Adhesion film forming material, pattern forming method, and method for forming adhesion film

Abstract

The present invention relates to an adhesion film forming material, a pattern forming method, and an adhesion film forming method. The present invention provides an adhesion film forming material for an adhesion film which is formed immediately below an upper resist film, the adhesion film forming material containing (A) a resin having at least one structural unit containing a fluorine-substituted organic sulfonyl anion structure and at least one structural unit represented by the following general formula (2) which is different from the structural unit containing the fluorine-substituted organic sulfonyl anion structure, (B) a thermal acid generator, and (C) an organic solvent.

Description

TECHNICAL FIELD

[0001] The present application relates to an adhesion film forming material, a pattern forming method, and an adhesion film forming method. BACKGROUND

[0002] With the high integration and high speed of LSIs, the miniaturization of pattern size has also been rapidly progressing. The photolithography technique has gradually achieved the formation of fine patterns in response to the miniaturization by the shortening of the wavelength of the light source and the appropriate selection of the resist composition corresponding to the light source. The center of attention is a positive photoresist composition used in a single layer. The single layer positive photoresist composition is dissolved at the exposed portion and a pattern is formed by the etching resistance of the skeleton having etching resistance to chlorine or fluorine gas plasma in the resist resin and the resist mechanism of the dissolution at the exposed portion, and the dry etching processing of the processed substrate coated with the photoresist composition is performed using the remaining resist pattern as an etching mask.

[0003] However, the direct miniaturization of the film thickness of the photoresist film used, that is, the making of the pattern width even smaller, reduces the resolution performance of the photoresist film, and, when the photoresist film is developed into a pattern using a developer, the so-called aspect ratio becomes too large, and as a result, the pattern collapses. Therefore, with the miniaturization, the film thickness of the photoresist film has also been gradually thinned.

[0004] On the other hand, in the processing of the processed substrate, a method of using the patterned photoresist film as an etching mask and processing the processed substrate by dry etching is generally used, but in reality, there is no dry etching method that can achieve complete etching selectivity between the photoresist film and the processed substrate, and therefore, in the processing of the processed substrate, the photoresist film is still damaged, and in the processing of the processed substrate, the photoresist film collapses, and the resist pattern cannot be correctly transferred to the processed substrate. Therefore, with the miniaturization of the pattern, a higher dry etching resistance of the photoresist composition has also been sought. Also, with the shortening of the wavelength of the exposure light, the resin used in the photoresist composition has sought a resin having a small light absorption in the exposure wavelength, and therefore, in response to the change to i-ray, KrF, ArF, the resin has gradually changed to a novolak resin, a polyhydroxystyrene, and a resin having an aliphatic polycyclic skeleton, but in reality, the etching speed in the aforementioned dry etching conditions has become faster and faster, and the latest photoresist composition having a high resolution has tended to have a weaker etching resistance.

[0005] Therefore, it has become urgent to ensure the material and the process in the processing step of the processed substrate by dry etching using a thinner and weaker etching resistant photoresist film.

[0006] As one of the methods for solving such a problem, there is a multilayer resist method. This method is a method in which a resist intermediate film that is different in etching selectivity from a photoresist film (i.e., a resist upper film) is interposed between the resist upper film and a substrate to be processed, after a pattern is obtained in the resist upper film, the pattern is transferred to the resist intermediate film by dry etching using the resist upper film pattern as a dry etching mask, and then the pattern is transferred to the substrate to be processed by dry etching using the resist intermediate film as a dry etching mask.

[0007] One of the multilayer resist methods is a three-layer resist method that can be implemented using a general resist composition used in a single-layer resist method. This three-layer resist method is, for example, a method in which an organic film derived from novolak or the like is formed on a substrate to be processed as a resist lower film, a silicon-containing film is formed on the resist lower film as a silicon-containing resist intermediate film, and a general organic photoresist film is formed on the silicon-containing resist intermediate film as a resist upper film. For dry etching by a plasma of a fluorine-based gas or the like, the resist upper film of the organic system can achieve a good etching selectivity ratio with respect to the silicon-containing resist intermediate film, and thus the resist upper film pattern is transferred to the silicon-containing resist intermediate film by dry etching using a plasma of a fluorine-based gas or the like. In addition, for etching using oxygen or hydrogen, the silicon-containing resist intermediate film can achieve a good etching selectivity ratio with respect to the resist lower film, and thus the silicon-containing resist intermediate film pattern is transferred to the resist lower film by etching using oxygen or hydrogen. According to this method, even if a photoresist composition that is not easy to form a pattern having a film thickness sufficient to directly process a substrate to be processed, or a photoresist composition whose dry etching resistance is not sufficient when used to process a substrate, is used, a pattern can be transferred to a silicon-containing film (a silicon-containing resist intermediate film), and thus a pattern of an organic film (a resist lower film) of novolak resin or the like having sufficient dry etching resistance when processing can be obtained.

[0008] In recent years, as a technique for replacing the powerful technique of combining ArF immersion lithography and a multiple exposure process, EUV (extreme ultraviolet) lithography using a vacuum ultraviolet light source with a wavelength of 13.5 nm has attracted attention. By using this technique, a fine pattern with a half pitch of 25 nm or less can be formed by one exposure.

[0009] On the other hand, in EUV lithography, high sensitivity of a resist material is strongly sought in order to compensate for the insufficient output of a light source. However, an increase in shot noise accompanying high sensitivity is closely related to an increase in line pattern edge roughness (LER, LWR), and thus achieving both high sensitivity and low edge roughness can be cited as one of the important issues in EUV lithography.

[0010] In recent years, the use of metal materials in resist materials has been investigated in an attempt to increase the sensitivity of the resist or to reduce the effects of shot noise. Compounds containing metal elements such as barium, titanium, hafnium, zirconium, and tin have a higher absorbance of EUV light than organic materials that do not contain metals, and it is expected that the photosensitivity of the resist or the effects of shot noise will be improved. Furthermore, a resist pattern containing metal can be combined with an underlayer film composed of a non-metal material, and a high selectivity etching process is expected.

[0011] For example, resist materials to which metal salts or organometallic complexes have been added (Patent Documents 1 and 2) or non-chemically amplified resist materials using nanoparticles of metal oxides (Patent Document 3, Non-Patent Document 1) have been investigated. However, the resolution of these metal-containing resists has not yet reached the level necessary for practical use, and further improvement in resolution is sought.

[0012] Furthermore, with the advent of ArF immersion lithography, EUV lithography, and the like, it has become possible to form even finer patterns. On the other hand, however, since the area of contact of a super-fine pattern is small, collapse of the pattern occurs very easily, and the suppression of pattern collapse is a very large problem. It is now believed that the interaction at the interface between the resist upper layer film and the resist underlayer film in a fine pattern has an effect on pattern collapse, and it is also necessary to improve the properties of the resist underlayer film.

[0013] In order to suppress pattern collapse, materials that contain polar functional groups such as lactone structures and urea structures and that improve the adhesion of the resist upper layer film have been reported (Patent Documents 4 and 5). However, in the current situation in which finer patterns are sought, these materials are not sufficient in terms of their ability to suppress pattern collapse. For the reasons above, materials that have a higher degree of ability to suppress pattern collapse and adhesion are sought.

[0014] Prior Art Documents

[0015] Patent Documents

[0016] [Patent Document 1] Japanese Patent No. 5708521

[0017] [Patent Document 2] Japanese Patent No. 5708522

[0018] [Patent Document 3] U.S. Patent No. 9310684

[0019] [Patent Document 4] International Publication No. 2003 / 017002

[0020] [Patent Document 5] International Publication No. 2018 / 143359

[0021] [Patent Document 6] Japanese Patent No. 5415982

[0022] Non-patent literature

[0023] [Non-patent literature 1] Proc. SPIE Vol. 7969, 796915 (2011) SUMMARY

[0024] [Problems to be solved by the Invention]

[0025] The present application was made in view of the foregoing circumstances, and aims to provide: an adhesion film forming material which can provide an adhesion film having high adhesion to an upper resist film and having an effect of suppressing collapse of a fine pattern in a fine patterning process using a multi-layer resist method in a semiconductor device manufacturing step, while forming a good pattern shape; a pattern forming method using the material; and a method for forming the adhesion film.

[0026] [Means for solving the problems]

[0027] To solve the above problems, the present application provides an adhesion film forming material for forming an adhesion film immediately below an upper resist film, the adhesion film forming material comprising:

[0028] (A) a resin having at least one structural unit containing a fluorine-substituted organic sulfonyl anion structure, and at least one structural unit represented by the following general formula (2) different from the structural unit containing the fluorine-substituted organic sulfonyl anion structure,

[0029] (B) a thermal acid generator, and

[0030] (C) an organic solvent.

[0031] [Chemical Formula 1]

[0032]

[0033] In the above general formula (2), R6 is a hydrogen atom or a methyl group, and R7 is a group selected from the following formulae (2-1) to (2-3).

[0034] [Chemical Formula 2]

[0035]

[0036] In the above formulae, a dotted line represents an atomic bond.

[0037] If the adhesion film forming material is as described above, an adhesion film having high adhesion to an upper resist film and having an effect of suppressing collapse of a fine pattern, while forming a good pattern shape, can be formed.

[0038] Further, in the present application, the aforementioned fluorine-substituted organic sulfonyl anion structure is preferably a structure represented by the following general formula (1).

[0039] [Chemical Formula 3]

[0040]

[0041] In the formula, R1 is a hydrogen atom or a methyl group. R2 is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -O-C(=O)-, Z 21 is a saturated hydrocarbylene group having 1 to 12 carbon atoms, and can also have a carbonyl group, an ester bond, or an ether bond. R3 to R5 are each independently a hydrocarbyl group having 1 to 21 carbon atoms, which can also have a hetero atom. Further, any two of R3, R4, and R5 can also be bonded to each other, and form a ring together with the sulfur atom to which they are bonded. A1 is a hydrogen atom or a trifluoromethyl group.

[0042] Further, in the present application, the aforementioned R2 in the aforementioned general formula (1) is preferably a bivalent organic group having a structure of an alicyclic ring.

[0043] If the adhesion film-forming material is such, an adhesion film having higher adhesion to the upper resist film and having higher collapse suppression effect of a fine pattern, while providing a better pattern shape, can be formed.

[0044] Further, in the present application, the aforementioned (C) organic solvent is preferably a mixture of one or more organic solvents having a boiling point of not more than 150°C and one or more organic solvents having a boiling point of more than 150°C and not more than 220°C.

[0045] If the adhesion film-forming material is such, since it has excellent film-forming properties and has sufficient solvent solubility, occurrence of coating defects can be suppressed.

[0046] Further, in the present application, the weight average molecular weight of the aforementioned (A) resin is preferably 5,000 to 70,000.

[0047] If the adhesion film-forming material contains a resin having a weight average molecular weight within such a range, it can have excellent film-forming properties, and can suppress generation of sublimates at the time of heat hardening, and can suppress contamination of the apparatus caused by the sublimates.

[0048] Further, in the present application, at least one or more of (D) a photoacid generator, (E) a surfactant, (F) a crosslinking agent, and (G) a plasticizer is preferably further contained.

[0049] By the presence or absence of these various additives or by the selection of these various additives, the film-forming properties, filling properties, optical properties, reduction of sublimates, and other properties that are required by the customer can be fine-tuned, and a more practical result is obtained.

[0050] Further, in the present application, the aforementioned resist upper layer film is preferably formed using a negative resist composition.

[0051] Further, in the present application, the aforementioned resist upper layer film is preferably formed using a resist upper layer film material that contains at least an organometallic compound and a solvent.

[0052] Further, the aforementioned organometallic compound preferably contains at least one selected from the group consisting of titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium.

[0053] If such a close film-forming material is used, the collapse of fine patterns can be suppressed, and the pattern shape, exposure sensitivity, and the like of the resist upper layer film can be appropriately adjusted. At the same time, contamination of the processed substrate caused by the metal compound when using a resist upper layer film material that contains an organometallic compound and a solvent can be prevented.

[0054] Further, the present application provides a pattern forming method that forms a pattern on a processed substrate, and includes the following steps:

[0055] (I-1) applying the close film-forming material described above to a processed substrate, and forming a close film by heat treatment,

[0056] (I-2) forming a resist upper layer film on the close film using a photoresist material,

[0057] (I-3) forming a circuit pattern on the aforementioned resist upper layer film by performing pattern exposure on the resist upper layer film and then developing using a developer,

[0058] (I-4) using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the aforementioned close film by dry etching, and

[0059] (I-5) using the close film on which the pattern has been transferred as a mask, processing the aforementioned processed substrate, and forming a pattern on the aforementioned processed substrate.

[0060] Further, the present application provides a pattern forming method that forms a pattern on a processed substrate, and includes the following steps:

[0061] (II-1) forming a resist lower layer film on a processed substrate,

[0062] (II-2) forming a silicon-containing resist intermediate film on the resist lower layer film,

[0063] (II-3) after coating the adhesion film forming material described above on the silicon-containing resist intermediate film, forming an adhesion film by heat treatment,

[0064] (II-4) forming a resist upper layer film on the adhesion film using a photoresist material,

[0065] (II-5) after subjecting the resist upper layer film to pattern exposure, developing it with a developer, forming a circuit pattern on the aforementioned resist upper layer film,

[0066] (II-6) using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the aforementioned adhesion film by dry etching,

[0067] (II-7) using the adhesion film on which the pattern has been formed as a mask, transferring the pattern to the aforementioned silicon-containing resist intermediate film by dry etching,

[0068] (II-8) using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask, transferring the pattern to the aforementioned resist lower layer film by dry etching, and

[0069] (II-9) using the resist lower layer film on which the pattern has been transferred as a mask, processing the aforementioned processed substrate, and forming a pattern on the aforementioned processed substrate.

[0070] Further, the present application provides a pattern forming method, which is a method of forming a pattern on a processed substrate, comprising the following steps:

[0071] (III-1) forming a resist lower layer film on a processed substrate,

[0072] (III-2) forming an inorganic hard mask intermediate film selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist lower layer film,

[0073] (III-3) after coating the adhesion film forming material described above on the inorganic hard mask intermediate film, forming an adhesion film by heat treatment,

[0074] (III-4) forming a resist upper layer film on the adhesion film using a photoresist material,

[0075] (III-5) after subjecting the resist upper layer film to pattern exposure, developing it with a developer, forming a circuit pattern on the aforementioned resist upper layer film,

[0076] (III-6) using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the aforementioned adhesion film by dry etching,

[0077] (III-7) using the patterned adhesion film as a mask, a pattern is transferred to the aforementioned inorganic hard mask interlayer film by dry etching,

[0078] (III-8) using the pattern-transferred inorganic hard mask interlayer film as a mask, a pattern is transferred to the aforementioned resist underlayer film, and

[0079] (III-9) using the pattern-transferred resist underlayer film as a mask, and processing the aforementioned processed substrate to form a pattern on the processed substrate.

[0080] Thus, the adhesion film forming material of the present application can be used in various pattern forming methods such as a 2-layer resist process, a 4-layer resist process in which the aforementioned adhesion film is formed on a silicon-containing interlayer film (a silicon-containing resist interlayer film, an inorganic hard mask interlayer film), and the like. If these pattern forming methods are used, pattern collapse can be effectively mitigated by adhesion film formation, and the optical lithography of the resist upper layer film is suitable.

[0081] At this time, the aforementioned inorganic hard mask interlayer film is preferably formed by a CVD method or an ALD method.

[0082] Further, the present application preferably uses optical lithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof as a method for forming a circuit pattern on the aforementioned resist upper layer film.

[0083] Further, the present application preferably uses alkali development or development with an organic solvent as a development method.

[0084] In the present application, by using the aforementioned pattern forming method, pattern formation can be performed well and efficiently.

[0085] Further, the present application preferably uses a semiconductor device substrate or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film is formed as the aforementioned processed substrate.

[0086] At this time, silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof is preferably used as the aforementioned metal.

[0087] If the pattern forming method of the present application is used, the aforementioned processed substrate is processed as described above to form a pattern.

[0088] Further, the present application provides a method for forming an adhesion film, which is a method for forming an adhesion film functioning as an adhesion layer used in a manufacturing step of a semiconductor device, wherein the adhesion film forming material described above is spin-coated on a substrate to be processed, and the substrate coated with the adhesion film forming material is heat-treated at a temperature of 100°C or higher and 300°C or lower for 10 to 600 seconds, thereby forming a hardened film.

[0089] Further, the present application provides a method for forming an adhesion film, which is a method for forming an adhesion film functioning as an adhesion layer used in a manufacturing step of a semiconductor device, wherein the adhesion film forming material described above is spin-coated on a substrate to be processed, and the substrate coated with the adhesion film forming material is heat-treated in an ambient gas having an oxygen concentration of 0.1% or higher and 21% or lower, thereby forming a hardened film.

[0090] By such a method, the cross-linking reaction at the time of forming the adhesion film can be promoted, and the intermixing with the resist upper layer film can be more highly suppressed. Further, by appropriately adjusting the heat treatment temperature, time, and oxygen concentration within the aforementioned ranges, the effect of suppressing the collapse of the pattern of the adhesion film for the application can be obtained, and the pattern shape adjustment property of the resist upper layer film can be obtained.

[0091] Further, the present application provides a method for forming an adhesion film, which is a method for forming an adhesion film functioning as an adhesion layer used in a manufacturing step of a semiconductor device, wherein the adhesion film forming material described above is spin-coated on a substrate to be processed, and the substrate coated with the adhesion film forming material is heat-treated in an ambient gas having an oxygen concentration of 0.1% or higher and 21% or lower, thereby forming a hardened film.

[0092] By such a method, even when the substrate to be processed contains a material unstable to heating in an oxygen ambient gas, the deterioration of the substrate to be processed will not occur, and the cross-linking reaction at the time of forming the adhesion film can be promoted, and the intermixing with the upper layer film can be more highly suppressed, and thus the method is useful.

[0093] [Effects of the Invention]

[0094] As explained above, the present invention provides a bonding film forming material that exhibits high adhesion to the upper resist film and suppresses the collapse of fine patterns. Furthermore, this bonding film forming material, possessing both high adhesion and the ability to suppress the collapse of fine patterns, allows for appropriate adjustment of the pattern shape and exposure sensitivity of the upper resist film. Therefore, it is extremely useful in multilayer resist processes, such as a four-layer resist process where the bonding film is formed on a silicon-containing intermediate film. Moreover, the bonding film forming method of the present invention allows for sufficient curing on the processed substrate, resulting in a bonding film with high adhesion to the upper resist film. Furthermore, the pattern forming method of the present invention enables the formation of fine patterns on the processed substrate with high precision in multilayer resist processes. Attached Figure Description

[0095] [ Figure 1 Figures (A) to (G) are explanatory diagrams of an example of the patterning method performed by the four-layer resist process of the present invention.

[0096] [ Figure 2 [This is an explanatory diagram showing the fit measurement method in the embodiments.] Detailed Implementation

[0097] In this specification, when an element is mentioned as being "immediately below" another element, the element and the other element are in direct contact, and there is no inserting element. Conversely, when an element is mentioned as being "below" another element, an inserting element can exist between them. Similarly, when an element is mentioned as being "immediately above" another element, the element and the other element are in direct contact, and there is no inserting element; while when an element is mentioned as being "above" another element, an inserting element can exist between them.

[0098] As mentioned above, we seek a bonding film forming material that has high adhesion to the upper layer of the resist film and has the effect of suppressing the collapse of the micro-pattern in the micro-patterning process using the multilayer resist method in the semiconductor device manufacturing process, a pattern forming method using the material, and a bonding film forming method.

[0099] To date, it has been demonstrated that resist underlayer film materials containing (meth)acrylate resins with α-fluorosulfonic acid bonded to the main chain by light and / or heat as repeating units are effective in improving the resist pattern shape and adhesion to the resist (Patent Document 6). This invention is believed to prevent tailing and scum formation in the gaps after development by having α-fluorosulfonic acid present at the bottom of the resist film and preventing the deactivation of acids within the film. However, the applicability of this invention is limited to positive resists, and its effectiveness in negative resists is particularly unclear.

[0100] In a pattern (hereinafter referred to as a negative pattern) obtained by negative development, if the film properties of the photoresist film before exposure and the negative pattern after exposure are compared, the amount of hydrophilic groups such as carboxyl groups and phenolic hydroxyl groups increases due to the dissociation of acid-labile groups caused by the acid generated by exposure.

[0101] Therefore, the inventors of the present application conceived that by using a resin that generates a sulfonic acid bonded to the main chain, which forms a hydrogen bond with the aforementioned carboxyl group and phenolic hydroxyl group, a superiorly adherent film to a negative pattern can be developed. As a result of repeated and intensive studies, it was found that an adherent film-forming material using a compound having a specific structure as a main component, a pattern-forming method using the material, and a method for forming an adherent film are very effective, and thus the present application was completed.

[0102] That is, the present application is an adherent film-forming material for forming an adherent film immediately below an upper layer film of a resist, the adherent film-forming material comprising:

[0103] (A) a resin having at least one structural unit having a structure containing a fluorine-substituted organic sulfonyl anion, and at least one structural unit represented by the following general formula (2) that is different from the structural unit having the structure containing a fluorine-substituted organic sulfonyl anion,

[0104] (B) a thermal acid generator, and

[0105] (C) an organic solvent.

[0106] [Chemical Formula 4]

[0107]

[0108] In the general formula (2), R6 is a hydrogen atom or a methyl group, and R7 is a group selected from the following formulae (2-1) to (2-3).

[0109] [Chemical Formula 5]

[0110]

[0111] In the formulae, the dotted line represents an atomic bond.

[0112] Hereinafter, the present application will be described in detail, but the present application is not limited thereto.

[0113] [Adherent film-forming material]

[0114] The present application provides an adherent film-forming material for forming an adherent film immediately below an upper layer film of a resist, the adherent film-forming material comprising:

[0115] (A) a resin having at least one structural unit containing a fluorine-substituted organic sulfonyl anion structure, and having at least one structural unit represented by the following general formula (2) which is different from the aforementioned structural unit containing a fluorine-substituted organic sulfonyl anion structure,

[0116] (B) a thermal acid generator, and

[0117] (C) an organic solvent.

[0118] [Chemical Formula 6]

[0119]

[0120] In the aforementioned general formula (2), R6is a hydrogen atom or a methyl group, and R7is a group selected from the following formulae (2-1) to (2-3).

[0121] [Chemical Formula 7]

[0122]

[0123] In the aforementioned formulae, a dotted line represents an atomic bond.

[0124] In addition, in the adhesion film-forming material of the present application, the (A) resin can be used alone or in combination with two or more kinds. Furthermore, the aforementioned adhesion film-forming material can contain components other than the aforementioned (A) to (C) components. Each component is described below.

[0125] [(A) Resin]

[0126] The (A) resin contained in the adhesion film-forming material of the present application has at least one structural unit containing a fluorine-substituted organic sulfonyl anion structure, and has at least one structural unit represented by the following general formula (2) which is different from the aforementioned structural unit containing a fluorine-substituted organic sulfonyl anion structure.

[0127] [Chemical Formula 8]

[0128]

[0129] In the aforementioned general formula (2), R6is a hydrogen atom or a methyl group, and R7is a group selected from the following formulae (2-1) to (2-3).

[0130] [Chemical Formula 9]

[0131]

[0132] In the aforementioned formulae, a dotted line represents an atomic bond.

[0133] The fluorine-substituted organic sulfonyl anion structure is preferably a structure represented by the following general formula (1), but is not limited thereto.

[0134] [Chem. 10]

[0135]

[0136] In the formula, R1is a hydrogen atom or a methyl group. R2is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -O-C(=O)-, Z 21 is a saturated hydrocarbylene group having 1 to 12 carbon atoms, and can also contain a carbonyl group, an ester bond, or an ether bond. R3to R5are each independently a hydrocarbyl group having 1 to 21 carbon atoms which can also contain a hetero atom. Also, any two of R3, R4, and R5may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. A1is a hydrogen atom or a trifluoromethyl group.

[0137] R2in the above general formula (1) is -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -O-C(=O)-, Z 21 The saturated hydrocarbylene group having 1 to 12 carbon atoms which can also contain a carbonyl group, an ester bond, or an ether bond represented by R2in the above general formula (1) can be specifically exemplified as follows, but is not limited thereto.

[0138] [Chem. 11]

[0139]

[0140] In the formula, the dotted line represents an atomic bond.

[0141] The aforementioned R2in the above general formula (1) is preferably a bivalent organic group containing an alicyclic structure.

[0142] The structural unit represented by the above general formula (1) functions as an acid generating group. A sulfonic acid is generated from this structural unit, and it improves the adhesion to a resist by forming a hydrogen bond with the pattern. Also, since the generated acid is bonded to the polymer main chain, it is possible to prevent the deterioration of the pattern roughness of the upper layer of the resist film and the like caused by excessive acid diffusion.

[0143] The anion of the monomer of the above general formula (1) can be specifically exemplified as follows, but is not limited thereto. In the following formula, R1is the same as described above.

[0144] [Chem. 12]

[0145]

[0146] [Chem. 13]

[0147]

[0148] Cations of the monomer represented by the above general formula (1) include triphenyl sulfonium, 4-hydroxyphenyldiphenyl sulfonium, bis(4-hydroxyphenyl)phenyl sulfonium, tris(4-hydroxyphenyl) sulfonium, 4-t-butoxyphenyldiphenyl sulfonium, bis(4-t-butoxyphenyl)phenyl sulfonium, tris(4-t-butoxyphenyl) sulfonium, 3-t-butoxyphenyldiphenyl sulfonium, bis(3-t-butoxyphenyl)phenyl sulfonium, tris(3-t-butoxyphenyl) sulfonium, 3,4-di(t-butoxyphenyl)diphenyl sulfonium, bis(3,4-di(t-butoxy)phenyl)phenyl sulfonium, tris(3,4-di(t-butoxy)phenyl) sulfonium, diphenyl(4-thiophenoxyphenyl) sulfonium, 4-t-butoxycarbonylmethyloxyphenyldiphenyl sulfonium, tris(4-t-butoxycarbonylmethyloxyphenyl) sulfonium, (4-t-butoxyphenyl)bis(4-dimethylaminophenyl) sulfonium, tris(4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenyl sulfonium, (4-hydroxy-3,5-dimethylphenyl)diphenyl sulfonium, (4-n-hexyloxy-3,5-dimethylphenyl)diphenyl sulfonium, dimethyl(2-naphthyl) sulfonium, 4-hydroxyphenyldimethyl sulfonium, 4-methoxyphenyldimethyl sulfonium, trimethyl sulfonium, 2-oxocyclohexylcyclohexylmethyl sulfonium, trinaphthyl sulfonium, tribenzyl sulfonium, diphenylmethyl sulfonium, dimethylphenyl sulfonium, 2-oxo-2-phenylethylthiacyclopentanium, diphenyl 2-thienyl sulfonium, 4-n-butoxynaphthyl-1 -thiacyclopentanium, 2-n-butoxynaphthyl-1 -thiacyclopentanium, 4-methoxynaphthyl-1 -thiacyclopentanium, 2-methoxynaphthyl-1 -thiacyclopentanium, and the like. More desirably, triphenyl sulfonium, 4-t-butoxyphenyldiphenyl sulfonium, tris(4-t-butoxyphenyl) sulfonium, dimethylphenyl sulfonium, and the like can be mentioned. In addition, the following structural representations and the like can also be mentioned, but are not limited thereto.

[0149] [Chemical Formula 14]

[0150]

[0151] The structural unit represented by the above general formula (2) functions as a crosslinking group, and imparts hardenability without impairing adhesion to the upper layer of the resist and the processed substrate or the silicon-containing intermediate film, through the interaction of the hydroxyl groups generated by the ring-opening reaction of the epoxide or oxetane structure upon hardening.

[0152] Further, the structural unit represented by the above general formula (2) can be specifically exemplified as follows, and the like. R6is the same as described above.

[0153] [Chemical Formula 15]

[0154]

[0155] Further, the (A) resin of the adhesion film-forming material of the present application preferably contains a structural unit represented by the above general formula (1) and (2) in the structural unit, and one or two or more of the structural units represented by the above general formula (1) or (2) can be used in combination.

[0156] By combining a plurality of structural units, not only the adhesion can be improved and the effect of suppressing collapse of a fine pattern can be enhanced, but also the pattern shape of the resist upper layer film, the exposure sensitivity, and the like can be appropriately adjusted.

[0157] Further, in the present application, the molar fraction of the structural unit represented by the above general formula (1) in the (A) resin is preferably 5% or more and 50% or less, and more preferably 5% or more and 30% or less. Further, the molar fraction of the structural unit represented by the above general formula (2) is preferably 30% or more and 95% or less, and more preferably 40% or more and 90% or less. By combining the structural units in such a range, the hardenability can be maintained while imparting adhesion.

[0158] Further, when the total of the molar fractions of the structural units represented by the above general formula (1) and (2) is less than 100%, the (A) resin contains other structural units. In this case, any of the following structural units can be used in combination: other acrylates, other methacrylates, other acrylamides, other methacrylamides, crotonates, maleates, itaconates, and other α,β-unsaturated carboxylates; methacrylic acid, acrylic acid, maleic acid, itaconic acid, and other α,β-unsaturated carboxylic acids; acrylonitrile; methacrylonitrile; 5,5-dimethyl-3-methylene-2-oxotetrahydrofuran and other α,β-unsaturated lactones; norbornene derivatives, cyclododecene derivatives, and other cyclic olefins; maleic anhydride, itaconic anhydride, and other α,β-unsaturated carboxylic anhydrides; allyl ethers; vinyl ethers; vinyl esters; and vinyl silanes. 2,5 .1 7,10

[0159] If the adhesion film-forming material containing such a resin is used, an adhesion film-forming material having high adhesion to a resist upper layer film and having an effect of suppressing collapse of a fine pattern, and which is easy to manufacture, can be formed.

[0160] By using the adhesion film-forming material containing such a resin in the formation of a multilayer resist film used in fine processing in the manufacturing process of a semiconductor device or the like, an adhesion film-forming material for forming an adhesion film having high adhesion to a resist upper layer film and having an effect of suppressing collapse of a fine pattern, a method for forming an adhesion film, and a pattern forming method can be provided.

[0161] ​The aforementioned resin can be synthesized by polymerizing each monomer protected with a protecting group as necessary using a known method, and then performing a deprotection reaction as necessary. The polymerization reaction is not particularly limited, and is preferably radical polymerization, anionic polymerization. For these methods, reference can be made to Japanese Patent Application Publication No. 2004-115630.

[0162] The weight average molecular weight (Mw) of the aforementioned resin is preferably 5,000 to 70,000, more preferably 15,000 to 50,000. If the Mw is 5,000 or more, excellent film formability can be obtained, and the generation of sublimates during heat hardening can be suppressed, and the contamination of the apparatus due to sublimates can be suppressed. On the other hand, if the Mw is 70,000 or less, the occurrence of poor coatability, coating defects due to insufficient solubility in a solvent can be suppressed. Also, the molecular weight distribution (Mw / Mn) of the aforementioned resin is preferably 1.0 to 2.8, more preferably 1.0 to 2.5. In addition, in the present application, the Mw and the molecular weight distribution are measured values converted to polystyrene using gel permeation chromatography (GPC) with tetrahydrofuran (THF) as the solvent.

[0163] [(B) Thermal acid generator]

[0164] In the adhesion film forming material of the present application, a (B) thermal acid generator is added in order to promote the crosslinking reaction due to heat.

[0165] The thermal acid generator (B) that can be used in the organic film material for semiconductor device production of the present application can be exemplified by the following general formula (3) or the like.

[0166] [Chemical 16]

[0167]

[0168] In the formula, K - represents a non-nucleophilic counter ion. R8, R9, R 10 and R 11 each represent a hydrogen atom or a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having a carbon number of 1 to 12, an aryl group having a carbon number of 6 to 20, or an aralkyl group or aralkyloxyalkyl group having a carbon number of 7 to 12, and a part or all of the hydrogen atoms of these groups can be substituted with an alkoxy group or the like. Also, R8and R9, R8and R9and R 10 may form a ring, and when a ring is formed, R8and R9and R 10 represents an alkylene group having a carbon number of 3 to 10, or an aromatic heterocycle having a nitrogen atom in the ring.

[0169] In the above, R8, R9, R 10 and R 11The same or different, in particular, in the case of alkyl, can be listed: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl, etc. In the case of alkenyl, can be listed: vinyl, allyl, propenyl, butenyl, hexenyl, cyclohexenyl, etc. In the case of oxoalkyl, can be listed: 2-oxocyclopentyl, 2-oxocyclohexyl, 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, 2-(4-methylcyclohexyl)-2-oxoethyl, etc. In the case of oxoalkenyl, can be listed: 2-oxo-4-cyclohexenyl, 2-oxo-4-propenyl, etc. In the case of aryl, can be listed: phenyl, naphthyl, etc., or p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-t-butoxyphenyl, m-t-butoxyphenyl, etc. alkoxyphenyl; 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-t-butylphenyl, 4-butylphenyl, dimethylphenyl, etc. alkylphenyl; methylnaphthyl, ethylnaphthyl, etc. alkyl naphthyl; methoxynaphthyl, ethoxynaphthyl, etc. alkyloxynaphthyl; dimethylnaphthyl, diethylnaphthyl, etc. dialkyl naphthyl; dimethoxynaphthyl, diethoxynaphthyl, etc. dialkoxy naphthyl, etc. In the case of aralkyl, can be listed: benzyl, phenylethyl, phenethyl, etc. In the case of aryloxoalkyl, can be listed: 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, 2-(2-naphthyl)-2-oxoethyl, etc. 2-aryl-2-oxoethyl, etc.

[0170] Further, R8, R9, R 10 , R 11When the aromatic heterocycle has a nitrogen atom in the ring of the formula, imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-l-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(l-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(l-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenoxazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, etc. can be exemplified.

[0171] The above, with respect to K - chloride ion, bromide ion, etc.; trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion, nonafluorobutanesulfonate ion, etc.; toluenesulfonate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, 1,2,3,4,5-pentafluorobenzenesulfonate ion, etc.; methanesulfonate ion, butanesulfonate ion, etc.; bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, bis(perfluorobutylsulfonyl)imide, etc.; tris(trifluoromethylsulfonyl)methide, tris(perfluoroethylsulfonyl)methide, etc.; and the like can be exemplified. Further, the following α-fluorine-substituted sulfonate ions represented by the following general formula (4) and the following α, β-fluorine-substituted sulfonate ions represented by the following general formula (5) can be exemplified.

[0172] [Chemical Formula 17]

[0173]

[0174] [Chemical Formula 18]

[0175] R 13 -CF2-CF2-SO3 - (5)

[0176] In the above general formula (4), R 12 is a hydrogen atom, a linear or branched or cyclic alkyl group having 1 to 23 carbon atoms, an acyl group, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group. In the above general formula (5), R 13 is a hydrogen atom, a linear or branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0177] The aforementioned thermal acid generator can be specifically exemplified by the following, etc.

[0178] [Chemical 19]

[0179]

[0180] The (B) thermal acid generator contained in the adhesion film forming material of the present application can be used alone or in combination with two or more kinds. The amount of the thermal acid generator to be added is preferably 0.05 to 30 parts, more preferably 0.1 to 10 parts, relative to 100 parts of the aforementioned (A) resin. If it is 0.05 parts or more, the amount of acid generated and the crosslinking reaction are sufficient, and if it is 30 parts or less, the concern about the mixing phenomenon caused by the movement of acid to the upper layer resist is low.

[0181] [(C) Organic solvent]

[0182] The (C) organic solvent contained in the adhesion film forming material used in the method for forming the adhesion film of the present application is not particularly limited if it is one that dissolves the aforementioned (A) resin, (B) thermal acid generator, and other additives if present, and is preferably a mixture of one or more organic solvents having a boiling point of 150°C or less and one or more organic solvents having a boiling point of 150°C or more and a boiling point of 220°C or less. Specifically, the following can be used: ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone as described in paragraphs

[0144] to

[0145] of Japanese Patent Application Publication No. 2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene 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. The organic solvents having a boiling point of 150°C or less can desirably be propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, cyclopentanone, and a mixture of two or more thereof. The organic solvents having a boiling point of 150°C or more and a boiling point of 220°C or less can desirably be cyclohexanone, diacetone alcohol, ethyl lactate, γ-butyrolactone, and a mixture of two or more thereof.

[0183] [Other additives]

[0184] The adhesion film forming material of the present application can contain one or more of (D) a photoacid generator, (E) a surfactant, (F) a crosslinking agent, and (G) a plasticizer in addition to the aforementioned (A) to (C) components. Each of these components is described below.

[0185] [(D) Photoacid generator]

[0186] The adhesion film forming material of the present application can contain (D) a photoacid generator in order to appropriately adjust the pattern shape, exposure sensitivity, and the like of the resist upper layer film. The photoacid generator can be used alone or in combination with two or more. The photoacid generator can be, for example, one described in paragraphs

[0160] to

[0179] of Japanese Patent Application Publication No. 2009-126940. The amount of photoacid generator added is preferably 0.05 to 30 parts, and more preferably 0.1 to 10 parts, relative to 100 parts of the aforementioned (A) resin. When the amount of photoacid generator added is within the aforementioned range, the resolution is good, and there is no concern that foreign matter will occur after development of the resist or at the time of peeling.

[0187] [(E) Surfactant]

[0188] In the adhesion film-forming material of the present application, (E) a surfactant can be added in order to improve the coatability in spin coating. The surfactant can be used alone or in combination with two or more. The surfactant can be used, for example, as described in

[0142] to

[0147] of Japanese Patent Application Publication No. 2009-269953. When the surfactant is added, the amount of addition is preferably 0.001 to 20 parts, more preferably 0.01 to 10 parts, relative to 100 parts of the aforementioned (A) resin.

[0189] [(F) crosslinking agent]

[0190] Further, in the adhesion film-forming material of the present application, (F) a crosslinking agent can also be added in order to improve the hardening property and more inhibit the mutual mixing with the resist upper layer film. The crosslinking agent is not particularly limited and various crosslinking agents of known systems can be widely used. As examples, melamine-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, epoxy-based crosslinking agents, and phenol-based crosslinking agents can be exemplified. The aforementioned (F) crosslinking agent can be used alone or in combination with two or more, and the amount of addition of the crosslinking agent is preferably 5 to 50 parts, more preferably 10 to 40 parts, relative to 100 parts of the aforementioned (A) resin. If the amount of addition is 5 parts or more, sufficient hardening property can be exhibited and the mutual mixing with the resist upper layer film can be inhibited. On the other hand, if the amount of addition is 50 parts or less, there is no concern of adhesion property deterioration caused by the decrease in the ratio of the (A) resin in the composition.

[0191] The melamine-based crosslinking agent can specifically include, for example, hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxyl and / or hydroxyl substituted bodies, and their partial self-condensates. The glycoluril-based crosslinking agent can specifically include, for example, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, their alkoxyl and / or hydroxyl substituted bodies, and their partial self-condensates. The benzoguanamine-based crosslinking agent can specifically include, for example, tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxyl and / or hydroxyl substituted bodies, and their partial self-condensates. The urea-based crosslinking agent can specifically include, for example, dimethoxymethylated dimethoxy ethylene urea, its alkoxyl and / or hydroxyl substituted bodies, and their partial self-condensates. The β-hydroxyalkylamide-based crosslinking agent can specifically include, for example, N,N,N',N'-tetra(2-hydroxyethyl)adipamide. The isocyanurate-based crosslinking agent can specifically include, for example, trisglycidyl isocyanurate, triallyl isocyanurate. The aziridine-based crosslinking agent can specifically include, for example, 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. The oxazoline-based crosslinking agent can specifically include, for example, 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tert-butyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), 2-isopropenyl oxazoline copolymer. The epoxy-based crosslinking agent can specifically include, for example, diepoxypropyl ether, ethylene glycol diepoxypropyl ether, 1,4-butanediol diepoxypropyl ether, 1,4-cyclohexanedimethanol diepoxypropyl ether, poly(epoxypropyl methacrylate), trimethylolethane triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, neopentatetraol tetraepoxypropyl ether.

[0192] The phenol-based crosslinking agent can specifically include a compound represented by the following general formula (6).

[0193] [Chemical Formula 20]

[0194]

[0195] In the formula, Q is a single bond, or a q-valent hydrocarbon group having 1 to 20 carbons. R 14 is a hydrogen atom, or an alkyl group having 1 to 20 carbons. q is an integer of 1 to 5.

[0196] Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbons. q is an integer of 1 to 5, and is more preferably 2 or 3. Q can be exemplified by, for example, methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, methylnaphthalene, ethylnaphthalene, eicosane. R 14 is a hydrogen atom or an alkyl group having 1 to 20 carbons. The alkyl group having 1 to 20 carbons can be exemplified by, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, eicosyl, and is preferably a hydrogen atom or a methyl group.

[0197] Examples of the compound represented by the above general formula (6) can be exemplified by the following compounds. Among them, from the viewpoint of improving the curing properties of the adhesion film and the film thickness uniformity, it is preferable to use triphenylol methane, triphenylol ethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and hexamethoxymethylate of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene.

[0198] [Chemical Formula 21]

[0199]

[0200] [Chemical Formula 22]

[0201]

[0202] The aforementioned (F) crosslinking agent can be used alone or in combination with two or more kinds. The amount of the (F) crosslinking agent to be added is preferably 10 to 50% by mass, and more preferably 15 to 30% by mass, relative to 100 parts by mass of the aforementioned (A) resin. If the amount of the (F) crosslinking agent to be added is 10% by mass or more, sufficient curing properties can be obtained, and the mutual mixing of the upper layer film and the resist can be suppressed. On the other hand, if the amount of the (F) crosslinking agent to be added is 50% by mass or less, the ratio of the (A) resin in the composition does not become low, and there is no concern about the adhesion being deteriorated.

[0203] [(G) Plasticizer]

[0204] Further, a plasticizer can be added to the adhesion film-forming material of the present application. The plasticizer is not particularly limited, and various kinds of plasticizers known in the art can be widely used. Examples of the plasticizer include, for example, low molecular compounds such as phthalate esters, adipate esters, phosphate esters, trimellitate esters, citrate esters, and the like; polymers such as polyether-based polymers, polyester-based polymers, and polyacetal-based polymers described in Japanese Patent Application Publication No. 2013-253227. The amount of the (G) plasticizer to be added is preferably 5 to 500% by mass, relative to 100 parts by mass of the aforementioned (A) resin. If the amount of the (G) plasticizer to be added is within this range, the filling and the averaging of the pattern are excellent.

[0205] The thickness of the adhesion film forming material used in the present application is appropriately selected and is preferably set to 2 to 100 nm, and is more preferably set to 5 to 20 nm.

[0206] Further, the adhesion film forming material of the present application is extremely useful as an adhesion film material for a multi-layer resist process such as a 2-layer resist process, or a 4-layer resist process using a resist underlayer film and a silicon-containing intermediate film.

[0207] The aforementioned silicon-containing intermediate film can be set to a silicon-containing resist intermediate film or an inorganic hard mask intermediate film in accordance with a later-described pattern forming method. The aforementioned inorganic hard mask intermediate film is preferably selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film.

[0208] [Method for forming adhesion film]

[0209] The present application provides a method for forming an adhesion film having high adhesion to a resist upper layer film and having an effect of suppressing collapse of a fine pattern in a fine patterning process using a multi-layer resist method in a semiconductor device manufacturing step using the aforementioned adhesion film forming material.

[0210] In the method for forming an adhesion film of the present application, the aforementioned adhesion film forming material is applied onto a substrate to be processed by a spin coating method or the like. After the spin coating, baking (heat treatment) is performed to evaporate an organic solvent, prevent mixing with a resist upper layer film or a silicon-containing intermediate film, and promote cross-linking reaction. The baking is preferably performed at a temperature of 100°C or higher and 300°C or lower for 10 to 600 seconds, and is more preferably performed at a temperature of 200°C or higher and 250°C or lower for 10 to 300 seconds. In consideration of damage to the adhesion film and influence on wafer distortion, the upper limit of the heating temperature during wafer processing in photolithography is preferably set to 300°C or lower, and is more preferably set to 250°C or lower.

[0211] That is, the present application provides a method for forming an adhesion film that functions as an adhesion layer used in a manufacturing step of a semiconductor device, in which an adhesion film forming material described above is spin-coated on a substrate to be processed, and the substrate on which the adhesion film forming material has been applied is subjected to heat treatment at a temperature of 100°C or higher and 300°C or lower for 10 to 600 seconds, thereby forming a hardened film.

[0212] Further, in the method for forming an adhesion film of the present application, the adhesion film forming material of the present application and the aforementioned adhesion film forming material can also be applied onto a substrate to be processed by a spin coating method or the like, and the adhesion film forming material can be calcined in an ambient gas having an oxygen concentration of 0.1% or higher and 21% or lower and hardened, thereby forming an adhesion film. By calcining the adhesion film forming material of the present application in such an oxygen ambient gas, a sufficiently hardened film can be obtained.

[0213] That is, the present application provides a method for forming an adhesion film, which is a method for forming an adhesion film functioning as an adhesion layer used in a manufacturing step of a semiconductor device, wherein an adhesion film forming material described above is spin-coated on a substrate to be processed, and the substrate to which the adhesion film forming material has been coated is heat-treated in an ambient gas having an oxygen concentration of 0.1% or more and 21% or less, thereby forming a hardened film.

[0214] The ambient gas in the baking can be not only air but also a noble gas such as N2, Ar, He, etc. In this case, the ambient gas can be set to have an oxygen concentration of less than 0.1%. Also, the baking temperature, etc. can be set as described above. Even when the substrate to be processed contains a material unstable to heating in an oxygen-containing ambient gas, the degradation of the substrate to be processed can be prevented, and the cross-linking reaction at the time of forming the adhesion film can be promoted.

[0215] That is, the present application provides a method for forming an adhesion film, which is a method for forming an adhesion film functioning as an adhesion layer used in a manufacturing step of a semiconductor device, wherein an adhesion film forming material described above is spin-coated on a substrate to be processed, and the substrate to which the adhesion film forming material has been coated is heat-treated in an ambient gas having an oxygen concentration of less than 0.1%, thereby forming a hardened film.

[0216] [Pattern forming method]

[0217] The present application provides a pattern forming method, which is a method for forming a pattern on a substrate to be processed, having the following steps:

[0218] (I-1) forming an adhesion film by heat-treating an adhesion film forming material described above after coating the adhesion film forming material on a substrate to be processed,

[0219] (I-2) forming a resist upper layer film using a photoresist material on the adhesion film,

[0220] (I-3) forming a circuit pattern on the resist upper layer film by developing the resist upper layer film after performing pattern exposure on the resist upper layer film,

[0221] (I-4) transferring a pattern on the adhesion film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask, and

[0222] (I-5) forming a pattern on the substrate to be processed by processing the substrate to be processed using the adhesion film on which the pattern has been transferred as a mask.

[0223] The present application provides a pattern forming method. The pattern forming method includes the following steps: (I-1) forming an organic film on a substrate to be processed; (I-2) forming a silicon-containing intermediate film on the organic film; (I-3) forming a tight film on the silicon-containing intermediate film; and (I-4) forming a photoresist upper film on the tight film. The pattern forming method further includes the following steps: (I-5) exposing the photoresist upper film to light and developing the photoresist upper film to form a circuit pattern; (I-6) using the circuit patterned photoresist upper film as a mask to transfer the circuit pattern to the tight film by dry etching; (I-7) using the patterned tight film as a mask to transfer the circuit pattern to the silicon-containing intermediate film by dry etching; and (I-8) using the patterned silicon-containing intermediate film as a mask to transfer the circuit pattern to the organic film by dry etching.

[0224] The present application provides a pattern forming method. The pattern forming method includes the following steps: (I-1) forming an organic film on a substrate to be processed; (I-2) forming a silicon-containing intermediate film on the organic film; (I-3) forming a tight film on the silicon-containing intermediate film; and (I-4) forming a photoresist upper film on the tight film. The pattern forming method further includes the following steps: (I-5) exposing the photoresist upper film to light and developing the photoresist upper film to form a circuit pattern; (I-6) using the circuit patterned photoresist upper film as a mask to transfer the circuit pattern to the tight film by dry etching; (I-7) using the patterned tight film as a mask to transfer the circuit pattern to the silicon-containing intermediate film by dry etching; and (I-8) using the patterned silicon-containing intermediate film as a mask to transfer the circuit pattern to the organic film by dry etching.

[0225] (I-1) forming an organic film on a substrate to be processed,

[0226] (I-2) forming a silicon-containing intermediate film on the organic film,

[0227] (I-3) forming a tight film on the silicon-containing intermediate film by applying a tight film forming material to the silicon-containing intermediate film and then performing a heat treatment,

[0228] (I-4) forming a photoresist upper film on the tight film,

[0229] (I-5) exposing the photoresist upper film to light and developing the photoresist upper film to form a circuit pattern,

[0230] (I-6) using the circuit patterned photoresist upper film as a mask to transfer the circuit pattern to the tight film by dry etching,

[0231] (I-7) using the patterned tight film as a mask to transfer the circuit pattern to the silicon-containing intermediate film by dry etching,

[0232] (II-8) using the pattern-transferred silicon-containing resist intermediate film as a mask, the pattern is transferred to the aforementioned resist underlayer film and

[0233] (II-9) using the pattern-transferred resist underlayer film as a mask, the aforementioned processed substrate is processed to form a pattern on the aforementioned processed substrate.

[0234] The silicon-containing resist intermediate film of the aforementioned 4-layer resist process can also desirably use a polysilsequioxane-based intermediate film. By having an antireflection effect in the silicon-containing resist intermediate film, reflection can be suppressed. In particular, for 193 nm exposure, if a material containing a large amount of aromatic groups and having high substrate etching resistance is used as the resist underlayer film, the k value becomes high and substrate reflection becomes high, but by suppressing reflection with the silicon-containing resist intermediate film, substrate reflection can be controlled to 0.5% or less. For a silicon-containing resist intermediate film having an antireflection effect, a polysilsequioxane having a pendant anthracene group and crosslinked by acid or heat can be desirably used for 248 nm and 157 nm exposure, and a polysilsequioxane having a pendant phenyl group or a light-absorbing group having a silicon-silicon bond and crosslinked by acid or heat can be desirably used for 193 nm exposure.

[0235] In this case, the formation of the silicon-containing resist intermediate film by spin coating is simpler and more cost-effective than by CVD.

[0236] Also, an inorganic hard mask intermediate film can be formed as the silicon-containing intermediate film, in which case an organic film material can be used to form the resist underlayer film on at least the processed substrate, an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the resist underlayer film, a film adhesion layer is formed on the inorganic hard mask intermediate film using the film adhesion layer-forming material of the present application, a resist upper layer film is formed on the film adhesion layer using a resist upper layer film-forming material composed of a photoresist composition, the pattern circuit region of the aforementioned resist upper layer film is exposed, and development is performed using a developer to form a resist upper layer film pattern in the aforementioned resist upper layer film, the resulting resist upper layer film pattern is used as an etching mask to etch the aforementioned film adhesion layer and form a film adhesion layer pattern, the resulting film adhesion layer pattern is used as an etching mask to etch the aforementioned inorganic hard mask intermediate film and form an inorganic hard mask intermediate film pattern, the resulting inorganic hard mask intermediate film pattern is used as an etching mask to etch the aforementioned resist underlayer film and form a resist underlayer film pattern, and the resulting resist underlayer film pattern is used as an etching mask to etch the aforementioned processed substrate and form a pattern on the aforementioned processed substrate.

[0237] That is, a pattern forming method is provided, which is a method of forming a pattern on a processed substrate, having the following steps:

[0238] (III-1) forming a resist underlayer film on a substrate to be processed,

[0239] (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film,

[0240] (III-3) applying the adhesion film forming material described above to the inorganic hard mask intermediate film, and forming an adhesion film by heat treatment,

[0241] (III-4) forming a resist upper layer film using a photoresist material on the adhesion film,

[0242] (III-5) forming a circuit pattern on the resist upper layer film by performing pattern exposure on the resist upper layer film and then developing it using a developer,

[0243] (III-6) transferring the pattern to the adhesion film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask,

[0244] (III-7) transferring the pattern to the inorganic hard mask intermediate film by dry etching using the adhesion film on which the pattern has been formed as a mask,

[0245] (III-8) transferring the pattern to the resist underlayer film by dry etching using the inorganic hard mask intermediate film on which the pattern has been transferred as a mask, and

[0246] (III-9) forming a pattern on the substrate to be processed by processing the substrate to be processed using the resist underlayer film on which the pattern has been transferred as a mask.

[0247] When forming the inorganic hard mask intermediate film on the resist underlayer film as described above, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. It is particularly preferable to form the inorganic hard mask intermediate film by a CVD method or an ALD method. For example, in the case of a method for forming a silicon nitride film, Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377 are described. The film thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, and more preferably 10 to 100 nm. In the case of the inorganic hard mask intermediate film, it is most preferable to use a SiON film having a high effect as an antireflection film. Since the substrate temperature during formation of the SiON film reaches 300 to 500°C, the resist underlayer film needs to withstand a temperature of 300 to 500°C.

[0248] The upper resist film in the foregoing 4-layer resist process can be either positive or negative, and the same photoresist composition as conventionally used can be used, but one formed using a negative resist composition is preferable. Also, the upper resist film is preferably one formed using an upper resist film material containing at least an organic metal compound and a solvent, and the organic metal compound is preferably at least one selected from the group consisting of titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium. The prebake after spin-coating the photoresist composition is preferably in the range of 60 to 180°C for 10 to 300 seconds. Thereafter, exposure is performed following the conventional method, and post-exposure baking (PEB), development, and the like are performed to obtain a resist upper film pattern. The thickness of the resist upper film is not particularly limited, and is preferably in the range of 30 to 500 nm, and more preferably in the range of 50 to 400 nm.

[0249] The circuit pattern is formed in the resist upper film to form a resist upper film pattern. The circuit pattern is formed using optical lithography with light having a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprint, or a combination thereof.

[0250] In addition, as the exposure light, high-energy rays having a wavelength of 300 nm or less can be used, and specific examples include far ultraviolet rays, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 laser (157 nm), a Kr2 laser (146 nm), an Ar2 laser (126 nm), soft X-rays (EUV) having a wavelength of 3 to 20 nm, an electron beam (EB), an ion beam, X-rays, and the like.

[0251] Also, in the formation of the circuit pattern, the development method is preferably alkali development or development using an organic solvent.

[0252] Then, etching is performed using the obtained resist upper film pattern as a mask. The etching of the adhesion film in the 4-layer resist process is performed using an oxygen-based gas with the resist upper film pattern as a mask. Thereby, an adhesion film pattern is formed.

[0253] Then, etching is performed using the obtained adhesion film pattern as a mask. The etching of the silicon-containing resist intermediate film and the inorganic hard mask intermediate film is performed using a fluorine-based gas with the adhesion film pattern as a mask. Thereby, a silicon-containing resist intermediate film pattern and an inorganic hard mask intermediate film pattern are formed.

[0254] In some cases, the etching of the adhesion film is performed continuously before the etching of the silicon-containing intermediate film, or the etching of the silicon-containing intermediate film can be performed after the etching of the adhesion film by changing the etching apparatus or the like.

[0255] Then, the obtained silicon-containing resist intermediate film pattern and inorganic hard mask intermediate film pattern are used as masks to perform the etching process of the resist lower layer film.

[0256] The etching of the substrate can then be performed using common methods. For example, if the substrate is a low-dielectric-constant insulating film based on SiO2, SiN, or silicon dioxide, etching with fluorine-based gases is performed. If it is p-Si, Al, or W, etching with chlorine-based or bromine-based gases is performed. When etching the substrate with fluorine-based gases, the silicon-containing intermediate film pattern in the three-layer resist process will be stripped simultaneously with the substrate processing. When etching the substrate with chlorine-based or bromine-based gases, the stripping of the silicon-containing intermediate film pattern must be performed separately using dry etching stripping with fluorine-based gases after the substrate processing.

[0257] Furthermore, there are no particular restrictions on the substrate being processed; a semiconductor device substrate or a semiconductor device substrate having any one of the following films formed on it: a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film. Silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof can be used as the aforementioned metals.

[0258] Specifically, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al can be used, or substrates on which the processed layer is formed. The processed layer can be various Low-k films and their barrier films, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, typically forming a film thickness of 50–10,000 nm, and particularly 100–5,000 nm. Furthermore, when forming the processed layer, the substrate and the processed layer can be made of different materials.

[0259] For an example of a 4-layer resist process, if using Figure 1 Specifically, this is described below. For a 4-layer resist process, such as... Figure 1 As shown in (A), after forming a lower resist film 3 on the processed layer 2 stacked on the substrate 1 using an organic film material, a silicon-containing intermediate film 4 is formed, and an adhesive film 5 is formed thereon using the adhesive film forming material of the present invention, and then an upper resist film 6 is formed thereon.

[0260] Then, as Figure 1 As shown in (B), the exposed portion 7 of the upper resist film is exposed and subjected to PEB and development to form a resist pattern 6a. Figure 1 (C)). Using the obtained resist pattern 6a as a mask, the sealing film 5 is etched using O2-based gas to form the sealing film pattern 5a.Figure 1 (E). After the adhesion film pattern 5a is removed, the resist underlayer film 3 is etched using an O2-based gas with the resultant silicon-containing intermediate film pattern 4a as a mask, to form a resist underlayer film pattern 3a (F). After the silicon-containing intermediate film pattern 4a is removed again, the processed layer 2 is etched using the resist underlayer film pattern 3a as a mask, to form a pattern 2a (G). Figure 1 (E). After the adhesion film pattern 5a is removed, the resist underlayer film 3 is etched using an O2-based gas with the resultant silicon-containing intermediate film pattern 4a as a mask, to form a resist underlayer film pattern 3a (F). After the silicon-containing intermediate film pattern 4a is removed again, the processed layer 2 is etched using the resist underlayer film pattern 3a as a mask, to form a pattern 2a (G). Figure 1 (E). After the adhesion film pattern 5a is removed, the resist underlayer film 3 is etched using an O2-based gas with the resultant silicon-containing intermediate film pattern 4a as a mask, to form a resist underlayer film pattern 3a (F). After the silicon-containing intermediate film pattern 4a is removed again, the processed layer 2 is etched using the resist underlayer film pattern 3a as a mask, to form a pattern 2a (G). Figure 1 (E). After the adhesion film pattern 5a is removed, the resist underlayer film 3 is etched using an O2-based gas with the resultant silicon-containing intermediate film pattern 4a as a mask, to form a resist underlayer film pattern 3a (F). After the silicon-containing intermediate film pattern 4a is removed again, the processed layer 2 is etched using the resist underlayer film pattern 3a as a mask, to form a pattern 2a (G).

[0261] Thus, if the pattern forming method of the present application is used, a fine pattern can be formed on a processed substrate with high precision in a multilayer resist process.

[0262] [Example]

[0263] Hereinafter, the present application will be described more specifically by way of synthesis examples, comparative synthesis examples, examples and comparative examples, but the present application is not limited by them. Further, the measurement of molecular weight is performed by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as a mobile phase, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) are used to calculate the dispersity (Mw / Mn).

[0264] The synthesis of polymers (Al) to (A15) and comparative polymers (Rl) to (R5) used as the (A) resin for the adhesion film forming material was performed using the following monomers (Bl) to (B9).

[0265] [Chemical 23]

[0266]

[0267] [Synthesis Example 1] Synthesis of Polymer (Al)

[0268] A monomer-polymerization initiator solution was prepared by measuring monomer (Bl) 45.1 g, monomer (B5) 34.8 g, monomer (B6) 20.0 g, V-601 (2,2'-azobis(isobutyric acid) dimethyl ester, manufactured by Wako Pure Chemical Industries, Ltd.) 4.70 g, SEA (2-mercaptoethanol, manufactured by Tokyo Chemical Industry Co., Ltd.) 1.28 g, and DAA (diacetone alcohol) 340 g in a 1 L flask under a nitrogen atmosphere, and performing degassing while stirring. After measuring DAA 60 g in another 1 L flask which had been adjusted to a nitrogen atmosphere, degassing was performed while stirring, and then heating was performed until the internal temperature reached 80°C. After the aforementioned monomer-polymerization initiator solution was added dropwise over 4 hours, the temperature of the polymerization solution was maintained at 80°C while stirring was continued for 16 hours, and then cooling was performed to room temperature. The obtained polymerization solution was added dropwise to hexane 1,500 g which was being stirred vigorously, and the polymer which had been separated out was filtered. After the obtained polymer was washed twice with hexane 600 g, vacuum drying was performed at 50°C for 20 hours, and a white powdery polymer (Al) was obtained (yield 101.5 g, yield 96%). When the polymerization average molecular weight (Mw), the dispersity (Mw / Mn) of the polymer (Al) were measured by GPC, Mw = 15,300, Mw / Mn = 1.98.

[0269] [Chemical Formula 24]

[0270]

[0271] [Synthesis Example 2] Synthesis of Polymer (A2)

[0272] A monomer-polymerization initiator solution was prepared by measuring monomer (Bl) 45.1 g, monomer (B5) 34.8 g, monomer (B6) 20.0 g, V-601 4.70 g, and DAA 340 g in a 1 L flask under a nitrogen atmosphere, and performing degassing while stirring. After measuring DAA 60 g in another 1 L flask which had been adjusted to a nitrogen atmosphere, degassing was performed while stirring, and then heating was performed until the internal temperature reached 80°C. After the aforementioned monomer-polymerization initiator solution was added dropwise over 4 hours, the temperature of the polymerization solution was maintained at 80°C while stirring was continued for 16 hours, and then cooling was performed to room temperature. The obtained polymerization solution was added dropwise to hexane 1,500 g which was being stirred vigorously, and the polymer which had been separated out was filtered. After the obtained polymer was washed twice with hexane 600 g, vacuum drying was performed at 50°C for 20 hours, and a white powdery polymer (Al) was obtained (yield 101.5 g, yield 96%). When the polymerization average molecular weight (Mw), the dispersity (Mw / Mn) of the polymer (Al) were measured by GPC, Mw = 15,300, Mw / Mn = 1.98.

[0273] [Chemical Formula 24]

[0274]

[0275] [Synthesis Example 3] Synthesis of Polymer (A3)

[0276] Under a nitrogen atmosphere, a monomer-polymerization initiator solution was prepared by measuring monomer (Bl) 45.1 g, monomer (B5) 34.8 g, monomer (B6) 20.0 g, V-601 0.94 g, and DAA 340 g in a 1 L flask, and performing degassing while stirring. After measuring DAA 60 g in another 1 L flask which had been adjusted to a nitrogen atmosphere, and performing degassing while stirring, the temperature was raised to 80°C. After adding the foregoing monomer-polymerization initiator solution dropwise over 4 hours, the temperature of the polymerization solution was maintained at 80°C while stirring was continued for 16 hours, and then the temperature was allowed to cool to room temperature. The resulting polymerization solution was added dropwise to hexane 1,500 g which was being stirred vigorously, and the polymer which separated out was filtered. The resulting polymer was washed twice with hexane 600 g, and then dried in a vacuum at 50°C for 20 hours, to obtain polymer (A3) as a white powder (yield 99.3 g, yield 98%). The weight average molecular weight (Mw) and the dispersity (Mw / Mn) of polymer (A3) were found to be Mw = 52,500, Mw / Mn = 2.29 by GPC.

[0277] [Synthesis Example 3] Synthesis of Polymer (A3)

[0278]

[0279] [Synthesis Example 4-15] Synthesis of Polymers (A4)-(A15)

[0280] Using the monomers and polymerization initiators shown in Table 1, and otherwise under the same conditions as in Synthesis Examples 1-3, the reaction and post-treatment were performed, to obtain polymers (A4)-(A15) as products. Also, the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were found to be as shown in Table 1 by GPC.

[0281] [Table 1]

[0282]

[0283] [Synthesis Example 3] Synthesis of Polymer (A3)

[0284] A monomer-polymerization initiator solution was prepared by measuring monomer (B5) 100.0 g, V-601 1.62 g, and PGMEA (propylene glycol monomethyl ether acetate) 340 g in a 1 L flask under a nitrogen atmosphere, and then performing degassing while stirring. After measuring PGMEA 60 g in another 1 L flask which had been adjusted to a nitrogen atmosphere, and performing degassing while stirring, the temperature was raised to 80°C. After adding the above monomer-polymerization initiator solution dropwise over 4 hours, the temperature of the polymerization solution was maintained at 80°C while stirring was continued for 16 hours, and then the solution was cooled to room temperature. The resulting polymerization solution was added dropwise to hexane 1,500 g which was being stirred vigorously, and the resulting polymer was separated by filtration. After the resulting polymer was washed twice with hexane 600 g, it was dried in a vacuum at 50°C for 20 hours to obtain a white powdery polymer (R1) (yield 98.2 g, yield 97%). The polymerization average molecular weight (Mw), and the dispersity (Mw / Mn) of the polymer (R1) were found to be Mw = 30,300, and Mw / Mn = 1.51 by GPC.

[0285] [Chem. 27]

[0286]

[0287] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer (R2)

[0288] A monomer-polymerization initiator solution was prepared by measuring monomer (B5) 62.8 g, monomer (B6) 37.2 g, V-601 1.45 g, and PGMEA 340 g in a 1 L flask under a nitrogen atmosphere, and then performing degassing while stirring. After measuring PGMEA 60 g in another 1 L flask which had been adjusted to a nitrogen atmosphere, and performing degassing while stirring, the temperature was raised to 80°C. After adding the above monomer-polymerization initiator solution dropwise over 4 hours, the temperature of the polymerization solution was maintained at 80°C while stirring was continued for 16 hours, and then the solution was cooled to room temperature. The resulting polymerization solution was added dropwise to hexane 1,500 g which was being stirred vigorously, and the resulting polymer was separated by filtration. After the resulting polymer was washed twice with hexane 600 g, it was dried in a vacuum at 50°C for 20 hours to obtain a white powdery polymer (R2) (yield 97.5 g, yield 96%). The polymerization average molecular weight (Mw), and the dispersity (Mw / Mn) of the polymer (R2) were found to be Mw = 33,500, and Mw / Mn = 1.88 by GPC.

[0289] [Chem. 28]

[0290]

[0291] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer (R3)

[0292] A monomer-polymerization initiator solution was prepared by measuring monomer (B5) 64.3 g, monomer (B7) 35.7 g, V-601 1.49 g, and PGMEA 340 g in a 1 L flask under a nitrogen atmosphere, and then deaerating with stirring. After deaerating with stirring by measuring PGMEA 60 g in another 1 L flask which had been adjusted to a nitrogen atmosphere, heating was performed until the internal temperature reached 80°C. After dropwise adding the aforementioned monomer-polymerization initiator solution over 4 hours, the temperature of the polymerization solution was maintained at 80°C while stirring was continued for 16 hours, and then cooling was performed to room temperature. The obtained polymerization solution was added dropwise to hexane 1,500 g which was stirred vigorously, and the precipitated polymer was separated by filtration. After the obtained polymer was washed twice with hexane 600 g, vacuum drying was performed at 50°C for 20 hours, and a white powdery polymer (R3) was obtained (yield 96.5 g, yield 95%). When the polymerization average molecular weight (Mw), and the dispersity (Mw / Mn) of the polymer (R3) were measured by GPC, Mw = 32,200, and Mw / Mn = 1.80.

[0293] [Chemical Formula 29]

[0294]

[0295] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer (R4)

[0296] A monomer-polymerization initiator solution was prepared by measuring monomer (B5) 64.3 g, monomer (B7) 35.7 g, V-601 1.49 g, and PGMEA 340 g in a 1 L flask under a nitrogen atmosphere, and then deaerating with stirring. After deaerating with stirring by measuring PGMEA 60 g in another 1 L flask which had been adjusted to a nitrogen atmosphere, heating was performed until the internal temperature reached 80°C. After dropwise adding the aforementioned monomer-polymerization initiator solution over 4 hours, the temperature of the polymerization solution was maintained at 80°C while stirring was continued for 16 hours, and then cooling was performed to room temperature. The obtained polymerization solution was added dropwise to hexane 1,500 g which was stirred vigorously, and the precipitated polymer was separated by filtration. After the obtained polymer was washed twice with hexane 600 g, vacuum drying was performed at 50°C for 20 hours, and a white powdery polymer (R3) was obtained (yield 96.5 g, yield 95%). When the polymerization average molecular weight (Mw), and the dispersity (Mw / Mn) of the polymer (R3) were measured by GPC, Mw = 32,200, and Mw / Mn = 1.80.

[0297] [Chemical Formula 29]

[0298]

[0299] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer (R4)

[0300] A monomer-polymerization initiator solution was prepared by measuring 100.0 g of the monomer (B9), 2.21 g of V-601, and 340 g of PGMEA in a 1-L flask under a nitrogen atmosphere, and degassing while stirring. After measuring 60 g of PGMEA in another 1-L flask which had been adjusted to a nitrogen atmosphere, and degassing while stirring, the temperature was raised to 80°C. After adding the above monomer-polymerization initiator solution dropwise over 4 hours, the temperature of the polymerization solution was maintained at 80°C while stirring was continued for 16 hours, and then the solution was cooled to room temperature. The resulting polymerization solution was added dropwise to 1,500 g of hexane which was being stirred vigorously, and the resulting polymer was separated by filtration. After the resulting polymer was washed twice with 600 g of hexane, it was dried in a vacuum at 50°C for 20 hours to obtain a white powder of the polymer (R5) (yield 95.2 g, yield 93%). The polymerization average molecular weight (Mw) and the dispersity (Mw / Mn) of the polymer (R5) were found to be Mw = 33,200 and Mw / Mn = 1.95 by GPC.

[0301] [Chem. 31]

[0302]

[0303] [Preparation of Adhesion Film Forming Materials (AL-1 to 27, Comparative AL-1 to 13)]

[0304] In the preparation of the adhesion film forming materials, the aforementioned polymers (A1) to (A15) and comparative polymers (R1) to (R5), (AG1) to (AG4) as thermal acid generators, (AG5) as a photo acid generator, and (X1) to (X3) as crosslinking agents were used. After dissolving in an organic solvent containing PF636 (manufactured by OMNOVA) at 0.1% by mass in the proportions shown in Table 2, filtration was performed using a filter made of a fluorine resin having a pore size of 0.1 μm, whereby the adhesion film forming materials (AL-1 to 27, Comparative AL-1 to 13) were prepared, respectively.

[0305] [Chem. 32]

[0306]

[0307] [Table 2]

[0308]

[0309]

[0310] The components in Table 2 are described below.

[0311] Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) CyH (cyclohexanone)

[0312] DAA (diacetone alcohol)

[0313] EL (ethyl lactate)

[0314] GBL (γ-butyrolactone)

[0315] [Example 1 Solvent resistance evaluation (Examples 1-1 to 1-27, Comparative Examples 1-1 to 1-13)]

[0316] The adhesion film forming material (AL-1 to 27, Comparative AL-1 to 13) prepared above was coated on a silicon substrate, and after calcination at 215°C for 60 seconds, the film thickness was measured, and PGMEA solvent was dispensed thereon, left for 30 seconds and spin-dried, and the PGMEA solvent was evaporated by baking at 100°C for 60 seconds, and the film thickness was again measured, and the solvent resistance was evaluated by finding the difference in film thickness before and after the PGMEA treatment. The results are shown in Table 3.

[0317] [Table 3]

[0318]

[0319]

[0320] As shown in Table 3, Examples 1-1 to 1-27 and Comparative Examples 1-5 to 1-13, which used the adhesion film forming material (AL-1 to 27) of the present application, hardly had a decrease in film thickness due to solvent treatment, and a film with good solvent resistance could be obtained. On the other hand, it was found that Comparative Examples 1-1 to 1-4, which did not contain a thermal acid generator and a crosslinking agent, could not ensure sufficient solvent resistance.

[0321] [Example 2 Adhesion test (Examples 2-1 to 2-27, Comparative Examples 2-1 to 2-9)]

[0322] The adhesion film forming material (AL-1 to 27, Comparative AL-5 to 13) was coated on a SiO2 wafer substrate, and using a hot plate, calcination was performed at 215°C for 60 seconds in the atmosphere, thereby forming an adhesion film with a film thickness of 5 nm (AL-1 to 19, Comparative AL-5 to 11, 13) or 20 nm (AL-20 to 27, Comparative AL-12). A wafer with the adhesion film attached was cut into a square of 1 x 1 cm, and an aluminum pin with an epoxy adhesive attached was installed in the wafer cut using a dedicated jig. Thereafter, the aluminum pin was adhered to the substrate using an oven at 150°C for 1 hour. After cooling to room temperature, the initial adhesion was evaluated by the resistance force using a film adhesion strength measuring device (Sebastian Five-A).

[0323] Figure 2 Explanatory diagram showing the adhesion measurement method. Figure 28 indicates a silicon wafer (substrate), 9 indicates a hardened film, 10 indicates an aluminum pin provided with an adhesive, 11 indicates a support table, 12 indicates a clamping portion, and 13 indicates a stretching direction. The adhesion force is an average value measured at 12 points, and the higher the value, the higher the adhesion of the adhesion film to the substrate. The adhesion was evaluated by comparing the values obtained. The results are shown in Table 4.

[0324] [Table 4]

[0325]

[0326] As shown in Table 4, it was confirmed that the adhesion force of Examples 2-1 to 2-27 using the adhesion film forming materials (AL-1 to AL-27) of the present application was excellent. It was also confirmed that Comparative Examples 2-1 to 2-8 using polymers containing the structural unit represented by General Formula (2) also had good adhesion. On the other hand, Comparative Example 2-9 using a polymer not containing the structural unit represented by General Formula (2) had poor adhesion compared to the other examples.

[0327] [ArF immersion exposure pattern formation test of positive resist (Examples 3-1 to 3-27, Comparative Examples 3-1 to 3-8)]

[0328] A spin-on carbon ODL-301 (carbon content 88 mass%) manufactured by Showa Denko K.K. was applied to a silicon wafer substrate, and baked at 350°C for 60 seconds to form a resist underlayer film having a film thickness of 200 nm. A CVD-SiON hard mask intermediate film was formed thereon, and the above adhesion film forming material (AL-1 to AL-27, Comparative AL-5 to AL-12) was applied and baked at 215°C for 60 seconds to form an adhesion film having a film thickness of 5 nm (AL-1 to AL-19, Comparative AL-5 to AL-11) or 20 nm (AL-20 to AL-27, Comparative AL-12), and an ArF single-layer resist of the positive resist upper layer film material described in Table 5 was applied to the adhesion film and baked at 105°C for 60 seconds to form a resist upper layer film having a film thickness of 100 nm. An immersion protective film material (TC-1) was applied to the resist upper layer film and baked at 90°C for 60 seconds to form a protective film having a film thickness of 50 nm.

[0329] The positive resist upper layer film material (ArF single-layer resist) was prepared by dissolving the polymer (PRP-A1), acid generator (PAG1), and basic compound (Amine1) in the proportions shown in Table 5 in a solvent containing 0.1 mass% of FC-430 (manufactured by Sumitomo 3M Company) and filtering through a 0.1 μm fluororesin filter.

[0330] [Table 5]

[0331]

[0332] Polymer for resist: PRP-A1

[0333] Molecular weight (Mw) = 8,600

[0334] Dispersity (Mw / Mn) = 1.88

[0335] [Chem. 33]

[0336]

[0337] Acid generator: PAG1

[0338] [Chem. 34]

[0339]

[0340] Basic compound: Amine1

[0341] [Chem. 35]

[0342]

[0343] Infiltration protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in the organic solvent at the proportions of Table 6, and filtering with a filter made of a fluorine resin at 0.1 μm.

[0344] [Table 6]

[0345]

[0346] Protective film polymer: PP1

[0347] Molecular weight (Mw) = 8,800

[0348] Dispersity (Mw / Mn) = 1.69

[0349] [Chem. 36]

[0350]

[0351] Then, exposure was performed with an ArF immersion exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized light illumination, 6% half-order phase shift mask), and post-exposure baking (PEB) was performed at 100°C for 60 seconds, and development was performed with a 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution for 30 seconds, to obtain a 40-nm 1 : 1 line-and-space pattern. The cross-sectional shape and the roughness of the pattern were observed with an electron microscope using the pattern as a target. Further, the minimum size at which the line did not collapse and could be resolved when the line size was made finer by increasing the exposure amount was found, and was made the collapse limit (nm). The smaller the value, the higher the collapse resistance, and the more desirable.

[0352] The cross-sectional shape of the obtained pattern was evaluated with an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the roughness of the pattern was evaluated with an electron microscope (CG4000) manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 7.

[0353] [Table 7]

[0354]

[0355] As shown in Table 7, Examples 3-1 to 3-27 using the adhesion film-forming material (AL-1 to AL-27) of the present application exhibited superior collapse-inhibiting performance to Comparative Examples, and the pattern shape was also a vertical shape. On the other hand, Comparative Examples 3-1 to 3-8 not containing the resin contained in the adhesion film-forming material of the present application, although the adhesion was also high and the collapse-inhibiting performance was also superior, the pattern was in a tailing shape or an inverted taper shape, and it was found that Examples 3-1 to 3-27 using the adhesion film-forming material of the present application were superior in pattern-forming ability. It was also found that the polymer did not have a photoacid generation site, but Comparative Example 3-4 in which a photoacid generator (AG5) was additionally added had a pattern in an inverted taper shape and the pattern roughness was deteriorated.

[0356] [ArF immersion exposure pattern-forming test of a negative resist (Examples 4-1 to 4-27, Comparative Examples 4-1 to 4-8)]

[0357] An organic underlayer film and a CVD-SiON hard mask intermediate film were formed on a silicon wafer in the same manner as in the patterning test using a positive resist described above, and an adhesion film was formed thereon. An ArF single-layer resist of the negative resist upper film material described in Table 8 was applied thereon, and a photoresist layer having a film thickness of 100 nm was formed by baking at 100°C for 60 seconds. A dip protection film (TC-1) was applied to the photoresist film and baked at 90°C for 60 seconds to form a protection film having a film thickness of 50 nm.

[0358] A negative resist upper layer film material was prepared by dissolving the aforementioned polymer (PRP-A1), acid generator (PAG1), basic compound (Amine1) in a solvent containing FC-430 (Sumitomo 3M (Co.) Ltd.) 0.1 mass% at the proportions of Table 8, and filtering with a filter made of fluorine resin of 0.1 μm.

[0359] [Table 8]

[0360]

[0361] Then, exposure was performed with an ArF immersion exposure device (Nikon (Co.) Ltd.; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized light illumination, 6% half-order phase shift mask), and baking (PEB) was performed at 100°C for 60 seconds, while rotating at 30 rpm, and butyl acetate was sprayed from a developing nozzle as a developing solution for 3 seconds, after which rotation was stopped and standing development was performed for 27 seconds, and after rinsing with diisopentyl ether, spin drying was performed, and the rinsing solvent was evaporated by baking at 100°C for 20 seconds. With this patterning, a negative line-and-space pattern of 43 nm was obtained. The cross-sectional shape was observed with an electron microscope using this pattern as a target. Also, the minimum size at which the line did not collapse and could be resolved by making the line size finer by reducing the exposure amount was found, and was made the collapse limit (nm). The smaller the value, the higher the collapse resistance, and the more desirable.

[0362] The cross-sectional shape of the obtained pattern was evaluated with an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the collapse of the developed pattern was evaluated with an electron microscope (CG4000) manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 9.

[0363] [Table 9]

[0364]

[0365]

[0366] As shown in Table 9, in the pattern formation test using a negative resist, a pattern of vertical shape was obtained in any of the examples. The collapse limit values were smaller in Examples 4-1 to 4-27 using the adhesion film-forming material (AL-1 to AL-27) of the present application than in the case of using a positive resist, and it was found that the adhesion was more excellent in the negative resist. On the other hand, it was found that Comparative Examples 4-1 to 4-8, which did not contain the resin contained in the adhesion film-forming material of the present application, had high adhesion and excellent performance of suppressing collapse, but the collapse limit values were smaller and the adhesion was more excellent in Examples 4-1 to 4-27 using the adhesion film-forming material of the present application.

[0367] [Example 5 Electron beam pattern formation test (Example 5-1, Comparative Example 5-1)]

[0368] The adhesion film forming material (AL-4, Comparative AL-5) was applied to a silicon wafer substrate and baked at 215°C for 60 seconds to form an adhesion film having a film thickness of 5 nm, and then a metal-containing resist composition as the resist upper layer film material was applied thereto and baked at 180°C for 60 seconds to form a resist upper layer film having a film thickness of 60 nm.

[0369] The resist upper layer film material (metal-containing resist composition) was prepared by dissolving a titanium-containing compound (AM-1) and a metal salt sensitizer (S-1) in 4-methyl-2-pentanol (MIBC) containing FC-4430 (Sumitomo 3M Company) at a ratio shown in Table 10, and filtering with a 0.1 μm fluororesin filter.

[0370] [Table 10]

[0371]

[0372] Synthesis of titanium-containing compound (AM-1)

[0373] A 500 g solution of deionized water 27 g in 2-propanol (IPA) was added dropwise to a 500 g solution of titanium tetraisopropoxide (Tokyo Chemical Industry Co., Ltd.) 284 g in 2-propanol over 2 hours with stirring at room temperature. To the resulting solution was added 2,4-dimethyl-2,4-octanediol 180 g, and stirred for 30 minutes at room temperature. The solution was concentrated under reduced pressure at 30°C, and then heated to 60°C, and continuously heated under reduced pressure until no distillate appeared. When no distillate was observed, 4-methyl-2-pentanol (MIBC) 1,200 g was added, and heated under reduced pressure at 40°C until no IPA distilled. This gave a MIBC solution of the titanium-containing compound AM-1, 1,000 g (compound concentration 25 mass %). The polystyrene-equivalent molecular weight thereof was Mw = 1,200.

[0374] Metal salt sensitizer: S-1

[0375] [Chemical 37]

[0376]

[0377] Then, in-vacuum chamber drawing was performed using a JBX-9000MV (Nikon Corporation) at an acceleration voltage of 50 kV. Immediately after the drawing, baking (PEB) was performed at 200°C for 60 seconds, and immersion development was performed using butyl acetate for 20 seconds, to obtain a negative pattern.

[0378] The obtained resist pattern was evaluated as follows. The exposure amount at which a line of 100 nm and a line space (LS) were resolved at 1 : 1 was the sensitivity, and the minimum size at which the line was not collapsed and could be resolved in the aforementioned exposure amount was found, and was made the collapse limit (nm). The smaller the value, the higher the collapse resistance, and the more desirable. The results are shown in Table 11.

[0379] [Table 11]

[0380] Adhesion film forming material Collapse limit (nm) Example 5-1 AL-4 55 Comparative Example 5-1 Comparative AL-5 65

[0381] As shown in Table 11, Example 5-1 using the adhesion film-forming material (AL-4) of the present application had a smaller value of the collapse limit than Comparative Example 5-1 not using the adhesion material of the present application, and it was understood that the adhesion of the present application was excellent even in a metal-containing resist.

[0382] In summary, if the adhesion film-forming material of the present application, it has high adhesion with the resist upper layer film and has the effect of suppressing collapse of a fine pattern, and is extremely useful as an adhesion film material used in a multilayer resist method, and, if the pattern forming method of the present application using the adhesion film-forming material, it can form a fine pattern on a substrate to be processed with high precision.

[0383] In addition, the present application is not limited to the above-described embodiments. The above-described embodiments are illustrative, and those having substantially the same configuration as the technical idea described in the claims of the present application and exerting the same effects are included in the technical scope of the present application.

[0384] Explanation of Reference Signs

[0385] 1: substrate

[0386] 2: layer to be processed

[0387] 2a: pattern (pattern formed on the layer to be processed)

[0388] 3: resist lower layer film

[0389] 3a: resist lower layer film pattern

[0390] 4: silicon-containing intermediate film

[0391] 4a: silicon-containing intermediate film pattern

[0392] 5: adhesion film

[0393] 5a: adhesion film pattern

[0394] 6: resist upper layer film

[0395] 6a: resist upper layer film pattern

[0396] 7: exposed portion

[0397] 8: silicon wafer

[0398] 9: hardened film

[0399] 10: aluminum pin provided with an adhesive

[0400] 11: support table

[0401] 12: pinching point

[0402] 13: stretching direction

Claims

1. An adhesion film forming material for forming an adhesion film immediately below an upper layer of resist, characterized by comprising: (A) a resin having at least one structural unit having a fluorine-substituted organic sulfonyl anion structure, and having two or more structural units represented by the following general formula (2) that are different from the structural unit having the fluorine-substituted organic sulfonyl anion structure, (B) a thermal acid generator, and (C) an organic solvent; the general formula (2) is: wherein R6 is a hydrogen atom or a methyl group, and R7 is a group selected from the following formulas (2-1) to (2-3); wherein the dotted line represents a bond between atoms. The fluorine-substituted organic sulfonyl anion structure is a structure represented by the following general formula (1). The R2 in the general formula (1) is a divalent organic group having alicyclic structure. The (C) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 150°C and one or more organic solvents having a boiling point of 150°C or more and less than 220°C. The (A) resin has a weight average molecular weight of 5,000 to 70,000.

6. The adhesion film forming material according to any one of claims 1 to 3, further comprising at least one or more of (D) a photo acid generator, (E) a surfactant, (F) a crosslinking agent, and (G) a plasticizer.

2. The adhesion film forming material according to claim 1, wherein The upper layer of resist is formed using a negative resist composition. wherein R1 is a hydrogen atom or a methyl group; R2 is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -O-C(=O)-, Z 21 is a saturated hydrocarbylene group having 1 to 12 carbon atoms, and can also contain a carbonyl group, an ester bond or an ether bond; R3 to R5 are each independently a hydrocarbyl group having 1 to 21 carbon atoms which can also contain a hetero atom; furthermore, any two of R3, R4 and R5 can also be bonded to each other and form a ring together with the sulfur atom to which they are bonded; and A1 is a hydrogen atom or a trifluoromethyl group.

3. The adhesion film forming material according to claim 2, wherein The upper layer of resist is formed using an upper layer of resist material containing at least an organic metal compound and a solvent.

4. The adhesion film forming material according to any one of claims 1 to 3, wherein The organic metal compound contains at least one selected from titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium.

5. The adhesion film forming material according to any one of claims 1 to 3, wherein 10. A pattern forming method for forming a pattern on a substrate to be processed, characterized by comprising the steps of: (I-1) forming an adhesion film on a substrate to be processed by applying the adhesion film forming material according to any one of claims 1 to 9 and then performing heat treatment, (I-2) forming an upper layer of resist on the adhesion film using a photoresist material, (I-3) forming a circuit pattern on the upper layer of resist by performing pattern exposure and then developing using a developer, (I-4) transferring the pattern to the adhesion film by dry etching using the upper layer of resist having the circuit pattern as a mask, and (I-5) forming a pattern on the substrate to be processed by processing the substrate to be processed using the adhesion film having the pattern transferred as a mask.

11. A pattern forming method for forming a pattern on a substrate to be processed, characterized by comprising the steps of: (II-1) forming a lower layer of resist on a substrate to be processed, (II-2) forming a silicon-containing intermediate resist film on the lower layer of resist, (II-3) forming an adhesion film on the silicon-containing intermediate resist film by applying the adhesion film forming material according to any one of claims 1 to 9 and then performing heat treatment, (II-4) forming an upper layer of resist on the adhesion film using a photoresist material, (II-5) forming a circuit pattern on the upper layer of resist by performing pattern exposure and then developing using a developer, (II-6) transferring the pattern to the adhesion film by dry etching using the upper layer of resist having the circuit pattern as a mask, and (II-7) forming a pattern on the substrate to be processed by processing the substrate to be processed using the adhesion film having the pattern transferred as a mask.

7. The adhesion film forming material according to any one of claims 1 to 3, wherein ​ 8. The adhesion film forming material according to any one of claims 1 to 3, wherein ​ 9. The adhesion film forming material according to claim 8, wherein ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ (II-5) After the resist upper layer film is subjected to pattern exposure, development is performed using a developer, and a circuit pattern is formed in the resist upper layer film, (II-6) Using the resist upper layer film in which the circuit pattern has been formed as a mask, a pattern is transferred to the adhesion film by dry etching, (II-7) Using the adhesion film in which the pattern has been formed as a mask, a pattern is transferred to the silicon-containing resist intermediate film by dry etching, (II-8) Using the silicon-containing resist intermediate film in which the pattern has been transferred as a mask, a pattern is transferred to the resist lower layer film by dry etching, and (II-9) Using the resist lower layer film in which the pattern has been transferred as a mask, and the processed substrate is processed, and a pattern is formed in the processed substrate.

12. A pattern forming method, which is a method of forming a pattern in a processed substrate, characterized by comprising the steps of: (III-1) forming a resist lower layer film on a processed substrate, (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist lower layer film, (III-3) after the inorganic hard mask intermediate film is coated with the adhesion film forming material according to any one of claims 1 to 9, an adhesion film is formed by heat treatment, (III-4) using a photoresist material to form a resist upper layer film on the adhesion film, (III-5) after the resist upper layer film is subjected to pattern exposure, development is performed using a developer, and a circuit pattern is formed in the resist upper layer film, (III-6) Using the resist upper layer film in which the circuit pattern has been formed as a mask, a pattern is transferred to the adhesion film by dry etching, (III-7) Using the adhesion film in which the pattern has been formed as a mask, a pattern is transferred to the inorganic hard mask intermediate film by dry etching, (III-8) Using the inorganic hard mask intermediate film in which the pattern has been transferred as a mask, a pattern is transferred to the resist lower layer film by dry etching, and (III-9) Using the resist lower layer film in which the pattern has been transferred as a mask, and the processed substrate is processed, and a pattern is formed in the processed substrate.

13. The pattern forming method according to claim 12, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

14. The pattern forming method according to any one of claims 10 to 13, wherein optical lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof is used as the method of forming a circuit pattern in the resist upper layer film.

15. The pattern forming method according to any one of claims 10 to 13, wherein alkali development or development using an organic solvent is used as the development method.

16. The pattern forming method according to any one of claims 10 to 13, wherein a semiconductor device substrate or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film has been formed is used as the processed substrate.

17. The pattern forming process according to claim 16, which uses silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof as the metal.

18. A method for forming a film for adhesion, which is a method for forming a film for adhesion that functions as an adhesion layer used as a manufacturing step of a semiconductor device, characterized by: forming a film for adhesion on a substrate by a method for forming a film for adhesion according to any one of claims 1 to 17. A hardening film is formed by spin-coating the adhesion film-forming material according to any one of claims 1 to 9 on a substrate to be processed, and heat-treating the substrate coated with the adhesion film-forming material at a temperature of 100°C or higher and 300°C or lower for 10 to 600 seconds.

19. A method for forming a close contact film, which is a method for forming a close contact film functioning as a close contact layer used as a manufacturing step of a semiconductor device, characterized by: forming a close contact film on a substrate by a method for forming a close contact film according to any one of claims 1 to 18. A hardening film is formed by spin-coating the adhesion film-forming material according to any one of claims 1 to 9 on a substrate to be processed, and heat-treating the substrate coated with the adhesion film-forming material in an ambient gas having an oxygen concentration of 0.1% or higher and 21% or lower.

20. A method for forming a film for adhesion, which is a method for forming a film for adhesion functioning as an adhesion layer used as a manufacturing step of a semiconductor device, characterized by: forming a film for adhesion on a substrate by a method for forming a film for adhesion according to any one of claims 1 to 19. A hardening film is formed by spin-coating the adhesion film-forming material according to any one of claims 1 to 9 on a substrate to be processed, and heat-treating the substrate coated with the adhesion film-forming material in an ambient gas having an oxygen concentration of less than 0.1%.

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