern is formed by a development step. The mechanism by which this occurs is not completely clear, but is presumed to be as follows, for example.

[0175] The resist film obtained from the resist composition contains a polymer to which a hypervalent iodine compound is bonded during film formation. However, when this polymer is decomposed by light, it becomes a monovalent iodine compound, and at the same time, the bond between the carboxyl group-containing compound and the hypervalent iodine compound is released, resulting in a decrease in molecular weight. As a result, a positive pattern is formed in which the exposed areas are removed by an organic solvent.

[0176] Based on the above assumption, the resist composition can be said to be a non-chemically amplified resist composition. The resist composition does not require an acid-labile group-containing polymer or a photoacid generator, as in conventional chemically amplified resist compositions. Therefore, adverse effects due to acid diffusion (e.g., image blurring) do not occur, and fine patterns can be resolved.

[0177] The resist composition is particularly effective in EUV lithography because it contains iodine atoms with high absorption capacity for EUV light, which reduces shot noise and enables higher resolution and lower LWR.

[0178] Metal resists containing metal tin compounds as their main component, which have a high absorption capacity for EUV light similar to that of iodine atoms, have been reported as EUV resist compositions capable of forming fine patterns (e.g., Patent Document 2). However, as mentioned above, such metal resists have many problems, such as insufficient solubility in solvents, poor storage stability, and defects due to post-etching residues caused by the presence of metal elements. On the other hand, the resist composition of the present invention is advantageous over metal resists in terms of defects because it does not contain metal elements, and it also has no issues with solubility in solvents. Furthermore, the resist composition of the present invention can be applied to positive resists, and therefore has a wide range of uses. For example, in the contact hole formation process, metal resists developed using negative tone development require a reversal process step after pillar pattern formation, whereas positive tone resists do not require such a step. Therefore, from the perspective of process simplicity, the resist composition of the present invention can be said to be more useful than metal resists.

[0179] The resist film preferably has a thickness of 10 to 70 nm, more preferably 20 to 50 nm.

[0180] [Method of manufacturing laminate] The method for producing the laminate of the present invention, which is used in a two-layer resist process, includes a step of applying the adhesion film-forming composition onto a substrate and heat-treating it to form an adhesion film, and a step of applying the resist composition onto the adhesion film and heat-treating it to form a resist film.

[0181] The adhesion film can be formed by applying the adhesion film-forming composition to a substrate by spin coating or the like, evaporating the solvent, and baking to promote the crosslinking reaction. The baking temperature is preferably 100 to 400° C., more preferably 150 to 300° C. The baking time is preferably 10 to 600 seconds, more preferably 10 to 300 seconds.

[0182] Alternatively, the adhesion film can be formed by applying the adhesion film-forming composition to a substrate by spin coating or the like, as described above, and then baking and curing the adhesion film-forming composition in an atmosphere with an oxygen concentration of 0.1 to 21%. By baking the adhesion film-forming composition in such an oxygen atmosphere, a sufficiently cured film can be obtained. In this case, the baking temperature and time can be the same as those described above.

[0183] The atmosphere during baking may be air or may contain an inert gas such as N2, Ar, or He. The atmosphere may have an oxygen concentration of less than 0.1%. The baking temperature and time may be the same as those described above. Even if the substrate contains a material that is unstable when heated in an oxygen atmosphere, the crosslinking reaction during adhesion film formation can be promoted without causing deterioration of the substrate.

[0184] The resist film can be formed by applying the resist film onto the adhesion film by an appropriate application method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, and then pre-baking the applied resist film on a hot plate, preferably at 60 to 200°C for 10 seconds to 30 minutes, more preferably at 80 to 180°C for 30 seconds to 20 minutes.

[0185] The method for producing the laminate of the present invention, which is used in a four-layer resist process, includes the steps of applying a resist underlayer film-forming material onto a substrate and heat-treating it to form a resist underlayer film, forming a silicon-containing intermediate film on the resist underlayer film, applying the adhesion film-forming composition onto the silicon-containing intermediate film and heat-treating it to form an adhesion film, and applying the resist composition onto the adhesion film and heat-treating it to form a resist film.

[0186] The resist underlayer film can be formed by applying a resist underlayer film-forming composition to a substrate by spin coating or the like, evaporating the solvent, and baking the resulting film. The baking temperature can be set appropriately depending on the type of resist underlayer film to be formed, but is typically about 100 to 400° C., and preferably about 150 to 300° C. The baking time can be set appropriately depending on the type of resist underlayer film to be formed, but is typically about 10 to 600 seconds, and preferably about 10 to 300 seconds.

[0187] When forming the silicon-containing resist interlayer film as the silicon-containing interlayer film, a method can be used in which a solution of a silicon-containing resist interlayer film-forming composition is applied to the resist underlayer film by spin coating or the like, the solvent is evaporated, and the resulting film is baked. The baking temperature can be set appropriately depending on the type of silicon-containing resist interlayer film to be formed, but is typically about 100 to 400°C, preferably about 150 to 300°C. The baking time can be set appropriately depending on the type of silicon-containing resist interlayer film to be formed, but is typically about 10 to 600 seconds, preferably about 10 to 300 seconds.

[0188] When forming an inorganic hard mask intermediate film as a silicon-containing intermediate film, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, methods for forming a silicon nitride film include those described in JP 2002-334869 A and WO 2004 / 066377 A. When using a SiON film, which is highly effective as an anti-reflective film, as the inorganic hard mask intermediate film, the substrate temperature during the formation of the SiON film is 300 to 500°C, so the resist underlayer film must be able to withstand temperatures of 300 to 500°C.

[0189] In the four-layer resist process, the adhesive film can be formed by applying the adhesive film-forming composition onto the silicon-containing intermediate film by spin coating or the like, evaporating the solvent, and baking to promote the crosslinking reaction. At this time, the baking time and temperature can be the same as the temperature and time in the adhesive film formation method in the two-layer resist process.

[0190] In the four-layer resist process, the resist film can be formed by the same method as the method for forming the resist film in the two-layer resist process.

[0191] [Pattern formation method] The pattern forming method of the present invention includes the steps of exposing the resist film of the laminate to i-line, KrF excimer laser light, ArF excimer laser light, EB, or EUV, and developing the exposed resist film using a developer.

[0192] When exposing with i-line, KrF excimer laser light, ArF excimer laser light or EUV, the exposure dose is preferably 1 to 300 mJ / cm 2 directly or using a mask for forming a desired pattern. 2 approximately, more preferably 10 to 200 mJ / cm 2 When exposing using EB, the exposure dose is preferably 0.1 to 8000 μC / cm 2 directly or using a mask for forming a desired pattern. 2approximately, more preferably 0.5 to 5000 μC / cm 2 The pattern forming method of the present invention is particularly suitable for fine patterning using EB or EUV among high energy rays.

[0193] After exposure, PEB is performed as needed, preferably on a hot plate or in an oven at 30 to 200°C for 10 seconds to 30 minutes, more preferably at 60 to 120°C for 30 seconds to 20 minutes.

[0194] After exposure or PEB, the film is developed with a developer as needed to perform patterning. The developer used in this case may be 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, 5-methyl-2-hexanone, methylcyclohexanone, acetophenone, methylacetophenone, isopropyl alcohol, isoamyl alcohol, n-butanol, tert-butyl alcohol, tert-pentyl alcohol, n-pentanol, cyclohexanol, formic acid, acetic acid, propionic acid, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, cyclohexyl acetate, 4-tert-butylcyclohexyl acetate, octyl acetate, isobornyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, Examples of organic solvents include ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, 2-propanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methyl-1-butanol, diacetone alcohol, 4-methyl-2-pentanol, 3-methylcyclohexanol, 3,5,5-trimethylhexyl alcohol, 2,6-dimethyl-4-heptanol, toluene, anisole, and ε-caprolactone. These developers may be used alone or in combination of two or more.

[0195] After development, rinsing is performed as necessary. A preferred rinsing solution is a solvent that is miscible with the developer but does not dissolve the resist film. Preferred examples of such solvents include alcohols having 3 to 10 carbon atoms, ether compounds having 8 to 12 carbon atoms, alkanes, alkenes, alkynes, and aromatic solvents having 6 to 12 carbon atoms.

[0196] Rinsing can reduce the occurrence of resist pattern collapse and defects. Rinsing is not always necessary, and not performing rinsing can reduce the amount of solvent used. [Example]

[0197] The present invention will be specifically explained below with reference to Synthesis Examples, Preparation Examples, Comparative Preparation Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. The molecular weight was measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as an eluent to determine the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene, from which the polydispersity (Mw / Mn) was calculated.

[0198] [1] Synthesis of polymer for adhesive film-forming composition Compounds a-1 to a-6 shown below were used to synthesize polymers R-1 to R-8 for adhesive film-forming materials. Note that a 37% by mass aqueous solution of compound a-5 was used. [ka]

[0199] [Synthesis Example 1-1] Synthesis of Polymer R-1 [ka]

[0200] 20.0 g of compound a-1, 10.0 g of a 37% by weight aqueous solution of compound a-5, and 100 g of PGME were mixed and stirred under a nitrogen atmosphere at 100 °C to form a homogeneous solution. 3.0 g of a 20% by weight PGME solution of paratoluenesulfonic acid monohydrate (prepared) was slowly added and stirred at 110 °C for 24 hours. After cooling to room temperature, 200 mL of ethyl acetate was added, and the organic layer was washed with 100 g of a 5% by weight aqueous solution of nitric acid, followed by five washes with 300 g of pure water, and then evaporated to dryness under reduced pressure. 60 g of THF was added to the residue to form a homogeneous solution, and 150 g of hexane was added dropwise to precipitate the polymer in a mochi-like form. After allowing to stand for a while, the supernatant was removed by decantation. 60 g of THF was added to homogenize the mixture, and the same procedure was repeated twice more. The precipitated mochi-like polymer was then dried under reduced pressure at 80 °C to obtain Polymer R-1. The Mw and Mw / Mn of polymer R-1 were determined by GPC, and were found to be 1100 and 1.34.

[0201] [Synthesis Example 1-2] Synthesis of Polymer R-2 [ka]

[0202] Under a nitrogen atmosphere, 10.0 g of polymer R-1, 25.0 g of potassium carbonate, and 200 g of DMF were added to a reaction vessel and stirred at 50°C to form a uniform dispersion. 28.6 g of propargyl bromide was slowly added, and the reaction was carried out for 16 hours at 50°C. After the reaction was completed, 200 mL of MIBK was added, and the mixture was washed six times with 100 mL of pure water. The organic layer was then evaporated to dryness under reduced pressure. 50 g of THF, 50 g of pure water, and 4.8 g of sodium hydroxide were added to the residue to form a uniform dispersion, which was then reacted for 6 hours at 60°C. After the reaction was completed, 200 mL of MIBK was added, and while cooling in an ice bath, 66 g of 10% by weight aqueous hydrochloric acid was slowly added dropwise to neutralize the mixture. After neutralization, the aqueous layer was removed, and the organic layer was washed five times with 100 g of pure water. The organic layer was then recovered, the solvent was distilled off, and the mixture was evaporated to dryness under reduced pressure at 80°C to obtain polymer R-2. The Mw and Mw / Mn of polymer R-2 were determined by GPC, and were found to be 1560 and 1.31, respectively.

[0203] [Synthesis Example 1-3] Synthesis of Polymer R-3 [ka]

[0204] 20.0 g of compound a-2, 18.7 g of compound a-6, and 200 g of PGME were mixed and stirred under a nitrogen atmosphere at a liquid temperature of 100 ° C to form a homogeneous solution. 4.0 g of 25% by mass aqueous sodium hydroxide was slowly added and stirred at a liquid temperature of 110 ° C for 24 hours. After cooling to room temperature, 300 mL of MIBK was added, and the organic layer was washed twice with 100 g of 5% by mass aqueous nitric acid solution, and then five times with 200 g of pure water, followed by drying under reduced pressure. 100 g of PGME was added to the residue to form a homogeneous solution, and 200 g of hexane was added dropwise to precipitate a mochi-like polymer. After standing for a while, the supernatant was removed by decantation, and 200 g of PGME was added to homogenize the mixture. The same procedure was repeated two more times. The mochi-like precipitated polymer was then dried under reduced pressure at 80 ° C to obtain polymer R-3. The Mw and Mw / Mn of polymer R-3 were determined by GPC, and were found to be 1620 and 1.89.

[0205] [Synthesis Example 1-4] Synthesis of Polymer R-4 [ka]

[0206] 20.0 g of compound a-3, 15.0 g of compound a-6, and 200 g of PGME were mixed and stirred under a nitrogen atmosphere at a liquid temperature of 100 ° C to form a homogeneous solution. 4.0 g of 25% by mass sodium hydroxide aqueous solution was slowly added and stirred at a liquid temperature of 110 ° C for 24 hours. After cooling to room temperature, 300 mL of MIBK was added, and the organic layer was washed twice with 100 g of 5% by mass nitric acid aqueous solution, and then five times with 200 g of pure water, and then evaporated to dryness under reduced pressure. 100 g of PGME was added to the residue to form a homogeneous solution, and 200 g of hexane was added dropwise to precipitate a mochi-like polymer. After standing for a while, the supernatant was removed by decantation, and 200 g of PGME was added to homogenize the mixture. The same procedure was repeated two more times. The mochi-like precipitated polymer was then dried under reduced pressure at 80 ° C to obtain polymer R-4. The Mw and Mw / Mn of polymer R-4 were determined by GPC, and were found to be 2820 and 2.34.

[0207] [Synthesis Example 1-5] Synthesis of Polymer R-5 [ka]

[0208] Under a nitrogen atmosphere, 10.0 g of polymer R-4, 14.2 g of potassium carbonate, and 150 g of DMF were added to a reaction vessel and stirred at 50°C to form a uniform dispersion. 16.3 g of propargyl bromide was slowly added, and the reaction was carried out for 16 hours at 50°C. After the reaction was completed, 200 mL of MIBK was added, and the mixture was washed six times with 100 mL of pure water. The organic layer was evaporated to dryness under reduced pressure. 50 g of THF, 50 g of pure water, and 2.7 g of sodium hydroxide were added to the residue to form a uniform dispersion, which was then reacted for 6 hours at 60°C. After the reaction was completed, 200 mL of MIBK was added, and while cooling in an ice bath, 38 g of 10% by weight aqueous hydrochloric acid was slowly added dropwise to neutralize the mixture. After neutralization, the aqueous layer was removed, and the organic layer was washed five times with 100 g of pure water. The organic layer was then recovered, the solvent was removed, and the mixture was evaporated to dryness under reduced pressure at 80°C to obtain polymer R-5. The Mw and Mw / Mn of polymer R-5 were determined by GPC, and were found to be 4390 and 2.41, respectively.

[0209] [Synthesis Example 1-6] Synthesis of Polymer R-6 [ka]

[0210] 20.0 g of compound a-4, 6.4 g of compound a-5 as an aqueous solution, and 100 g of PGME were mixed and stirred under a nitrogen atmosphere at a liquid temperature of 100 ° C to form a homogeneous solution. 4.0 g of 25% by mass sodium hydroxide aqueous solution was slowly added and stirred at a liquid temperature of 110 ° C for 24 hours. After cooling to room temperature, 200 mL of MIBK was added, and the organic layer was washed twice with 100 g of 5% by mass nitric acid aqueous solution, and then five times with 200 g of pure water, and then evaporated to dryness under reduced pressure. 60 g of PGME was added to the residue to form a homogeneous solution, and 150 g of hexane was added dropwise to precipitate a mochi-like polymer. After standing for a while, the supernatant was removed by decantation, and 60 g of PGME was added to homogenize the mixture. The same procedure was repeated two more times. The mochi-like precipitated polymer was then dried under reduced pressure at 80 ° C to obtain polymer R-6. The Mw and Mw / Mn of polymer R-6 were determined by GPC, and were found to be 3800 and 2.46.

[0211] [Synthesis Example 1-7] Synthesis of Polymer R-7 [ka]

[0212] Under a nitrogen atmosphere, 10.0 g of polymer R-6, 19.2 g of potassium carbonate, and 150 g of DMF were added to a reaction vessel and stirred at 50°C to form a uniform dispersion. 22.0 g of propargyl bromide was slowly added, and the reaction was carried out for 16 hours at 50°C. After the reaction was completed, 150 mL of MIBK was added, and the mixture was washed six times with 100 mL of pure water. The organic layer was evaporated to dryness under reduced pressure. 50 g of THF, 50 g of pure water, and 3.7 g of sodium hydroxide were added to the residue to form a uniform dispersion, which was then reacted for 6 hours at 60°C. After the reaction was completed, 200 mL of MIBK was added, and while cooling in an ice bath, 51 g of 10% by weight aqueous hydrochloric acid was slowly added dropwise to neutralize. After neutralization, the aqueous layer was removed, and the organic layer was washed five times with 100 g of pure water. The organic layer was then recovered, the solvent was distilled off, and the mixture was evaporated to dryness under reduced pressure at 80°C to obtain polymer R-7. The Mw and Mw / Mn of polymer R-7 were determined by GPC, and were found to be 6600 and 2.58.

[0213] [Synthesis Example 1-8] Synthesis of Polymer R-8 [ka]

[0214] 20.0 g of compound a-4, 111.8 g of compound a-6, and 200 g of PGME were mixed and stirred under a nitrogen atmosphere at a liquid temperature of 100 ° C to form a homogeneous solution. 4.0 g of 25% by mass sodium hydroxide aqueous solution was slowly added and stirred at a liquid temperature of 110 ° C for 24 hours. After cooling to room temperature, 300 mL of MIBK was added, and the organic layer was washed twice with 100 g of 5% by mass nitric acid aqueous solution, and then five times with 200 g of pure water, and then evaporated to dryness under reduced pressure. 100 g of PGME was added to the residue to form a homogeneous solution, and 200 g of hexane was added dropwise to precipitate a mochi-like polymer. After standing for a while, the supernatant was removed by decantation, and 200 g of PGME was added to homogenize. The same procedure was repeated two more times. The mochi-like precipitated polymer was then dried under reduced pressure at 80 ° C to obtain polymer R-8. The Mw and Mw / Mn of polymer R-8 were determined by GPC, and were found to be 1050 and 1.28, respectively.

[0215] [2] Synthesis of polymers for resist compositions The compounds shown below were used to synthesize the polymers P-1 to P-5 for resist compositions. [ka]

[0216] [ka]

[0217] [ka]

[0218] [Synthesis Example 2-1] Synthesis of Polymer P-1 A monomer-polymerization initiator solution was prepared by placing 56 g of monomer b-1, 36 g of monomer c-1, 5.4 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.), and 180 g of MEK in a flask under a nitrogen atmosphere. 55 g of MEK was placed in a separate flask under a nitrogen atmosphere and heated to 80°C with stirring. The monomer-polymerization initiator solution was then added dropwise over 4 hours. After the addition, the polymerization solution was stirred for 2 hours while maintaining the temperature at 80°C, and then cooled to room temperature. The resulting polymerization solution was added dropwise to 4,000 g of vigorously stirred hexane, and the precipitated polymer was filtered. The resulting polymer was washed twice with 1,200 g of hexane and then vacuum-dried at 50°C for 20 hours to obtain polymer P-1 as a white powder (yield: 90 g, 98%). The Mw of polymer P-1 was 8,000, and the Mw / Mn ratio was 1.42. The Mw is a polystyrene-equivalent value measured by GPC using THF as a solvent. [ka]

[0219] [Synthesis Examples 2-2 to 2-5] Synthesis of Polymers P-2 to P-5 The polymers shown in Table 1 below were synthesized in the same manner as in Synthesis Example 2-1, except that the types and blending ratios of the respective monomers were changed.

[0220] [Table 1]

[0221] [3] Preparation of adhesive film-forming composition [Preparation Examples 1-1 to 1-9] Each component shown in Table 2 below was dissolved in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Limited) as a surfactant, and the resulting solution was filtered through a 0.1 μm fluororesin filter to prepare compositions for forming adhesion films (UL-01 to UL-09).

[0222] [Table 2]

[0223] The thermal acid generator AG-1, crosslinking agents XL-1 to XL-3, polymer R-9 for comparative adhesion film-forming compositions, and organic solvents are as follows in Table 2. The Mw and Mw / Mn of polymer R-9 were determined by GPC, and were found to be 1100 and 1.22, respectively. [ka]

[0224] [ka]

[0225] [ka]

[0226] PGMEA: Propylene glycol methyl ether acetate PGEE: Propylene glycol ethyl ether

[0227] [4] Preparation of resist composition [Preparation Examples 2-1 to 2-10, Comparative Preparation Examples 1-1 to 1-2] Resist compositions (R-01 to R-10) were prepared by dissolving a hypervalent iodine compound and a carboxyl group-containing compound in a solvent containing 0.01% by mass of a surfactant (PF-636, Omnova) according to the compositions shown in Table 3 below, and filtering the resulting solution through a 0.2 μm Teflon (registered trademark) filter. Resist compositions (CR-01 and CR-02) were prepared by dissolving a polymer, a photoacid generator, and a sensitivity adjuster in a solvent containing 0.01% by mass of a surfactant (PF-636, Omnova) according to the compositions shown in Table 4 below, and filtering the resulting solution through a 0.2 μm Teflon (registered trademark) filter.

[0228] [Table 3]

[0229] [Table 4]

[0230] In Tables 3 and 4, the hypervalent iodine compounds I-1 to I-3, carboxy group-containing compounds m-1 to m-3, photoacid generator PAG-1, sensitivity adjuster Q-1 and solvents are as follows. [ka]

[0231] [ka]

[0232] [ka]

[0233] [ka]

[0234] Solvent: AcOH (acetic acid) GBL (γ-butyrolactone)

[0235] [5] Fabrication of laminate and EUV lithography evaluation (two-layer resist process, line and space pattern) [Examples 1-1 to 1-17, Comparative Examples 1-1 to 1-5] Each adhesion film-forming material composition (UL-01 to UL-09) was spin-coated onto a silicon substrate and baked for 60 seconds using a hot plate at the temperature shown in Table 5 to form an adhesion film with a thickness of 40 nm. In Comparative Example 1-2, a silicon-containing spin-on hard mask SHB-A940 (silicon content 43 mass%) manufactured by Shin-Etsu Chemical Co., Ltd. shown in Table 5 was formed on the substrate to a thickness of 40 nm, and in Comparative Example 1-3, an anti-reflection film DUV-42 manufactured by Nissan Chemical Industries, Ltd. was formed on the substrate to a thickness of 40 nm. Next, each resist composition (R-01 to R-10, CR-01 to CR-02) was spin-coated onto the film and pre-baked (PAB) for 60 seconds using a hot plate at the temperature listed in Table 5 to produce a 40 nm thick resist film. The resist film was exposed to a 36 nm line and space (LS) 1:1 pattern using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9, 90-degree dipole illumination), and then PEB was performed on a hot plate at the temperature listed in Table 5 for 60 seconds, followed by development for 30 seconds using the developer listed in Table 5 to form an LS pattern with a space width of 18 nm and a pitch of 36 nm.

[0236] The resulting resist patterns were evaluated as follows, and the results are shown in Table 5.

[0237] [Sensitivity evaluation] The LS pattern was observed using a length measurement SEM (CG-6300) manufactured by Hitachi High-Tech Corporation, and the optimum exposure dose Eop (mJ / cm) for obtaining an LS pattern with a space width of 18 nm and a pitch of 36 nm was determined. 2 ) was calculated and used as the sensitivity.

[0238] [LWR rating] The LS pattern obtained by irradiation with the optimum exposure dose was measured at 10 points in the longitudinal direction of the space width using a critical dimension SEM (CG-6300) manufactured by Hitachi High-Tech Corporation, and the LWR was calculated as three times the standard deviation (σ) (3σ). The smaller this value, the less roughness and the more uniform the space width pattern obtained.

[0239] [Limiting resolution evaluation] The limiting line width (nm) that can be resolved when forming a pattern by gradually increasing the exposure dose from the optimum exposure dose at which the LS pattern is formed was determined using a critical dimension SEM (CG-6300) manufactured by Hitachi High-Technologies Corporation, and this was taken as the limiting resolution (nm). The smaller this value, the better the limiting resolution, indicating that a finer pattern can be formed.

[0240] [Table 5]

[0241] Developer: nBA (butyl acetate) TMAH (2.38% by mass tetramethylammonium hydroxide aqueous solution)

[0242] From the results shown in Table 5, when comparing Comparative Examples 1-1 to 1-3 with the Examples, it was found that excellent resolution could be obtained by using the adhesion film-forming composition in a two-layer resist process. Furthermore, it was found that excellent sensitivity, resolution, and LWR were obtained compared with Comparative Examples 1-4 and 1-5, which used chemically amplified resist compositions using an acid-catalyzed reaction. Therefore, it was found that the two-layer resist process using the laminate of the present invention exhibited excellent resolution in LS pattern formation by EUV exposure.

[0243] [6] Stack manufacturing and EUV lithography evaluation (four-layer resist process, line and space pattern) [Examples 2-1 to 2-17, Comparative Examples 2-1 to 2-5] A silicon substrate was coated with spin-on carbon ODL-301 (carbon content: 88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. and baked at 350°C for 60 seconds to form a 200 nm thick resist underlayer film. A 40 nm thick SiON hard mask intermediate film was then formed thereon by CVD. Each of the adhesion film-forming compositions (UL-01 to UL-09) was spin-coated onto the intermediate film and baked for 60 seconds using a hot plate at the temperature listed in Table 6 to form a 5 nm thick adhesion film. In Comparative Example 2-2, a 40 nm thick silicon-containing spin-on hard mask SHB-A940 (silicon content: 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was formed on the substrate. In Comparative Example 2-3, a 40 nm thick anti-reflective film DUV-42 manufactured by Nissan Chemical Industries, Ltd. was formed on the substrate. Next, each resist composition (R-01 to R-10, CR-01 to CR-02) was spin-coated onto the film and pre-baked (PAB) for 60 seconds using a hot plate at the temperature listed in Table 6 to produce a 40 nm thick resist film. The resist film was exposed to a 36 nm line and space (LS) 1:1 pattern using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9, 90-degree dipole illumination), and then PEB was performed on a hot plate at the temperature listed in Table 6 for 60 seconds, followed by development for 30 seconds using the developer listed in Table 6 to form an LS pattern with a space width of 18 nm and a pitch of 36 nm.

[0244] The resulting resist patterns were evaluated as follows, and the results are shown in Table 6.

[0245] [Sensitivity evaluation] The LS pattern was observed using a length measurement SEM (CG-6300) manufactured by Hitachi High-Tech Corporation, and the optimum exposure dose Eop (mJ / cm) for obtaining an LS pattern with a space width of 18 nm and a pitch of 36 nm was determined. 2 ) was calculated and used as the sensitivity.

[0246] [LWR rating] The LS pattern obtained by irradiation with the optimum exposure dose was measured at 10 points in the longitudinal direction of the space width using a critical dimension SEM (CG-6300) manufactured by Hitachi High-Tech Corporation, and the LWR (nm) was calculated as three times the standard deviation (σ). The smaller this value, the less roughness and the more uniform the space width pattern obtained.

[0247] [Limiting resolution evaluation] The limiting line width (nm) that can be resolved when forming a pattern by gradually increasing the exposure dose from the optimum exposure dose at which the LS pattern is formed was determined using a critical dimension SEM (CG-6300) manufactured by Hitachi High-Technologies Corporation, and this was taken as the limiting resolution (nm). The smaller this value, the better the limiting resolution, indicating that a finer pattern can be formed.

[0248] [Table 6]

[0249] Developer: nBA (butyl acetate) TMAH (2.38% by mass tetramethylammonium hydroxide aqueous solution)

[0250] From the results shown in Table 6, when comparing Comparative Examples 2-1 to 2-3 with the Examples, it was found that excellent resolution could be obtained by using the adhesion film-forming composition in a four-layer resist process. Furthermore, it was found that excellent sensitivity, resolution, and LWR were obtained compared with Comparative Examples 2-4 and 2-5, which used chemically amplified resist compositions using an acid-catalyzed reaction. Therefore, it was found that the four-layer resist process using the laminate of the present invention exhibited excellent resolution in LS pattern formation by EUV exposure.

[0251] [7] Stack manufacturing and EUV lithography evaluation (four-layer resist process, contact hole pattern) [Examples 3-1 to 3-17, Comparative Examples 3-1 to 3-5] A silicon substrate was coated with spin-on carbon ODL-301 (carbon content: 88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., and baked at 350°C for 60 seconds to form a resist underlayer film with a thickness of 200 nm. A silicon-containing spin-on hard mask SHB-A940 (silicon content: 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was then coated thereon and baked at 220°C for 60 seconds to form a silicon-containing intermediate film with a thickness of 40 nm. Each of the adhesion film-forming compositions (UL-01 to UL-09) was spin-coated onto the intermediate film, and baked using a hot plate at the temperature listed in Table 7 for 60 seconds to form an adhesion film with a thickness of 5 nm. In Comparative Example 3-2, a silicon-containing spin-on hard mask SHB-A940 (silicon content: 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was formed on the substrate to a thickness of 40 nm, and in Comparative Example 3-3, an anti-reflective film DUV-42 manufactured by Nissan Chemical Industries, Ltd. was formed on the substrate to a thickness of 40 nm. Next, each resist composition (R-01 to R-10, CR-01 to CR-02) was spin-coated onto the film and pre-baked (PAB) for 60 seconds using a hot plate at the temperature listed in Table 7 to produce a resist film with a thickness of 50 nm. Next, the resist film was exposed using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9 / 0.6, quadruple pole illumination, wafer dimensions 64 nm pitch, +20% bias hole pattern mask), and PEB was performed on a hot plate at the temperature listed in Table 7 for 60 seconds. Development was performed for 30 seconds using the developer listed in Table 7 to obtain a hole pattern with a dimension of 32 nm.

[0252] The resulting resist patterns were evaluated as follows, and the results are shown in Table 7.

[0253] [Sensitivity evaluation] The contact hole pattern was observed using a length measuring SEM (CG-6300) manufactured by Hitachi High-Tech Corporation, and the optimum exposure dose Eop (mJ / cm) for obtaining a hole pattern with a dimension of 22 nm was determined. 2 ) was calculated and used as the sensitivity.

[0254] [CDU Rating] The dimensions of 50 hole patterns obtained by irradiation with the optimal exposure dose were measured, and the CDU was calculated as three times the standard deviation (σ). The smaller this value, the more uniform the hole diameter pattern obtained.

[0255] [Limiting resolution evaluation] The limiting hole diameter (nm) that can be resolved when forming a hole pattern by gradually decreasing the exposure dose from the optimum exposure dose required to form the hole pattern was determined using a critical dimension SEM (CG-6300) manufactured by Hitachi High-Technologies Corporation, and this was taken as the limiting resolution (nm). The smaller this value, the better the limiting resolution, indicating that a pattern with a finer hole diameter can be formed.

[0256] [Table 7]

[0257] Developer: nBA (butyl acetate) TMAH (2.38% by mass tetramethylammonium hydroxide aqueous solution)

[0258] From the results shown in Table 7, when comparing Comparative Examples 3-1 to 3-3 with the Examples, it was found that an excellent CDU pattern could be obtained by using the adhesion film-forming composition in a four-layer resist process. Furthermore, it was found that the sensitivity, resolution, and LWR were excellent even when compared with Comparative Examples 3-4 and 3-5, which used chemically amplified resist compositions using an acid catalysis. Therefore, it was found that the four-layer resist process using the laminate of the present invention provides excellent CDU in contact hole pattern formation by EUV exposure.

Claims

1. A substrate; an adhesion film obtained from an adhesion film-forming composition containing a polymer containing a repeating unit represented by formula (1) or (2) and an organic solvent; a resist film obtained from a resist composition containing at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by the following formula (3), a hypervalent iodine compound represented by the following formula (4), and a hypervalent iodine compound represented by the following formula (5), a carboxy group-containing compound, and a solvent; A laminate comprising the above in this order. 【Chemistry 1】 (In the formula, a is 0, 1, or 2. b is an integer that satisfies 0≦b≦4a+2. c is an integer that satisfies 1≦c≦4a+2, provided that 1≦b+c≦4a+2. d is 0, 1, 2, 3, 4, or 5. e is 0, 1, 2, 3, 4, or 5, provided that 1≦d+e≦5. R 1 is a hydroxy group or a 2-propynyloxy group. R 2 is a carboxy group or a carboxymethoxy group. R 3 is a hydroxy group or a 2-propynyloxy group. R 4 is a carboxy group or a carboxymethoxy group. 【Chemistry 2】 (In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, provided that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, provided that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R 11 ~R 18 are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. 11 and R 12 , R 13 and R 14 , R 15 and R 16 , or R 17 and R 18 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. R 21 ~R 24 are each independently a halogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. When n2 is 2 or more, each R 21 may be the same or different, and multiple R 21 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 22 may be the same or different, and multiple R 22 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 23 may be the same or different, and multiple R 23 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 24 may be the same or different, and multiple R 24 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. R 25 is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R 25 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and the -CH of the (n8)-valent hydrocarbon group may be substituted with a group containing a hetero atom. 2 A part of - may be substituted with a group containing a hetero atom, 24 and R 25 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.)

2. 2. The laminate according to claim 1, further comprising a resist underlayer film and a silicon-containing intermediate film disposed in this order from the substrate side between the substrate and the adhesive film.

3. 2. The laminate according to claim 1, wherein the polymer containing the repeating unit represented by formula (1) or (2) has a weight average molecular weight of 500 to 20,000.

4. 2. The laminate according to claim 1, wherein the adhesive film composition further comprises at least one selected from the group consisting of a surfactant, a crosslinking agent, and a thermal acid generator.

5. 2. The laminate according to claim 1, wherein the adhesive film has a thickness of 2 to 50 nm.

6. 2. The laminate according to claim 1, wherein the carboxy group-containing compound is a polymer containing a repeating unit represented by the following formula (6) or a compound represented by the following formula (7): 【Transformation 3】 (In the formula, R A is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A represents a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-X A1 - is. X A1 is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring. * represents a bond to a carbon atom in the main chain. p is 1, 2, 3 or 4. R 31 is a p-valent hydrocarbon group having 1 to 40 carbon atoms or a p-valent heterocyclic group having 2 to 40 carbon atoms, and when p is 2, R 31 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. In addition, some or all of the hydrogen atoms of the p-valent hydrocarbon group or the p-valent heterocyclic group may be substituted with a group containing a hetero atom, and the -CH 2 A portion of - may be substituted with a group containing a hetero atom. R 32 represents a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a hetero atom, and the —CH 2 When p is 2, 3, or 4, each R 32 may be the same as or different from each other.)

7. A step of applying an adhesion film-forming composition containing a polymer containing a repeating unit represented by the following formula (1) or (2) and an organic solvent onto a substrate, and then heat-treating the composition to form an adhesion film; a step of applying a resist composition containing at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by the following formula (3), a hypervalent iodine compound represented by the following formula (4), and a hypervalent iodine compound represented by the following formula (5), a carboxy group-containing compound, and a solvent onto the adhesion film, and then performing a heat treatment to form a resist film. A method for producing a laminate comprising the steps of: 【Chemistry 4】 (In the formula, a is 0, 1, or 2. b is an integer that satisfies 0≦b≦4a+2. c is an integer that satisfies 1≦c≦4a+2, provided that 1≦b+c≦4a+2. d is 0, 1, 2, 3, 4, or 5. e is 0, 1, 2, 3, 4, or 5, provided that 1≦d+e≦5. R 1 is a hydroxy group or a 2-propynyloxy group. R 2 is a carboxy group or a carboxymethoxy group. R 3 is a hydroxy group or a 2-propynyloxy group. R 4 is a carboxy group or a carboxymethoxy group. 【Transformation 5】 (In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, provided that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, provided that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R 11 ~R 18 are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. 11 and R 12 , R 13 and R 14 , R 15 and R 16 , or R 14 and R 18 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. R 21 ~R 24 are each independently a halogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. When n2 is 2 or more, each R 21 may be the same or different, and multiple R 21 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 22 may be the same or different, and multiple R 22 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 23 may be the same or different, and multiple R 23 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 24 may be the same or different, and multiple R 24 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. R 25 is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R 25 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and the -CH of the (n8)-valent hydrocarbon group may be substituted with a group containing a hetero atom. 2 A part of - may be substituted with a group containing a hetero atom, 24 and R 25 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.)

8. a step of applying a resist underlayer film-forming material onto a substrate and performing a heat treatment to form a resist underlayer film; forming a silicon-containing intermediate film on the resist underlayer film; a step of applying an adhesion film-forming composition containing a polymer containing a repeating unit represented by the following formula (1) or (2) and an organic solvent onto the silicon-containing interlayer film, and then heat-treating the composition to form an adhesion film; a step of applying a resist composition containing at least one hypervalent iodine compound selected from the group consisting of a hypervalent iodine compound represented by the following formula (3), a hypervalent iodine compound represented by the following formula (4), and a hypervalent iodine compound represented by the following formula (5), a carboxy group-containing compound, and a solvent onto the adhesion film, and then performing a heat treatment to form a resist film. A method for producing a laminate comprising the steps of: 【Transformation 6】 (In the formula, a is 0, 1, or 2. b is an integer that satisfies 0≦b≦4a+2. c is an integer that satisfies 1≦c≦4a+2, provided that 1≦b+c≦4a+2. d is 0, 1, 2, 3, 4, or 5. e is 0, 1, 2, 3, 4, or 5, provided that 1≦d+e≦5. R 1 is a hydroxy group or a 2-propynyloxy group. R 2 is a carboxy group or a carboxymethoxy group. R 3 is a hydroxy group or a 2-propynyloxy group. R 4 is a carboxy group or a carboxymethoxy group. 【Transformation 7】 (In the formula, m is 0, 1, or 2. When m is 0, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, or 5, and 1≦n1+n2≦6. When m is 1, n1 is 1, 2, or 3, and n2 is 0, 1, 2, 3, 4, 5, 6, or 7, and 1≦n1+n2≦8. When m is 2, n1 is 1, 2, or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, and 1≦n1+n2≦10. n3 is 1 or 2. n4 is 0, 1, 2, 3, or 4, provided that 1≦n3+n4≦5. n5 is 1 or 2. n6 is 0, 1, 2, 3, or 4, provided that 1≦n5+n6≦5. n7 is 0, 1, 2, 3, or 4. n8 is 1, 2, 3, or 4. R 11 ~R 18 are each independently a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may contain a heteroatom. 11 and R 12 , R 13 and R 14 , R 15 and R 16 , or R 14 and R 18 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms. R 21 ~R 24 are each independently a halogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. When n2 is 2 or more, each R 21 may be the same or different, and multiple R 21 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 22 may be the same or different, and multiple R 22 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 23 may be the same or different, and multiple R 23 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are bonded. 24 may be the same or different, and multiple R 24 may be bonded to each other to form a ring together with the carbon atoms of the aromatic ring to which they are attached. R 25 is an (n8)-valent hydrocarbon group having 1 to 40 carbon atoms or an (n8)-valent heterocyclic group having 2 to 40 carbon atoms, and when n8 is 2, R 25 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, a sulfonyl group, or a thioketone bond. In addition, some or all of the hydrogen atoms of the (n8)-valent hydrocarbon group or the (n8)-valent heterocyclic group may be substituted with a group containing a hetero atom, and the -CH of the (n8)-valent hydrocarbon group may be substituted with a group containing a hetero atom. 2 A part of - may be substituted with a group containing a hetero atom, 24 and R 25 may be bonded to each other to form a ring together with the carbon atoms to which they are bonded and the atoms between said carbon atoms.)

9. 9. The method for producing a laminate according to claim 8, wherein the silicon-containing intermediate film is formed by applying a silicon-containing resist intermediate film material onto the resist underlayer film and then heat-treating the applied material.

10. 9. The method for producing a laminate according to claim 8, wherein the silicon-containing intermediate film is an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film formed by a CVD method or an ALD method.

11. The method for producing a laminate according to any one of claims 7 to 10, wherein the carboxy group-containing compound is a polymer containing a repeating unit represented by the following formula (6) or a compound represented by the following formula (7): 【Transformation 8】 (In the formula, R A is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group. X A represents a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-X A1 - is. X A1 is a saturated hydrocarbylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group, and the saturated hydrocarbylene group may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring. * represents a bond to a carbon atom in the main chain. p is 1, 2, 3 or 4. R 31 is a p-valent hydrocarbon group having 1 to 40 carbon atoms or a p-valent heterocyclic group having 2 to 40 carbon atoms, and when p is 2, R 31 may be an ether bond, a carbonyl group, an azo group, a thioether bond, a carbonate bond, a carbamate bond, a sulfinyl group, or a sulfonyl group. In addition, some or all of the hydrogen atoms of the p-valent hydrocarbon group or the p-valent heterocyclic group may be substituted with a group containing a hetero atom, and the -CH 2 A portion of - may be substituted with a group containing a hetero atom. R 32 represents a single bond or a hydrocarbylene group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a hetero atom, and the —CH 2 When p is 2, 3, or 4, each R 32 may be the same as or different from each other.)

12. A pattern forming method comprising the steps of: exposing a resist film of the laminate according to any one of claims 1 to 6 to i-line, KrF excimer laser light, ArF excimer laser light, electron beam, or extreme ultraviolet light; and developing the exposed resist film using a developer.

13. 13. The pattern forming method according to claim 12, wherein the developer is an organic solvent.

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