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

Abstract

To provide a formation material, a pattern formation method, and an adhesion film formation method which give an adhesion film that has high adhesion to a resist upper layer film, has an effect for suppressing falling of a fine pattern, and enables formation of a good pattern shape, in a fine patterning process by a multilayer resist method in a semiconductor device manufacturing process.SOLUTION: An adhesion film formation material is formed immediately below a resist upper layer film, wherein the material contains (A) a resin having a structural unit containing an acid-dissociative group and a structural unit represented by at least two kinds of formulae (1), and (C) an organic solvent, further contains (B) an optical acid generator, or the resin (A) has an optical acid generator structural unit, or the material contains (B) and the resin (A) has the optical acid generator structural unit. In the formula, R1 is H or a methyl group, and R2 is a group selected from formulae (1-1) to (1-3).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an adhesion film forming material, a pattern forming method using the adhesion film forming material, and a method for forming an adhesion film using the adhesion film forming material. [Background technology]

[0002] With the increasing integration and speed of LSIs, the miniaturization of pattern dimensions is progressing rapidly. Lithography technology has achieved the formation of fine patterns in line with this miniaturization by shortening the wavelength of the light source and appropriately selecting the resist composition for it. At the heart of this is the single-layer positive-type photoresist composition. This single-layer positive-type photoresist composition has a framework in the resist resin that is resistant to dry etching by chlorine-based or fluorine-based gas plasma, and also has a resist mechanism that dissolves the exposed areas. By dissolving the exposed areas to form a pattern, the remaining resist pattern is used as an etching mask to dry etch the substrate to which the photoresist composition has been applied.

[0003] However, if the thickness of the photoresist film used is kept the same while miniaturization is achieved, i.e., if the pattern width is reduced, the resolution performance of the photoresist film decreases. Furthermore, when attempting to develop the photoresist film using a developer, the aspect ratio becomes too large, resulting in pattern collapse. For this reason, the thickness of the photoresist film has been reduced with miniaturization.

[0004] On the other hand, the processing of substrates typically involves using a photoresist film with a pattern formed on it as an etching mask and processing the substrate by dry etching. However, in reality, there is no dry etching method that can achieve complete etching selectivity between the photoresist film and the substrate. As a result, the photoresist film is damaged during processing, causing it to collapse and making it impossible to accurately transfer the resist pattern to the substrate. Therefore, with the miniaturization of patterns, high dry etching resistance has been required for photoresist compositions. Furthermore, with the shortening of exposure wavelengths, resins used in photoresist compositions are required to have low light absorption at the exposure wavelength. As a result, the transition from i-line, KrF, and ArF has been shifted to novolac resins, polyhydroxystyrene, and resins with aliphatic polycyclic skeletons. However, in reality, the etching rate under the aforementioned dry etching conditions has become fast, and recent photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] This necessitates dry etching of substrates using thinner photoresist films with weaker etching resistance, making the securing of materials and processes for this manufacturing stage a matter of urgency.

[0006] One way to solve these problems is the multilayer resist method. In this method, a photoresist film (i.e., a resist upper layer) and an intermediate film with different etching selectivity are interposed between the resist upper layer and the substrate to be processed. After obtaining a pattern on the resist upper layer, the resist upper layer pattern is used as a dry etching mask to transfer the pattern to the intermediate film by dry etching, and then the intermediate film is used as a dry etching mask to transfer the pattern to the substrate to be processed by dry etching.

[0007] One multilayer resist method is the three-layer resist method, which can be performed using the same resist compositions as those used in the single-layer resist method. In this three-layer resist method, for example, an organic film such as novolac is deposited on the substrate to be processed as the resist underlayer, a silicon-containing film is deposited on top of it as the silicon-containing resist interlayer, and a normal organic photoresist film is formed on top of that as the resist upper layer. For dry etching with fluorine-based gas plasma, the organic resist upper layer has a good etching selectivity ratio with respect to the silicon-containing resist interlayer, so the resist upper layer pattern is transferred to the silicon-containing resist interlayer by dry etching with fluorine-based gas plasma. Furthermore, for etching using oxygen gas or hydrogen gas, the silicon-containing resist interlayer has a good etching selectivity ratio with respect to the resist underlayer, so the silicon-containing interlayer pattern is transferred to the resist underlayer by etching with oxygen gas or hydrogen gas. According to this method, even when using photoresist compositions that are difficult to form patterns with sufficient thickness for direct processing of the substrate, or photoresist compositions that do not have sufficient dry etching resistance for processing the substrate, if the pattern can be transferred to the silicon-containing film (silicon-containing resist interlayer), it is possible to obtain a pattern for an organic film (resist underlayer) made of novolac or the like that has sufficient dry etching resistance for processing.

[0008] In recent years, vacuum ultraviolet (EUV) lithography with a wavelength of 13.5 nm has attracted attention as a promising alternative to the combined use of ArF immersion lithography and multiple exposure processes. This technology makes it possible to form fine patterns with a half-pitch of 25 nm or less in a single exposure.

[0009] On the other hand, in EUV lithography, high sensitivity is strongly required for the resist material to compensate for the insufficient output of the light source. However, the increase in shot noise associated with increased sensitivity leads to an increase in the edge roughness (LER, LWR) of the line pattern, and achieving both high sensitivity and low edge roughness is one of the important challenges in EUV lithography.

[0010] In recent years, the use of metallic materials in resists has been explored as an attempt to increase the sensitivity of resists and reduce the effects of shot noise. Compounds containing metallic elements such as barium, titanium, hafnium, zirconium, and tin have higher absorbance to EUV light compared to organic materials that do not contain metals, and are expected to improve the photosensitivity of resists and suppress the effects of shot noise. Furthermore, metal-containing resist patterns can be expected to enable highly selective etching by combining them with an underlayer made of non-metallic materials.

[0011] For example, resist materials with added metal salts or organometallic complexes (Patent Documents 1 and 2), and non-chemically amplified resist materials using metal oxide nanoparticles (Patent Documents 3 and 4, Non-Patent Document 1) have been investigated. However, the resolution of these metal-containing resists has not yet reached the level required for practical application, and further improvements in resolution are needed.

[0012] Furthermore, with the advent of ArF immersion lithography and EUV lithography, it is becoming possible to form even finer patterns. However, because ultrafine patterns have a small contact area, they are extremely susceptible to pattern collapse, making pattern collapse suppression a major challenge. Recently, it has been suggested that the interaction at the interface between the resist upper layer and the resist lower layer in fine patterns affects pattern collapse, and improvement in the performance of the resist lower layer is also necessary.

[0013] To suppress pattern collapse, materials have been reported that improve adhesion to the resist upper layer by using a resist underlayer containing polar functional groups such as lactone structures or urea structures (Patent Documents 4 and 5).

[0014] Furthermore, there is a report (Patent Document 6) that the rectangularity of the pattern can be improved by using a resist underlayer film formation composition containing a polymer, an acid generator, and a solvent.

[0015] However, in the current situation where finer pattern formation is required, these materials still do not provide sufficient resistance to pattern collapse. Furthermore, even when good adhesion is achieved, there is a problem of scum formation in the gaps due to the high adhesion.

[0016] Therefore, there is a need for a pattern material that has higher pattern collapse suppression performance and adhesion, while also preventing the formation of scum in the gaps. [Prior art documents] [Patent Documents]

[0017] [Patent Document 1] Patent No. 5708521 [Patent Document 2] Patent No. 5708522 [Patent Document 3] U.S. Patent No. 9310684 [Patent Document 4] International Publication No. 2003 / 017002 [Patent Document 5] International Publication No. 2018 / 143359 [Patent Document 6] International Publication No. 2022 / 244682 [Non-patent literature]

[0018] [Non-Patent Document 1] Proc. SPIE Vol. 7969, 796915 (2011) [Overview of the project] [Problems that the invention aims to solve]

[0019] The present invention has been made in view of the above circumstances, and aims to provide an adhesion film forming material that provides an adhesion film that has high adhesion to the resist upper layer film, has an effect of suppressing the collapse of fine patterns, and can form a good pattern shape in a fine patterning process by multilayer resist in the semiconductor device manufacturing process, a pattern forming method using the material, and a method for forming the adhesion film. [Means for solving the problem]

[0020] To solve the above problems, the present invention provides an adhesion film forming material for an adhesion film formed directly beneath a resist upper layer film, wherein the adhesion film forming material comprises (A) a resin having structural units containing acid-dissociable groups and at least two types of structural units represented by the following general formula (1), and (C) an organic solvent. Furthermore, the present invention provides an adhesive film-forming material characterized by containing (B) a photoacid generator, or the resin (A) having structural units that generate acid in the presence of light, or containing the photoacid generator (B) and the resin (A) having structural units that generate acid in the presence of light. [ka] (In the above general formula (1), R 1 R is a hydrogen atom or a methyl group, 2 (The base is selected from the following equations (1-1) to (1-3).) [ka] (In the above equation, dashed lines indicate connections.)

[0021] The adhesion film forming material of the present invention provides an adhesion film that exhibits high adhesion to the resist upper layer film, has an effect of suppressing the collapse of fine patterns, and can form a good pattern shape.

[0022] Furthermore, in the present invention, it is preferable that the structural unit containing the acid-dissociable group has one of the structures represented by the following general formulas (2) to (4). [ka] (wherein, R 3 , R 5 , R 10 is each independently a hydrogen atom or a methyl group. R 4 、 R 9 is each independently an acid dissociable group. X 1 is a single bond, or a linking group having 1 to 14 carbon atoms including a phenylene group, a naphthylene group, an ester bond, an ether bond or a lactone ring. X 2 is a single bond, an ester bond or an amide bond. X 3 is a single bond, an ether bond or an ester bond. R 6 is a single bond or a saturated hydrocarbylene group having 1 to 6 carbon atoms, and a part of the carbon atoms thereof may be substituted with an ether bond or an ester bond. R 8 is a fluorine atom, a trifluoromethyl group, a cyano group or a saturated hydrocarbyl group having 1 to 6 carbon atoms. a is 1 or 2. b is an integer of 0 to 4. However, 1 ≦ a + b ≦ 5. X 4 is a single bond, or an alkylene group having 1 to 10 carbon atoms which may contain an etheric oxygen atom in the middle of the chain. R 11 is each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms which may be substituted with a halogen, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen. R 12 and R 13 are each independently a linear or branched alkyl group having 1 to 15 carbon atoms which may be substituted with a hydrogen atom, a hydroxy group or an alkoxy group, or a monovalent aromatic ring-containing group which may have a substituent. R 14 is a hydrogen atom, a linear, branched or cyclic monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may contain an etheric oxygen atom in the middle of the chain, a carbonyl group or a carbonyloxy group in the middle or at the end of the chain, or a monovalent aromatic ring-containing group which may have a substituent, and OR 14This forms an acid-dissociating group. c is 0 or 1, d is an integer between 0 and 2, and f is an integer between 1 and 3. e is (5 + 2d - f).

[0023] Such an adhesive film-forming material offers better adhesion to the resist upper layer and a more desirable effect in preventing pattern deformation.

[0024] Furthermore, in the present invention, it is more preferable that the (A) resin further has at least one of the structural units represented by the following general formulas (5) to (6). [ka] (In the formula, R 15 , R 17 Each of these is independently either a hydrogen atom or a methyl group. 16 is an alkyl group having 1 to 3 carbon atoms, m is an integer of 1 or 2, n is an integer of 0 to 4, and m+n is an integer between 1 and 5 (inclusive). 5 R represents an alkylene group which may contain a single bond or an oxygen atom with 1 to 10 carbon atoms. 18 This is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -OC(=O)- and Z 21 R is a saturated hydrocarbylene group having 1 to 12 carbon atoms, and may contain a carbonyl group, an ester bond, or an ether bond. 19 ~R 21 Each of these is independently a hydrocarbyl group having 1 to 20 carbon atoms, which may contain heteroatoms. Also, R 19 , R 20 and R 21 Any two of these may bond with each other to form a ring with the sulfur atom to which they are bonded. 1 (This is either a hydrogen atom or a trifluoromethyl group.)

[0025] The structural unit represented by the general formula (5) above contributes to improved adhesion, and the structural unit represented by the general formula (6) functions as an acid generating group. When a resin has such structural units, it can exhibit good adhesion and scum prevention without the need to add an acid generating agent separately.

[0026] Furthermore, in the present invention, when the total number of moles of all structural units in the resin (A) is set to 1.0, it is more preferable that the total number of moles of structural units represented by general formula (1) is 0.10 or more and 0.99 or less, the total number of moles of structural units containing acid-dissociable groups is 0.001 or more and 0.60 or less, and the total number of moles of structural units represented by (5) to (6) is 0 or more and 0.60 or less.

[0027] With such an adhesive film-forming material, the amount of polar groups on the film surface changes as acid-dissociable groups are removed in the exposed area, allowing for the formation of an adhesive film with high adhesion to the resist upper layer and high ability to suppress scum formation in the patterned areas.

[0028] Furthermore, in the present invention, it is preferable that the weight-average molecular weight of the resin (A) is 3,000 to 70,000.

[0029] Adhesion film-forming materials containing resins within this weight-average molecular weight range exhibit excellent film-forming properties and can suppress the generation of sublimation during heat curing, thereby preventing contamination of equipment by sublimation.

[0030] Furthermore, it is preferable that the present invention further contains one or more of (D) surfactants, (E) crosslinking agents, and (F) thermal acid generators.

[0031] The presence or absence / selection of these various additives allows for fine-tuning of performance according to customer requirements, such as curability, film formation, embedding ability, optical properties, and reduction of sublimation, which is practically desirable.

[0032] Furthermore, the present invention provides an adhesion film forming material for negative-type resist films in which the structural unit containing the acid-dissociable group has a structure represented by the general formula (2) or (3), or an adhesion film forming material for positive-type resist films in which the structural unit containing the acid-dissociable group has a structure represented by the general formula (4).

[0033] In the present invention, by selecting an appropriate acid-dissociable group-containing structural unit in the above-mentioned adhesion film-forming material, an adhesion film-forming material for either negative-type resist films or positive-type resist films can be provided.

[0034] Furthermore, the present invention provides a coating film for forming an adhesive film, which is made of the above-mentioned adhesive film forming material and has a thickness of 2 nm to 50 nm.

[0035] With such an adhesive film-forming coating, the resulting adhesive film can be removed by etching in a short time, allowing for the selection of a thinner film as the upper resist.

[0036] Furthermore, the present invention relates to a method for forming a pattern on a substrate to be processed, (I-1) A step of forming an adhesion film by applying the adhesion film forming material of the present invention onto a substrate to be processed and then heat-treating it. (I-2) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (I-3) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (I-4) A step of transferring the pattern to the adhesion film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of etching the substrate to be processed using the adhesive film on which the pattern is formed as a mask to form a pattern on the substrate. The present invention provides a pattern forming method having the following characteristics.

[0037] Furthermore, the present invention relates to a method for forming a pattern on a substrate to be processed, (II-1) A step of forming a resist underlayer film on a substrate to be processed, (II-2) A step of forming a silicon-containing resist interlayer on the resist underlayer, (II-3) A step of forming an adhesion film by applying the adhesion film forming material of the present invention onto the silicon-containing resist interlayer and then heat-treating it. (II-4) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (II-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-6) A step of transferring the pattern to the adhesion film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (II-7) Using the contact film on which the pattern is formed as a mask, a step of transferring the pattern to the silicon-containing resist interlayer by dry etching. (II-8) A step of transferring the pattern to the resist underlayer film by dry etching, using the silicon-containing resist interlayer film on which the pattern has been transferred as a mask, and (II-9) A step of etching the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate. The present invention provides a pattern forming method having the following characteristics.

[0038] Furthermore, the present invention relates to a method for forming a pattern on a substrate to be processed, (III-1) A step of forming a resist underlayer film on a substrate to be processed. (III-2) A step of forming an inorganic hard mask interlayer film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film. (III-3) A step of forming an adhesion film by applying the adhesion film forming material of the present invention onto the inorganic hard mask interlayer and then heat-treating it. (III-4) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (III-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (III-6) A step of transferring the pattern to the adhesion film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (III-7) Using the adhesive film on which the pattern is formed as a mask, dry etching the above Inorganic hard mask The process of transferring a pattern to an interlayer film, (III-8) The pattern is transferred Inorganic hard mask A step of using the interlayer as a mask to transfer a pattern to the resist underlayer by dry etching, and (III-9) A step of etching the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method having the following characteristics.

[0039] Thus, the adhesion film forming material of the present invention can be suitably used in various pattern formation methods, such as a two-layer resist process and a four-layer resist process in which the adhesion film is formed on a silicon-containing interlayer (silicon-containing resist interlayer, inorganic hard mask interlayer). With these pattern formation methods, pattern collapse can be effectively mitigated by the formation of the adhesion film, making it suitable for photolithography of the resist upper layer film.

[0040] In this case, it is preferable to form the inorganic hard mask interlayer by CVD or ALD.

[0041] Furthermore, in the present invention, it is preferable to use photolithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof as a method for forming a pattern on the resist upper layer film.

[0042] Furthermore, in this invention, alkaline development or development with an organic solvent can be used as the development method.

[0043] In the present invention, by using the pattern formation method described above, pattern formation can be performed well and efficiently.

[0044] Furthermore, in the present invention, it is preferable to use a semiconductor device substrate, or a semiconductor device substrate on which any of the following films are deposited: a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film.

[0045] In this case, it is preferable to use 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.

[0046] With the pattern forming method of the present invention, a pattern can be formed by processing the above-described substrate as described above.

[0047] Furthermore, in the pattern forming method of the present invention, it is preferable to apply the adhesion film forming material to a thickness of 2 nm or more and 50 nm or less in the step of forming the adhesion film.

[0048] With this pattern formation method, it is possible to remove the formed adhesion film by etching in a short time, and a thinner film can be selected as the upper resist.

[0049] In the pattern formation method of the present invention, the resist upper film can be formed using a resist upper film material that includes at least an organometallic compound and a solvent.

[0050] In this case, it is more preferable that the organometallic compound contains at least one selected from titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium.

[0051] This pattern formation method has the effect of suppressing the collapse of fine patterns and allows for appropriate adjustment of the pattern shape and exposure sensitivity of the resist upper layer film. At the same time, it can prevent contamination of the workpiece substrate by metal compounds when using resist upper layer film materials containing organometallic compounds and solvents.

[0052] Furthermore, the present invention provides a method for forming an adhesion film that functions as an adhesion layer used in the manufacturing process of semiconductor devices, comprising: rotating and coating a substrate to be processed with the adhesion film forming material of the present invention; and heat-treating the substrate coated with the adhesion film forming material at a temperature of 100°C to 300°C for a range of 10 to 600 seconds to form a cured film.

[0053] Furthermore, the present invention provides a method for forming an adhesion film that functions as an adhesion layer used in the manufacturing process of a semiconductor device, comprising: rotating and coating a substrate with the adhesion film forming material of the present invention onto a substrate to be processed; and heat-treating the substrate coated with the adhesion film forming material in an atmosphere with an oxygen concentration of 0.1% to 21% to form a cured film.

[0054] This method promotes the crosslinking reaction during adhesion film formation, thereby more effectively suppressing mixing with the resist upper layer film. Furthermore, by appropriately adjusting the heat treatment temperature, time, and oxygen concentration within the aforementioned range, it is possible to obtain an adhesion film that has a pattern collapse suppression effect suitable for the application, as well as pattern shape adjustment characteristics for the resist upper layer film.

[0055] Furthermore, the present invention provides a method for forming an adhesion film that functions as an adhesion layer used in the manufacturing process of a semiconductor device, comprising: rotating and coating a substrate with the adhesion film forming material of the present invention onto a substrate to be processed; and heat-treating the substrate coated with the adhesion film forming material in an atmosphere with an oxygen concentration of less than 0.1% to form a cured film.

[0056] This method is useful because, even when the substrate to be processed contains materials that are unstable when heated in an oxygen atmosphere, it promotes the crosslinking reaction during adhesion film formation without causing deterioration of the substrate, and more effectively suppresses intermixing with the upper film. [Effects of the Invention]

[0057] As described above, the present invention provides an adhesion film forming material that has high adhesion to the resist upper layer film, prevents scum formation in the spaced areas, and has an effect of suppressing the collapse of fine patterns. Furthermore, this adhesion film forming material has high adhesion, prevents scum formation in the spaced areas, has an effect of suppressing the collapse of fine patterns, can form a good pattern shape, and can suppress the formation of scum in the spaced areas. This material is extremely useful in multilayer resist processes, such as a four-layer resist process in which the adhesion film is formed on a silicon-containing interlayer film, because it is possible to appropriately adjust the pattern shape and exposure sensitivity of the resist upper layer film. Furthermore, the adhesion film forming method of the present invention can form an adhesion film that hardens sufficiently on the substrate to be processed and has high adhesion to the resist upper layer film. Furthermore, the pattern forming method of the present invention can form fine patterns on the substrate to be processed with high precision in a multilayer resist process. [Brief explanation of the drawing]

[0058] [Figure 1] This is an explanatory diagram illustrating an example of a pattern formation method using the four-layer resist process of the present invention. [Figure 2] This is an explanatory diagram showing the adhesion measurement method in the example. [Modes for carrying out the invention]

[0059] As mentioned above, in the fine patterning process using the multilayer resist method in semiconductor device manufacturing processes, there was a need for an adhesion film forming material that has high adhesion to the resist upper layer film and an effect of suppressing the collapse of fine patterns, a pattern formation method using the material, and a method for forming the adhesion film.

[0060] Therefore, the inventors considered that if the amount of polar groups in the exposed and unexposed areas of the resist could be varied, it would be possible to simultaneously improve the adhesion of the resist and reduce scum in the space areas. As a means to achieve this, they focused on a combination of an acid generator and a resin having acid-dissociable groups. Specifically, they considered that the acid generator would generate acid in the exposed area, causing the detachment of acid-dissociable groups and resulting in a structural change accompanied by a change in the amount of polar groups in the exposed area. This would allow them to develop a resist underlayer film that exhibits excellent adhesion to the resist upper layer film while suppressing the formation of scum in the space areas. After diligent research, they found that an adhesion film-forming material mainly composed of a compound with a specific structure, a pattern-forming method using this material, and a method for forming an adhesion film are extremely effective, leading to the completion of the present invention.

[0061] In other words, the present invention relates to an adhesion film forming material for an adhesion film formed directly beneath a resist upper layer film, wherein the adhesion film forming material comprises (A) a resin having structural units containing acid-dissociable groups and at least two types of structural units represented by the following general formula (1), and (C) an organic solvent, and further comprises (B) a photoacid generator, or the resin (A) has structural units that generate acid in the presence of light, or the resin (B) comprises a photoacid generator and the resin (A) has structural units that generate acid in the presence of light. [ka] (In the above general formula (1), R 1 R is a hydrogen atom or a methyl group, 2 is a base selected from the above formulas (1-1) to (1-3). In the above formulas, dashed lines indicate bonding.

[0062] In this specification, when an element is said to be "directly below" another element, it is in direct contact with the other element and there are no intervening elements. In contrast, when an element is said to be "below" another element, there may be intervening elements between them. Similarly, when an element is said to be "directly above" another element, it is in direct contact with the other element and there are no intervening elements, while when an element is said to be "above" another element, there may be intervening elements between them.

[0063] Furthermore, in this specification, "acid dissociability" refers to the property of interatomic bonds being cleaved by the action of an acid, and "acid dissociable group" may be either (i) a group having acid dissociability in which the bond between the acid dissociable group and an atom adjacent to it can be cleaved by the action of an acid, or (ii) a group in which, after some of the bonds are cleaved by the action of an acid, a further elimination reaction such as a decarboxylation reaction occurs, and the bond between the acid dissociable group and an atom adjacent to it can be cleaved. The acid dissociable group generates a polar group upon dissociation.

[0064] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0065] [Adhesion film forming material] The present invention relates to an adhesion film forming material for an adhesion film formed directly beneath a resist upper layer film, wherein the adhesion film forming material comprises (A) a resin having structural units containing acid-dissociable groups and at least two types of structural units represented by the following general formula (1), and (C) an organic solvent, and further comprises (B) a photoacid generator, or the resin (A) has structural units that generate acid in the presence of light, or the resin (B) contains a photoacid generator and the resin (A) has structural units that generate acid in the presence of light. In the adhesion film forming material of the present invention, the resin (A) can be used alone or in combination of two or more types. Furthermore, the adhesion film forming material may also contain components other than the above components (A) to (C). The following explains each component.

[0066] [(A) Resin] The resin (A) contained in the adhesive film-forming material of the present invention has structural units containing acid-dissociable groups and at least two types of structural units represented by the following formula (1). [ka] (In the above general formula (1), R 1 R is a hydrogen atom or a methyl group, 2 is a base selected from the above formulas (1-1) to (1-3). In the above formulas, dashed lines indicate bonding.

[0067] The structural unit represented by the general formula (1) functions as a crosslinking group and an adhesion group. The interaction of hydroxyl groups generated by the ring-opening reaction that occurs during the curing of the epoxy or oxetane structure imparts curability without impairing adhesion between the resist upper film and the workpiece substrate or silicon-containing interfilm. Furthermore, by combining multiple of these structural units, the crosslinking network becomes more complex, enabling stronger interactions and further improving adhesion.

[0068] Furthermore, the following are examples of structural units that can be represented by the general formula (1) above. 1 This is the same as above. [ka]

[0069] The structural unit containing the acid-dissociable group is preferably one of the structures represented by the following general formulas (2) to (4), but is not limited thereto. [ka] (In the formula, R 3 , R 5 , R 10 Each of these is independently either a hydrogen atom or a methyl group. 4 、 R 9 These are each an independently acid-dissociable group. 1X is a single bond, or a linking group having 1 to 14 carbon atoms that includes a phenylene group, a naphthylene group, an ester bond, an ether bond, or a lactone ring. 2 X is a single bond, an ester bond, or an amide bond. 3 These are single bonds, ether bonds, or ester bonds. 6 R is a single bond or a saturated hydrocarbylene group having 1 to 6 carbon atoms, and some of its carbon atoms may be substituted with ether bonds or ester bonds. 8 a is a fluorine atom, a trifluoromethyl group, a cyano group, or a saturated hydrocarbyl group having 1 to 6 carbon atoms. a is 1 or 2. b is an integer from 0 to 4, where 1 ≤ a + b ≤ 5. 4 This is an alkylene group having 1 to 10 carbon atoms, which may contain an etheric oxygen atom in a single bond or in the middle of the chain. 11 Each of these is independently a hydrogen atom, a halogen atom, a linear, branched, or cyclic acyloxy group having 2 to 8 carbon atoms that may be halogen-substituted, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms that may be halogen-substituted, or a linear, branched, or cyclic alkoxy group having 1 to 6 carbon atoms that may be halogen-substituted. 12 and R 13 Each of these is independently a linear or branched alkyl group having 1 to 15 carbon atoms, which may be substituted with a hydrogen atom, a hydroxyl group, or an alkoxy group, or a monovalent aromatic ring-containing group which may have substituents. 14 OR is a linear, branched, or cyclic monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may contain a hydrogen atom, an etheric oxygen atom in the middle of the chain, or a carbonyl group or carbonyloxy group in the middle or at the end of the chain, or a monovalent aromatic ring-containing group which may have substituents. 14 This forms an acid-dissociating group. c is 0 or 1, d is an integer between 0 and 2, and f is an integer between 1 and 3. e is (5 + 2d - f).

[0070] The following are some examples of monomers that give rise to the general formula (2), but they are not limited to these. 3 and R 4 This is the same as above.

[0071] [ka]

[0072] Furthermore, the following are some examples of monomers that give rise to the general formula (3), but are not limited to these. 5 and R 9 This is the same as above. [ka]

[0073] R 4 or R 9 Various monovalent acid-dissociable groups can be selected, but examples include those represented by the following formulas (AL-1) to (AL-3). [ka] (In the equation, dashed lines indicate connections.)

[0074] In formula (AL-1), R L1 This group is a tertiary hydrocarbyl group having 4 to 61 carbon atoms, preferably 4 to 15 carbon atoms; a trihydrocarbylsilyl group in which each hydrocarbyl group is a saturated hydrocarbyl group having 1 to 6 carbon atoms; a carbonyl group; a saturated hydrocarbyl group having 4 to 20 carbon atoms including an ether bond or an ester bond; or a group represented by formula (AL-3). AX is an integer from 0 to 6. Note that a tertiary hydrocarbyl group refers to a group obtained by the removal of a hydrogen atom from a tertiary carbon atom of a hydrocarbon.

[0075] R L1The tertiary hydrocarbyl group represented by can be saturated or unsaturated, and can be branched or cyclic. Specific examples include tert-butyl group, tert-pentyl group, 1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, and 2-methyl-2-adamantyl group. Examples of the trihydrocarbyl group include trimethylsilyl group, triethylsilyl group, and dimethyl-tert-butylsilyl group. The saturated hydrocarbyl group containing the carbonyl group, ether bond, or ester bond may be linear, branched, or cyclic, but cyclic is preferred. Specific examples include 3-oxocyclohexyl group, 4-methyl-2-oxooxan-4-yl group, 5-methyl-2-oxooxolan-5-yl group, 2-tetrahydropyranyl group, and 2-tetrahydrofuranyl group.

[0076] Examples of acid-dissociable groups represented by formula (AL-1) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-pentyloxycarbonyl group, tert-pentyloxycarbonylmethyl group, 1,1-diethylpropyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, and 2-tetrahydrofuranyloxycarbonylmethyl group.

[0077] Furthermore, as an acid-dissociable group represented by formula (AL-1), the following groups represented by formulas (AL-1)-1 to (AL-1)-16 can also be mentioned. [ka] (In the formula, AX is the same as above. R L8Each of these is independently a saturated or unsaturated hydrocarbyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. L9 R is a hydrogen atom or a saturated or unsaturated hydrocarbyl group having 1 to 10 carbon atoms. L10 R is a saturated or unsaturated hydrocarbyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. L11 R is a hydrogen atom, a saturated or unsaturated hydrocarbyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. L12 R is a hydrogen atom, halogen atom, difluoromethyl group, trifluoromethyl group, difluoromethoxy group, trifluoromethoxy group, cyano group, nitro group, or saturated or unsaturated hydrocarbyl group having 1 to 6 carbon atoms, and may have an ether group or a sulfide group, and may have multiple R L12 They may also bond together to form a ring. L13 r is a hydrogen atom, or a saturated or unsaturated hydrocarbyl group having 1 to 6 carbon atoms. The saturated or unsaturated hydrocarbyl group may be linear, branched, or cyclic. r is an integer from 1 to 4, and r' is an integer from 1 to 6. Dashed lines indicate bonding.

[0078] In formula (AL-2), R L2 and R L3 Each of these is independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, and the like.

[0079] In formula (AL-2), R L4This is a hydrocarbyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, which may contain heteroatoms. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Examples of the hydrocarbyl group include saturated hydrocarbyl groups having 1 to 18 carbon atoms, and some of these hydrogen atoms may be substituted with hydroxyl groups, alkoxy groups, oxo groups, amino groups, alkylamino groups, etc. Examples of such substituted saturated hydrocarbyl groups are shown below. [ka] (In the equation, dashed lines indicate connections.)

[0080] In formula (AL-2), R L2 and R L3 , R L2 and R L4 , or R L3 and R L4 These atoms may bond with each other to form a ring with the carbon atoms to which they are bonded, or with carbon atoms and oxygen atoms, in which case the R atoms involved in ring formation L2 and R L3 , R L2 and R L4 , or R L3 and R L4 Each of these is an alkanediyl group having 1 to 18 carbon atoms, preferably 1 to 10. The number of carbon atoms in the ring obtained by bonding these is preferably 3 to 10, more preferably 4 to 10.

[0081] Among the acid-dissociable groups represented by formula (AL-2), linear or branched groups include, but are not limited to, those represented by formulas (AL-2)-1 to (AL-2)-69 below. In the following formulas, dashed lines represent bonds. [ka]

[0082] [ka]

[0083] [Chemical formula]

[0084] [Chemical formula]

[0085] Among the acid-dissociable groups represented by formula (AL-2), cyclic ones include a tetrahydrofuran-2-yl group, a 2-methyltetrahydrofuran-2-yl group, a tetrahydropyran-2-yl group, a 2-methyltetrahydropyran-2-yl group, and the like.

[0086] In addition, examples of the acid-dissociable group include a group represented by the following formula (AL-2a) or (AL-2b). The base polymer may be crosslinked intermolecularly or intramolecularly by the acid-dissociable group. [Chemical formula] (In the formula, the dashed line represents a bond.)

[0087] In formula (AL-2a) or (AL-2b), R L11 and R L12 are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 8 carbon atoms. The saturated hydrocarbyl group may be linear, branched, or cyclic. Also, R L11 and R L12 may be bonded to each other to form a ring together with the carbon atom to which they are bonded. In this case, R L11 and R L12 are each independently an alkanediyl group having 1 to 8 carbon atoms. R L13 is each independently a saturated hydrocarbylene group having 1 to 10 carbon atoms, and the saturated hydrocarbylene group may be linear, branched, or cyclic. B1 and D1 are each independently an integer of 0 to 10, preferably an integer of 0 to 5, and C1 is an integer of 1 to 7, preferably an integer of 1 to 3. L Ais an aliphatic saturated hydrocarbon group having (C1 + 1) valences and 1 to 50 carbon atoms, an alicyclic saturated hydrocarbon group having (C1 + 1) valences and 3 to 50 carbon atoms, an aromatic hydrocarbon group having (C1 + 1) valences and 6 to 50 carbon atoms, or a heterocyclic group having (C1 + 1) valences and 3 to 50 carbon atoms. Also, a part of the carbon atoms of these groups may be substituted with a heteroatom-containing group, and a part of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a hydroxy group, a carboxyl group, an acyl group, or a fluorine atom. L A As, saturated hydrocarbon groups such as a saturated hydrocarbylene group having 1 to 20 carbon atoms, a trivalent saturated hydrocarbon group, a tetravalent saturated hydrocarbon group, and an arylene group having 6 to 30 carbon atoms are preferable. The saturated hydrocarbon group may be linear, branched, or cyclic. L B is -C(=O)-O-, -NH-C(=O)-O-, or -NH-C(=O)-NH-.

[0088] Examples of the crosslinked acetal group represented by formula (AL-2a) or (AL-2b) include groups represented by the following formulas (AL-2)-70 to (AL-2)-77.

[0089]

Chemical formula

[0090] In formula (AL-3), R L5 , R L6 and R L7 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, which may contain a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a fluorine atom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cyclic unsaturated hydrocarbyl group having 3 to 二十 carbon atoms, an aryl group having 6 to 10 carbon atoms, etc. Also, R L5 and R L6 , R L5 and R L7 , or R L6 and RL7 These atoms may bond with each other to form an alicyclic ring with 3 to 20 carbon atoms, together with the carbon atoms to which they are bonded.

[0091] The group represented by formula (AL-3) is the tert-butyl group, 1 , 1-Diethylpropyl group, 1-ethyl norb Ru Examples include the nyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, 2-(2-methyl)adamantyl group, 2-(2-ethyl)adamantyl group, and tert-pentyl group.

[0092] In addition, the groups represented by formula (AL-3) include those represented by the following formulas (AL-3)-1 to (AL-3)-19. [ka] (In the equation, dashed lines represent connections.)

[0093] In equations (AL-3)-1 to (AL-3)-19, R L14 Each of these is independently a saturated hydrocarbyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms. L15 and R L17 Each of these is independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 20 carbon atoms. L16 This is an aryl group having 6 to 20 carbon atoms. The saturated hydrocarbyl group may be linear, branched, or cyclic. Furthermore, a phenyl group is preferred as the aryl group. F The atoms are fluorine, iodine, difluoromethyl, trifluoromethyl, cyano, and nitro. g is an integer from 0 to 5.

[0094] Furthermore, examples of acid-dissociable groups include groups represented by the following formulas (AL-3)-20 or (AL-3)-21. The polymer may be intramolecularly or intermolecularly crosslinked by these acid-dissociable groups. [ka] (In the equation, dashed lines represent connections.)

[0095] In equations (AL-3)-20 and (AL-3)-21, R L14 The same as above. R L18 This is a saturated or unsaturated hydrocarbylene group with 1 to 20 carbon atoms and a (E1+1) valency, or an arylene group with 6 to 20 carbon atoms and a (E1+1) valency, which may contain heteroatoms such as oxygen, sulfur, or nitrogen atoms. The saturated hydrocarbylene group may be linear, branched, or cyclic. E1 is an integer from 1 to 3.

[0096] Examples of monomers that give repeating units containing an acid-dissociable group represented by formula (AL-3) include (meth)acrylic acid esters containing the exo-isomer structure represented by the following formula (AL-3)-22. [ka]

[0097] In formula (AL-3)-22, R A is the aforementioned R 3 It is the same as R Lc1 This is a saturated hydrocarbyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may be substituted. The saturated hydrocarbyl group may be linear, branched, or cyclic. Lc2 ~R Lc11 Each of these is independently a C1-C15 hydrocarbyl group which may contain a hydrogen atom or a heteroatom. Examples of the heteroatom include an oxygen atom. Examples of the hydrocarbyl group include a C1-C15 alkyl group and a C6-C15 aryl group. Lc2 and R Lc3 , R Lc4 and R Lc6 , R Lc4 and R Lc7 , R Lc5 and R Lc7 , R Lc5 and R Lc11 , R Lc6 and R Lc10 , R Lc8 and R Lc9 , or R Lc9 and RLc10 These may be bonded to each other and form a ring with the carbon atoms to which they are bonded, and in this case, the groups involved in the bonding may be hydrocarbylene groups containing heteroatoms with 1 to 15 carbon atoms. Also, R Lc2 and R Lc11 And, R Lc8 and R Lc11 or R Lc4 and R Lc6 This means that adjacent carbon atoms bond to each other without any intermediary, forming a double bond. Furthermore, this formula also represents enantiomers.

[0098] Here, examples of monomers that give repeating units represented by formula (AL-3)-22 include those described in Japanese Patent Publication No. 2000-327633. Specifically, these include, but are not limited to, the following. Note that in the following formula, R A is the aforementioned R 3 It is the same as this. [ka]

[0099] Examples of monomers that give repeating units containing an acid-unstable group represented by formula (AL-3) include (meth)acrylic acid esters containing a franziyl group, a tetrahydrofranziyl group, or an oxanorbornanediyl group, represented by the following formula (AL-3)-23. [ka]

[0100] In formula (AL-3)-23, R A is the aforementioned R 3 It is the same as R Lc12 and R Lc13 These are, independently, hydrocarbyl groups having 1 to 10 carbon atoms. Lc12 and R Lc13 These atoms may bond with each other to form an alicyclic ring with the carbon atoms to which they are bonded. Lc14 This is a franziyl group, a tetrahydrofranziyl group, or an oxanorbornanediyl group.Lc15 This is a C1-C10 hydrocarbyl group which may contain a hydrogen atom or a heteroatom. The hydrocarbyl group may be linear, branched, or cyclic. Specific examples include a saturated C1-C10 hydrocarbyl group.

[0101] The monomers that give the repeating unit represented by formula (AL-3)-23 include, but are not limited to, the following. Note that in the following formula, R A is the aforementioned R 3 It is the same as, where Ac is an acetyl group and Me is a methyl group.

[0102] [ka]

[0103] [ka]

[0104] When a resin containing the structural units represented by the general formulas (2) and (3) is used, polar groups such as phenolic hydroxyl groups and carboxyl groups are locally generated in the areas where acid is produced. Therefore, by adding a photoacid generator to a resin having such structural units, polar groups can be generated in the exposed areas. This improves adhesion in the exposed areas, making it possible to achieve both high adhesion and scum prevention in the spaced areas, mainly in negative-type resists.

[0105] Among the repeating units represented by the general formula (4) above, those represented by the following formula (4') are particularly preferred, but are not limited thereto. 10 , R 12 , R 13 , R 14 , and f are the same as above. [ka]

[0106] Furthermore, the following are examples of structural units that can be represented by the general formula (4) mentioned above.

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] In the structural unit represented by the general formula (4) above, (OR 14 The ) group behaves as an acid-dissociable group. Protonation by acid causes (OR 14 ) The base is HOR 14 It is eliminated as such, and a carbon-carbon double bond (such as a styrene structure) is formed via a carbocation.

[0113] When a resin containing the structural unit represented by the general formula (4) is used, polar structures such as hydroxyl groups, ester bonds, and ether bonds are locally reduced in the areas where acid is generated. Therefore, by adding a photoacid generator to a resin having such structural units, the number of polar groups in the exposed areas can be reduced. As a result, the adhesion in the unexposed areas remains unchanged, while the peeling of the upper resist in the exposed areas improves, thus enabling both high adhesion and scum prevention in the spaced areas, mainly in positive-type resists.

[0114] Preferably, the resin (A) further has at least one of the structural units represented by the following general formulas (5) to (6), but is not limited to these. [ka] (In the formula, R 15 , R 17 Each of these is independently either a hydrogen atom or a methyl group. 16 is an alkyl group having 1 to 3 carbon atoms, m is an integer of 1 or 2, n is an integer of 0 to 4, and m+n is an integer between 1 and 5 (inclusive). 5 R represents an alkylene group which may contain a single bond or an oxygen atom with 1 to 10 carbon atoms. 18 This is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -OC(=O)- and Z 21 R is a saturated hydrocarbylene group having 1 to 12 carbon atoms, and may contain a carbonyl group, an ester bond, or an ether bond. 19 ~R 21 Each of these is independently a hydrocarbyl group having 1 to 20 carbon atoms, which may contain heteroatoms. Also, R 19 , R 20 and R 21 Any two of these may bond with each other to form a ring with the sulfur atom to which they are bonded. 1 (This is either a hydrogen atom or a trifluoromethyl group.)

[0115] X in the general formula (5) above 5 Examples include, but are not limited to, the following. [ka] (In the equation, dashed lines indicate connections.)

[0116] In the above general formula (5), R 16 Examples of suitable groups include methyl, ethyl, propyl, and isopropyl groups, but a methyl group is preferable from the viewpoint of adhesion to the resist upper film.

[0117] Examples of compounds represented by the general formula (5) above include, but are not limited to, the following: In the following formula, R 15 This is the same as above.

[0118] [ka]

[0119] [ka]

[0120] In the above general formula (6), R 18 ga-Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 If -OC(=O)-, then Z 21 Examples of saturated hydrocarbylene groups having 1 to 12 carbon atoms that may contain a carbonyl group, ester bond, or ether bond include, but are not limited to, the following.

[0121] [ka] (In the equation, dashed lines indicate connections.)

[0122] The structural unit represented by the general formula (6) functions as an acid generating group. Sulfonic acid is generated from this structural unit, and this forms hydrogen bonds with the pattern, thereby improving adhesion to the resist. Furthermore, since the generated acid is bound to the polymer main chain, it is possible to prevent deterioration of the pattern roughness of the resist upper film due to excessive acid diffusion. When the resin has such a structural unit, it can exhibit good adhesion and scum prevention ability without the need to add acid generating agents as described later.

[0123] The following are examples of monomer anions that give rise to the above general formula (6), but are not limited to these. In the following formula, R 17This is the same as above. [ka]

[0124] Examples of monomer cations that give rise to the above general formula (6) include triphenylsulfonium, 4-hydroxyphenyldiphenylsulfonium, bis(4-hydroxyphenyl)phenylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-tert-butoxyphenyldiphenylsulfonium, bis(4-tert-butoxyphenyl)phenylsulfonium, tris(4-tert-butoxyphenyl)sulfonium, 3-tert-butoxyphenyldiphenylsulfonium, and bis(3-tert-butoxyphenyl Phenyl(phenyl)phenylsulfonium, tris(3-tert-butoxyphenyl)sulfonium, 3,4-di-tert-butoxyphenyldiphenylsulfonium, bis(3,4-di-tert-butoxyphenyl)phenylsulfonium, tris(3,4-di-tert-butoxyphenyl)sulfonium, diphenyl(4-thiophenoxyphenyl)sulfonium, 4-tert-butoxycarbonylmethyloxyphenyldiphenylsulfonium, tris(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium Nium, (4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium, tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium, (4-hydroxy-3,5-dimethylphenyl)diphenylsulfonium, (4-n-hexyloxy-3,5-dimethylphenyl)diphenylsulfonium, dimethyl(2-naphthyl)sulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-O Examples include xocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, trybenzylsulfonium, diphenylmethylsulfonium, dimethylphenylsulfonium, 2-oxo-2-phenylethylthiacyclopentanium, diphenyl2-thienylsulfonium, 4-n-butoxynaphthyl-1-thiacyclopentanium, 2-n-butoxynaphthyl-1-thiacyclopentanium, 4-methoxynaphthyl-1-thiacyclopentanium, and 2-methoxynaphthyl-1-thiacyclopentanium.More preferably, triphenylsulfonium, 4-tert-butylphenyldiphenylsulfonium, 4-tert-butoxyphenyldiphenylsulfonium, tris(4-tert-butylphenyl)sulfonium, tris(4-tert-butoxyphenyl)sulfonium, dimethylphenylsulfonium, etc. can be mentioned. Furthermore, those represented by the following structures can also be exemplified, but are not limited thereto.

[0125] [Chemical formula]

[0126] Moreover, the (A) resin contained in the adherent film-forming material of the present invention has a structural unit containing an acid dissociable group and at least two structural units represented by the above general formula (1).

[0127] By combining a plurality of structural units, not only can the progress degree of the elimination reaction be adjusted to improve the adhesion and enhance the effect of suppressing the collapse of the fine pattern, but also the pattern shape, exposure sensitivity, etc. of the resist upper layer film can be appropriately adjusted.

[0128] Furthermore, in the present invention, the molar fraction of the structural unit represented by the above general formula (1) in the (A) resin is preferably 10% or more and 99% or less, and more preferably 60% or more and 95% or less. Also, the molar fraction of the structural unit containing an acid dissociable group is preferably 0.1% or more and 60% or less, and more preferably 3% or more and 20% or less. Also, the molar fraction of the structural unit represented by (5) to (6) is preferably 0% or more and 60% or less, and more preferably 3% or more and 20% or less. By combining the structural units within such a range, it becomes possible to impart adhesion while maintaining the curability. In particular, when the total number of moles of all structural units in the resin (A) is 1.0, the total number of moles of the structural units represented by the general formula (1) is 0.10 or more and 0.99 or less, the total number of moles of the structural units containing an acid dissociable group is 0.001 or more and 0.60 or less, and the total number of moles of the structural units represented by (5) to (6) is 0 or more and 0.60 or less. If the compositional ratio of the structural units in the resin (A) is like this, when the acid dissociable group dissociates in the exposed part, the amount of polar groups on the film surface changes, and it is possible to form an adhesion film having high adhesion to the resist upper layer film and high ability to suppress scum in the pattern part.

[0129] In addition, when the mole fractions of the structural units represented by the general formula (1), the structural units containing an acid dissociable group, and the repeating units represented by (5) to (6) do not total 100%, the resin (A) contains other structural units. As the other structural units in that case, other acrylic acid esters, other methacrylic acid esters, other acrylamides, other methacrylamides, crotonic acid esters, maleic acid esters, itaconic acid esters and other α,β-unsaturated carboxylic acid esters; α,β-unsaturated carboxylic acids such as methacrylic acid, acrylic acid, maleic acid, itaconic acid; acrylonitrile; methacrylonitrile; α,β-unsaturated lactones such as 5,5-dimethyl-3-methylene-2-oxotetrahydrofuran; norbornene derivatives, tetracyclo[4.4.0.1 2,5 .1 7,10 dodecene derivatives and other cyclic olefins; α,β-unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride; allyl ethers; vinyl ethers; vinyl esters; any structural units derived from vinyl silanes can be used in combination.

[0130] For an adhesion film forming material containing these resins, it is possible to form an adhesion film forming material having high adhesion to the resist upper layer film and having an effect of suppressing the collapse of fine patterns, and it can be easily manufactured.

[0131] By using such a resin-containing adhesion film-forming material for forming multilayer resist films applied to microfabrication in the manufacturing process of semiconductor devices, it becomes possible to provide an adhesion film-forming material, an adhesion film-forming method, and a pattern-forming method for forming an adhesion film that has high adhesion to the resist upper layer film and an effect of suppressing the collapse of fine patterns.

[0132] The aforementioned resin can be synthesized by known methods. The polymerization reaction is not particularly limited, but radical polymerization is preferred. For these methods, please refer to Japanese Patent Application Publication No. 2004-115630.

[0133] The resin preferably has a weight-average molecular weight (Mw) of 3,000 to 70,000, and more preferably 15,000 to 50,000. If Mw is 3,000 or higher, it has excellent film-forming properties and can suppress the generation of sublimation products during heat curing, thereby suppressing contamination of equipment by sublimation products. On the other hand, if Mw is 70,000 or lower, it can suppress the occurrence of poor coating properties and coating defects due to insufficient solubility in solvents. Furthermore, the resin preferably has a molecular weight distribution (Mw / Mn) of 1.0 to 3.8, and more preferably 1.0 to 2.8. In this invention, Mw and molecular weight distribution are polystyrene-converted values ​​measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the solvent.

[0134] [(B) Photoacid Generator] In the adhesive film-forming material of the present invention, (B) a photoacid generator can be added to locally remove acid-dissociable groups in the exposed area.

[0135] This invention Formation of an adhesion film Examples of photoacid generators (B) that can be used in the material include the structural unit represented by the general formula (6) contained in the resin, as well as the following general formula (7). [ka] (In the formula, R 22 , R 23and R 24 Each of these may independently be substituted with a heteroatom or may have a heteroatom interposed in a linear, branched, or cyclic alkyl or alkenyl group having 1 to 10 carbon atoms, or may be substituted with a heteroatom or may have a heteroatom interposed in a linear, branched, or cyclic alkyl or alkenyl group having 6 to 18 carbon atoms. 22 , R 23 and R 24 Any two of these may bond to each other to form a ring with the sulfur atom in the formula. - This represents either the following general formula (8) or (9). [ka] (In the formula, R 25 and R 26 This represents a monovalent hydrocarbon group containing an aliphatic ring structure with 3 to 40 carbon atoms, which may be mutually substituted with heteroatoms or may have heteroatoms interposed. In this case, it is more preferable that the above general formula (8) is represented by the following general formula (8'). [ka] (In the formula, R 27 R represents a hydrogen atom or a trifluoromethyl group. 28 This represents a monovalent hydrocarbon group containing an aliphatic ring structure with 3 to 30 carbon atoms, which may be substituted with heteroatoms or may have heteroatoms interposed.

[0136] R 22 , R 23 and R 24Examples include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; alkenyl groups such as vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl; aryl groups such as phenyl, naphthyl, and thienyl; and aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. An aryl group is preferred. Additionally, some of the hydrogen atoms in these groups may be replaced by heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, and heteroatoms such as oxygen, sulfur, and nitrogen may be interposed. As a result, hydroxy, cyano, carbonyl, ether, ester, sulfonic acid ester, carbonate, lactone, sultone, carboxylic anhydride, haloalkyl groups, etc. may be formed or interposed.

[0137] Also, Y in the general formula (7) - Examples include, but are not limited to, the following.

Chemical formula

[0138]

Chemical formula

[0139]

Chemical formula

[0140]

Chemical formula

[0141]

Chemical formula

[0142] [ka]

[0143] [ka]

[0144] [ka]

[0145] [ka]

[0146] The aforementioned photoacid generator can be used alone or in combination of two or more types to appropriately adjust the pattern shape, exposure sensitivity, etc., of the resist upper layer film. When adding the photoacid generator, the amount added is preferably 1% to 20% by mass, and more preferably 3% to 15% by mass, relative to 100% by mass of the resin. If the amount of photoacid generator added is within the above range, the detachment of acid-dissociable groups is good, and there is no risk of foreign matter problems occurring after resist development or during peeling.

[0147] [(C) Organic Solvents] The organic solvent (C) contained in the adhesion film forming material used in the adhesion film formation method of the present invention is not particularly limited as long as it dissolves the resin (A), the photoacid generator (B), and any other additives present. Specifically, it is the organic solvent (C) described in paragraphs

[0144] to

[0145] of Japanese Patent Application Publication No. 2008-111103, such as ketones including cyclohexanone and methyl-2-n-amyl ketone, alcohols including 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol diethyl ether. Examples include ethers such as methyl 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, propylene glycol monotert-butyl ether acetate, and lactones such as γ-butyrolactone. These can be used individually or in combination of two or more, but are not limited to these.

[0148] [Other additives] In addition to the components (A) to (C) above, the adhesive film-forming material of the present invention may further contain one or more of (D) surfactants, (E) crosslinking agents, and (F) thermal acid generators. Each component will be described below.

[0149] [(D) Surfactants] The adhesion film-forming material of the present invention may contain (D) a surfactant to improve its applicability in spin coating. One surfactant may be used alone or in combination of two or more. As a surfactant, for example, those described in

[0142] to

[0147] of Japanese Patent Application Publication No. 2009-269953 can be used. When adding a surfactant, the amount to be added is preferably 0.001 to 20 parts, more preferably 0.01 to 10 parts, per 100 parts of the (A) resin.

[0150] [(E) Crosslinking agent] Furthermore, the adhesion film-forming material of the present invention may also contain (E) crosslinking agents to enhance curability and further suppress intermixing with the resist upper layer film. The crosslinking agent is not particularly limited, and various known systems of crosslinking agents can be widely used. Examples include melamine-based crosslinking agents, glycoluryl-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. The (E) crosslinking agent can be used alone or in combination of two or more types, and when a crosslinking agent is added, the amount added is preferably 5 to 50 parts, more preferably 10 to 40 parts, per 100 parts of the (A) resin. If the amount added is 10 parts or more, sufficient curability is achieved and intermixing with the resist upper layer film can be suppressed. On the other hand, if the amount added is 50 parts or less, there is no risk of deterioration of adhesion due to the lower ratio of the (A) resin in the composition.

[0151] Examples of melamine-based crosslinking agents include hexamethoxymethylated melamine, hexasubtoxicmethylated melamine, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of glycoluryl-based crosslinking agents include tetramethoxymethylated glycoluryl, tetrabutoxymethylated glycoluryl, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of β-hydroxyalkylamide-based crosslinking agents include N,N,N',N'-tetra(2-hydroxyethyl)adipamide. Examples of isocyanurate-based crosslinking agents include triglycidyl isocyanurate and triallyl isocyanurate. Examples of aziridine-based crosslinking agents include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Examples of oxazoline-based crosslinking agents include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tertbutyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymers.Examples of epoxy crosslinking agents include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0152] Examples of polynuclear phenolic crosslinking agents include the compounds represented by the following general formula (13). [ka] (In the formula, Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. 35 (where is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; q is an integer from 1 to 5.)

[0153] Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. Q is an integer from 1 to 5, more preferably 2 or 3. Specific examples of Q include methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. A group obtained by removing q hydrogen atoms from a base This can be illustrated with R. 35 The C1-C20 alkyl group is either a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosanyl groups, with hydrogen atoms or methyl groups being preferred.

[0154] As examples of compounds represented by the above general formula (13), the following compounds can be specifically cited. Among these, triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and hexamethoxymethylated tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the viewpoint of improving the curability and uniformity of the adhesion film.

[0155] [ka]

[0156] [ka]

[0157] The crosslinking agent (E) can be used alone or in combination of two or more types. The amount of crosslinking agent (E) added is preferably 10% to 50% by mass, and more preferably 15% to 30% by mass, per 100 parts of the resin (A). If the amount added is 10% by mass or more, sufficient curability is achieved and intermixing with the resist upper layer film can be suppressed. On the other hand, if the amount added is 50% by mass or less, the proportion of resin (A) in the composition will be low, and there is no risk of deterioration in adhesion.

[0158] [(F) Thermal acid generator] In the adhesive film-forming material of the present invention, a (F) thermal acid generator can be added to promote the crosslinking reaction by heat and to partially remove the acid-dissociable groups.

[0159] This invention Formation of an adhesion film Examples of thermal acid generators (F) that can be used in materials include those represented by the following general formula (10).

[0160] [ka] (In the formula, K - R represents a non-nucleophilic counterion. 29 , R30 , R 31 and R 32 Each represents a hydrogen atom or a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy groups, etc. Also, R 29 and R 30 , R 29 and R 30 and R 31 This may form a ring, and if a ring is formed, R 29 and R 30 and R 29 and R 30 and R 31 (This represents an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring containing the nitrogen atom in the formula within the ring.)

[0161] The above, R 29 , R 30 , R 31 and R 32These groups may be identical or different from each other. Specifically, examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl groups. Examples of alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl groups. Examples of oxoalkyl groups include 2-oxocyclopentyl and 2-oxocyclohexyl groups, and can also include 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl groups. Examples of oxoalkenyl groups include 2-oxo-4-cyclohexenyl group and 2-oxo-4-propenyl group. Examples of aryl groups include phenyl group and naphthyl group, as well as alkoxyphenyl groups such as p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, and m-tert-butoxyphenyl group, alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group, alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group, alkoxynaphthyl groups such as methoxynaphthyl group and ethoxynaphthyl group, dialkylnaphthyl groups such as dimethylnaphthyl group and diethylnaphthyl group, and dialkoxynaphthyl groups such as dimethoxynaphthyl group and diethoxynaphthyl group. Examples of aralkyl groups include benzyl groups, phenylethyl groups, and phenethyl groups. Examples of aryloxoalkyl groups include 2-phenyl-2-oxoethyl groups, 2-(1-naphthyl)-2-oxoethyl groups, and 2-(2-naphthyl)-2-oxoethyl groups, as well as 2-aryl-2-oxoethyl groups.

[0162] Also, R 29 , R 30 , R31 , R 32 Heteroaromatic rings having a nitrogen atom in the ring include imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, Examples include 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-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-quinoline carbonitride, etc.), isoquinoline derivatives, sinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, etc.

[0163] The above, K -Examples of non-nucleophilic counterions include halide ions such as chloride ions and bromide ions, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate, aryl sulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate, alkyl sulfonates such as mesylate and butanesulfonate, imido acids such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and bis(perfluorobutylsulfonyl)imide, methido acids such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide, and further, sulfonates in which the α position is fluorosubstituted as shown in the general formula (11) below, and sulfonates in which the α and β positions are fluorosubstituted as shown in the general formula (12) below.

[0164] [ka] [ka] In general formula (11), R 33 R is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an allyloxy group. In general formula (12), R 34 These are hydrogen atoms, linear, branched, or cyclic alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms.

[0165] Examples of the aforementioned thermal acid generating agents include the following: [ka]

[0166] The (B) thermoacid generator contained in the adhesion film-forming material of the present invention can be used alone or in combination of two or more types. By adding the thermoacid generator, the crosslinking reaction is promoted and sufficient curability can be obtained. On the other hand, since the detachment of acid-dissociable groups proceeds partially due to the acid derived from the thermoacid generator, it is preferable to use a smaller amount. Specifically, the amount is preferably 0.01 to 3 parts, more preferably 0.01 to 0.05 parts, per 100 parts of the (A) resin. If the adhesion film-forming material contains 0.05 parts or less of thermoacid generator, sufficient curability is ensured, and at the same time, some of the acid-dissociable groups remain without being detached, so good adhesion and scum prevention ability can be expected.

[0167] [Method for forming an adhesive film] The present invention provides a method for forming an adhesion film that has high adhesion to the resist upper layer film and has an effect of suppressing the collapse of fine patterns in a fine patterning process using the multilayer resist method in the semiconductor device manufacturing process, using the aforementioned adhesion film forming material.

[0168] The thickness of the adhesion film-forming material used in the present invention can be selected as appropriate, but it is preferably 2 to 50 nm, and more preferably 5 to 20 nm.

[0169] Furthermore, the adhesion film-forming material of the present invention is extremely useful as an adhesion film material for multilayer resist processes such as a two-layer resist process and a four-layer resist process using a resist underlayer film and a silicon-containing interlayer film.

[0170] The silicon-containing interlayer can be a silicon-containing resist interlayer or an inorganic hard mask interlayer, depending on the pattern formation method described later. The inorganic hard mask interlayer is preferably selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film.

[0171] In the method for forming an adhesion film of the present invention, the adhesion film forming material is coated onto a substrate to be processed by a spin coating method or the like. After spin coating, the organic solvent is evaporated, and baking (heat treatment) is performed to promote the crosslinking reaction in order to prevent intermixing with the resist upper layer film and silicon-containing interlayer film. Baking is preferably performed at a temperature of 100°C to 300°C for 10 to 600 seconds, and more preferably at a temperature of 200°C to 250°C for 10 to 300 seconds. Considering the damage to the adhesion film and the impact on wafer deformation, the upper limit of the heating temperature in the lithography wafer process is preferably 300°C or less, and more preferably 250°C or less.

[0172] Furthermore, in the method for forming an adhesive film of the present invention, the adhesive film-forming material of the present invention can be coated onto a substrate to be processed by a spin coating method or the like, as described above, and the adhesive film-forming material can be fired and cured in an atmosphere with an oxygen concentration of 0.1% to 21% to form an adhesive film. By firing the adhesive film-forming material of the present invention in such an oxygen atmosphere, a sufficiently cured film can be obtained.

[0173] The atmosphere during baking may be not only air, but also an inert gas such as N2, Ar, or He. In this case, the oxygen concentration can be less than 0.1%. The baking temperature and other parameters can be the same as described above. Even if the substrate to be processed contains materials that are unstable when heated in an oxygen atmosphere, the crosslinking reaction during adhesion film formation can be promoted without causing deterioration of the substrate to be processed.

[0174] [Pattern formation method] The pattern forming method using the adhesive film-forming material of the present invention encompasses the following embodiments.

[0175] (i) A method for forming a pattern on a substrate to be processed, (I-1) A step of forming an adhesion film by applying the adhesion film forming material of the present invention onto a substrate to be processed and then heat-treating it. (I-2) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (I-3) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (I-4) A step of transferring the pattern to the adhesion film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of etching the substrate to be processed using the adhesive film on which the pattern is formed as a mask to form a pattern on the substrate. A pattern forming method having the following characteristics.

[0176] (ii) A method for forming a pattern on a substrate to be processed, (II-1) A step of forming a resist underlayer film on a substrate to be processed, (II-2) A step of forming a silicon-containing resist interlayer on the resist underlayer, (II-3) A step of forming an adhesion film by applying the adhesion film forming material of the present invention onto the silicon-containing resist interlayer and then heat-treating it. (II-4) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (II-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-6) A step of transferring the pattern to the adhesion film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (II-7) Using the contact film on which the pattern is formed as a mask, a step of transferring the pattern to the silicon-containing resist interlayer by dry etching. (II-8) A step of transferring the pattern to the resist underlayer film by dry etching, using the silicon-containing resist interlayer film on which the pattern has been transferred as a mask, and (II-9) A step of etching the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate. A pattern forming method having the following characteristics.

[0177] (iii) A method for forming a pattern on a substrate to be processed, (III-1) A step of forming a resist underlayer film on a substrate to be processed. (III-2) A step of forming an inorganic hard mask interlayer film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film. (III-3) A step of forming an adhesion film by applying the adhesion film forming material of the present invention onto the inorganic hard mask interlayer and then heat-treating it. (III-4) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (III-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (III-6) A step of transferring the pattern to the adhesion film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (III-7) Using the adhesive film on which the pattern is formed as a mask, dry etching the above Inorganic hard mask The process of transferring a pattern to an interlayer film, (III-8) The pattern is transferred Inorganic hard mask A step of using the interlayer as a mask to transfer a pattern to the resist underlayer by dry etching, and (III-9) A step of etching the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate to be processed. A pattern forming method having the following characteristics.

[0178] Thus, the adhesion film forming material of the present invention can be suitably used in various pattern formation methods, such as a two-layer resist process and a four-layer resist process in which the adhesion film is formed on a silicon-containing interlayer (silicon-containing resist interlayer, inorganic hard mask interlayer). With these pattern formation methods, pattern collapse can be effectively mitigated by the formation of the adhesion film, making it suitable for photolithography of the resist upper layer film.

[0179] In this case, it is preferable to form the inorganic hard mask interlayer by CVD or ALD.

[0180] Furthermore, in the present invention, it is preferable to use photolithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof as a method for forming a pattern on the resist upper layer film.

[0181] Furthermore, in the pattern forming method of the present invention, it is preferable to apply the adhesion film forming material to a thickness of 2 nm or more and 50 nm or less in the step of forming the adhesion film. With this pattern formation method, it is possible to remove the formed adhesion film by etching in a short time, and a thinner film can be selected as the upper resist.

[0182] The pattern formation method of the present invention will be described below using a four-layer resist process as an example, but it is not limited to this process. First, the present invention provides a method for forming a pattern on a substrate, comprising at least the following steps: forming a resist underlayer film on the substrate using an organic film material; forming a silicon-containing intermediate film (silicon-containing resist intermediate film) on the resist underlayer film using a resist intermediate film material containing silicon atoms; forming an adhesion film on the silicon-containing resist intermediate film using the adhesion film forming material of the present invention; forming a resist upper film on the adhesion film using a resist upper film material consisting of a photoresist composition to form a multilayer resist film; exposing the pattern circuit region of the resist upper film and then developing it with a developer to form a resist upper film pattern on the resist upper film; using the obtained resist upper film pattern as an etching mask to etch the adhesion film and form an adhesion film pattern; using the obtained adhesion film pattern as an etching mask to etch the silicon-containing resist intermediate film and form a silicon-containing resist intermediate film pattern; using the obtained silicon-containing resist intermediate film pattern as an etching mask to etch the resist underlayer film and form a resist underlayer pattern; and further, using the obtained resist underlayer pattern as an etching mask to etch the substrate and form a pattern on the substrate.

[0183] As the silicon-containing resist interlayer in the aforementioned four-layer resist process, a polysilsesquioxane-based interlayer is also preferably used. By giving the silicon-containing resist interlayer an anti-reflective effect, reflection can be suppressed. In particular, for 193nm exposure, if a material containing many aromatic groups and having high substrate etching resistance is used as the resist underlayer, the k value becomes high and substrate reflection becomes high, but by suppressing reflection with a silicon-containing resist interlayer, substrate reflection can be reduced to 0.5% or less. As silicon-containing resist interlayers with an anti-reflective effect, anthracene is preferably used for 248nm and 157nm exposure, and polysilsesquioxane, which has phenyl groups or absorbent groups having silicon-silicon bonds pendanted to it and is crosslinked with acid or heat, is preferably used for 193nm exposure.

[0184] In this case, forming a silicon-containing resist interlayer by spin coating is simpler and more cost-effective than using CVD.

[0185] Furthermore, an inorganic hard mask interlayer may be formed as a silicon-containing interlayer. In this case, at a minimum, a resist underlayer film is formed on the substrate to be processed using an organic film material, an inorganic hard mask interlayer film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the resist underlayer film, an adhesion film is formed on the inorganic hard mask interlayer film using the adhesion film forming material of the present invention, a resist upper layer film is formed on the adhesion film using a resist upper layer film material consisting of a photoresist composition, the pattern circuit region of the resist upper layer film is exposed, and then developed with a developer to form a resist upper layer film pattern on the resist upper layer film, the obtained resist upper layer film pattern is used as an etching mask to etch the adhesion film and form an adhesion film pattern, the obtained adhesion film pattern is used as an etching mask to etch the inorganic hard mask interlayer film and form an inorganic hard mask interlayer film pattern, the obtained inorganic hard mask interlayer film pattern is used as an etching mask to etch the resist underlayer film and form a resist underlayer film pattern, and furthermore, the obtained resist underlayer film pattern is used as an etching mask to etch the substrate to be processed and form a pattern on the substrate.

[0186] As described above, when forming an inorganic hard mask interlayer on a resist underlayer, silicon oxide films, silicon nitride films, and silicon oxynitride films (SiON films) can be formed by CVD or ALD methods. For example, a method for forming a silicon nitride film is described in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The thickness of the inorganic hard mask interlayer is preferably 5 to 200 nm, and more preferably 10 to 100 nm. Furthermore, as the inorganic hard mask interlayer, a SiON film, which has a high effect as an anti-reflective film, is most preferably used. Since the substrate temperature when forming the SiON film is 300 to 500°C, the resist underlayer needs to be able to withstand temperatures of 300 to 500°C.

[0187] The resist upper layer in the aforementioned four-layer resist process can be either positive or negative, and the same photoresist composition as commonly used can be used, but a negative type is more preferable. In the present invention, the adhesion film forming material can be an adhesion film forming material for negative-type resist films in which the structural unit containing the acid-dissociable group has a structure represented by the general formula (2) or (3), or an adhesion film forming material for positive-type resist films in which the structural unit containing the acid-dissociable group has a structure represented by the general formula (4). In the present invention, by selecting an appropriate acid-dissociable group-containing structural unit in the above-mentioned adhesion film-forming material, an adhesion film-forming material for either negative-type resist films or positive-type resist films can be provided.

[0188] First, we will explain the case in which an adhesion film for a negative-type resist film is formed using an adhesion film-forming material containing a resin having a structure represented by general formula (2) or (3) as component (A). In this case, when the contact film and the resist upper layer film formed directly above it are exposed, the acid-dissociable group R 4 , R 9 These groups are detached by the acid from the acid generator, generating polar groups such as hydroxyl and carboxyl groups. The action of these polar groups improves the adhesion between the contact film and the resist upper layer. On the other hand, in the unexposed areas, the hydroxyl and carboxyl groups remain protected by the acid-dissociable groups, making it easier for the resist upper layer to peel off from the contact film and suppressing scum formation. Next, we will explain the case in which an adhesion film for a positive resist film is formed using an adhesion film forming material containing a resin having a structure represented by general formula (4) as component (A). In this case, when the adhesion film and the resist upper layer film formed directly above it are exposed, they behave as acid-dissociable groups (OR 14 The group is affected by the acid from the acid generator, HOR 14 It is eliminated as such, and a carbon-carbon double bond is formed via a carbocation, which then crosslinks. Therefore, the exposed area becomes nonpolar, (OR 14The elimination of the ) group suppresses scum formation and allows for good development. On the other hand, the unexposed areas have polar groups (OR 14 Since the ) group remains, adhesion is maintained. In this invention, the polarity of the adhesion film surface is cleverly reversed between the exposed and unexposed areas, thereby simultaneously improving the adhesion of the resist and reducing scum in the space areas.

[0189] Furthermore, the resist upper layer film is preferably a composition comprising at least an organometallic compound and a solvent, and more preferably the organometallic compound comprises at least one selected from titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium.

[0190] After spin-coating the photoresist composition, pre-baking is performed, preferably at a temperature of 60 to 180°C for 10 to 300 seconds. Subsequently, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain the resist upper layer film pattern. The thickness of the resist upper layer film is not particularly limited, but is preferably 30 to 500 nm, and especially preferably 50 to 400 nm.

[0191] A circuit pattern (resist upper layer pattern) is formed on the resist upper layer. In forming the circuit pattern, it is preferable to form the circuit pattern by lithography using light with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0192] Examples of exposure light include high-energy rays with wavelengths of 300 nm or less, specifically far ultraviolet light, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 laser light (157 nm), Kr2 laser light (146 nm), Ar2 laser light (126 nm), soft X-rays (EUV) in the 3-20 nm range, electron beams (EB), ion beams, and X-rays.

[0193] Furthermore, in forming the circuit pattern, it is preferable to develop the circuit pattern using alkaline development or an organic solvent.

[0194] Next, etching is performed using the obtained resist upper layer pattern as a mask. In the four-layer resist process, etching of the adhesion film is performed using an oxygen-based gas with the resist upper layer pattern as a mask. This forms the adhesion film pattern.

[0195] Next, etching is performed using the obtained adhesion film pattern as a mask. Etching of the silicon-containing resist interlayer and the inorganic hard mask interlayer is performed using a fluorocarbon-based gas with the adhesion film pattern as a mask. This forms the silicon-containing resist interlayer pattern and the inorganic hard mask interlayer pattern.

[0196] The etching of the adhesion film may be performed consecutively prior to the etching of the silicon-containing interlayer, or the etching of only the adhesion film may be performed first, and then the etching of the silicon-containing interlayer may be performed by changing the etching equipment.

[0197] Next, the obtained silicon-containing resist interlayer pattern or inorganic hard mask interlayer pattern is used as a mask to etch the resist underlayer.

[0198] The etching of the next substrate to be processed can also be performed by conventional methods. For example, if the substrate to be processed is SiO2, SiN, or a silica-based low dielectric constant insulating film, etching is performed mainly with a fluorocarbon gas. If it is p-Si, Al, or W, etching is performed mainly with a chlorine-based or bromine-based gas. When the substrate is etched with a fluorocarbon gas, the silicon-containing interlayer pattern in the three-layer resist process is removed simultaneously with the substrate processing. When the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing interlayer pattern must be removed separately by dry etching with a fluorocarbon gas after the substrate processing.

[0199] The substrate to be processed is not particularly limited, and a semiconductor device substrate or a semiconductor device substrate on which any of the following films—metal film, metal carbide film, metal oxide film, metal nitride film, metal oxide carbide film, or metal oxide nitride film—has been deposited can be used. As the metal, 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.

[0200] Specifically, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, or substrates on which the workpiece layer has been deposited, are used. As the workpiece layer, various low-k films and their stopper films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si are used, and can usually be formed to a thickness of 50 to 10,000 nm, and especially 100 to 5,000 nm. When depositing the workpiece layer, the substrate and the workpiece layer are made of different materials.

[0201] An example of a four-layer resist process is shown below using Figure 1. In the four-layer resist process, as shown in Figure 1(A), a resist underlayer 3 is formed on the workpiece layer 2 stacked on the substrate 1 using an organic film material, then a silicon-containing interlayer 4 is formed, an adhesion film 5 is formed on top of that using the adhesion film forming material of the present invention, and finally a resist upper layer 6 is formed on top of that.

[0202] Next, as shown in Figure 1(B), the required portion 7 of the resist upper layer film is exposed, and PEB and development are performed to form a resist pattern 6a (Figure 1(C)). Using this obtained resist pattern 6a as a mask, the adhesion film 5 is etched using an O2-based gas to form an adhesion film pattern 5a (Figure 1(D)). Using this obtained adhesion film pattern 5a as a mask, the silicon-containing interlayer film 4 is etched using a CF-based gas to form a silicon-containing interlayer film pattern 4a (Figure 1(E)). After removing the adhesion film pattern 5a, using this obtained silicon-containing interlayer film pattern 4a as a mask, the resist lower layer film 3 is etched using an O2-based gas to form a resist lower layer film pattern 3a (Figure 1(F)). Furthermore, after removing the silicon-containing interlayer film pattern 4a, the layer to be processed 2 is etched using the resist lower layer film pattern 3a as a mask to form pattern 2a (Figure 1(G)).

[0203] Thus, with the pattern formation method of the present invention, fine patterns can be formed on a workpiece substrate with high precision in a multilayer resist process. [Examples]

[0204] The present invention will be described in more detail below with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited thereto. Molecular weight was measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as the eluent to determine the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in polystyrene terms, and the degree of dispersion (Mw / Mn) was determined from these.

[0205] The monomers (B1) to (B21) shown below were used to synthesize polymers (A1) to (A16) and comparative polymers (R1) to (R5) used as resins (A) for adhesive film-forming materials. [ka]

[0206] [Synthesis Example 1] Synthesis of Polymer (A1) Under a nitrogen atmosphere, 4.31 g of monomer (B1), 43.1 g of monomer (B14), 55.3 g of monomer (B15), 2.35 g of V-601 (2,2'-azobis(isobutyrate)dimethyl, manufactured by Wako Pure Chemical Industries, Ltd.), and 340 g of PGMEA (propylene glycol monomethyl ether acetate) were weighed into a 1 L graduated cylinder, and the mixture was degassed while stirring to prepare a monomer-polymerization initiator solution. 60 g of PGMEA was weighed into another 1 L flask under a nitrogen atmosphere, degassed while stirring, and then heated until the internal temperature reached 80°C. The monomer-polymerization initiator solution was added dropwise over 4 hours, and the polymerization solution was stirred for 16 hours while maintaining the temperature at 80°C, and then cooled to room temperature. The resulting polymerization solution was added dropwise to 5,000 g of vigorously stirred diisopropyl ether (DIPE), and the precipitated polymer was filtered off. Furthermore, the obtained polymer was washed twice with 600g of DIPE, and then vacuum-dried at 50°C for 20 hours to obtain a white powdery polymer (A1) (yield 99.5g, yield 97%). The weight of polymer (A1) was determined by GPC. amount The average molecular weight (Mw) and dispersion (Mw / Mn) were calculated to be Mw = 14,730 and Mw / Mn = 2.01, respectively. [ka]

[0207] [Synthesis Examples 2-16] Synthesis of polymers (A2)-(A16) Monomers and polymerization initiators shown in Table 1 ,oh The reaction and workup were carried out under the same conditions as in Synthesis Example 1, except for the use of a different solvent, to obtain polymers (A2) to (A16) as products. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) determined by GPC are also shown.

[0208] [Table 1]

[0209] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer (R1) 38.9 g of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") was heated and stirred at 80°C under a nitrogen atmosphere. To this, a mixture of 29.7 g of glycidyl methacrylate, 8.9 g of tert-butyl acrylate, 11.3 g of benzyl acrylate, and 38.9 g of PGMEA, and a mixture of 4.0 g of dimethyl 2,2-azobis(2-methylpropionate) and 38.9 g of PGMEA were added simultaneously and separately over 4 hours. After further heating and stirring for 20 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer compound (R1). Analysis revealed that the weight-average molecular weight (Mw) of polymer compound (R1) was 12,000 and the degree of dispersion (Mw / Mn) was 2.4. [ka]

[0210] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer (R2) Under a nitrogen atmosphere, 62.8 g of monomer (B14), 37.2 g of monomer (B15), 1.45 g of V-601, and 340 g of PGMEA were weighed into a 1 L flask, and the mixture was degassed while stirring to prepare a monomer-polymerization initiator solution. 60 g of PGMEA was weighed into another 1 L flask under a nitrogen atmosphere, degassed while stirring, and then heated until the internal temperature reached 80°C. The monomer-polymerization initiator solution was added dropwise over 4 hours, and the polymerization solution was stirred for 16 hours while maintaining the temperature at 80°C, and then cooled to room temperature. The obtained polymerization solution was added dropwise to 1,500 g of vigorously stirred hexane, and the precipitated polymer was filtered off. Furthermore, the obtained polymer was washed twice with 600 g of hexane, and then vacuum-dried at 50°C for 20 hours to obtain a white powdery polymer (R2) (yield 97.5 g, yield 96%). The weight of polymer (R2) was determined by GPC. amount The average molecular weight (Mw) and dispersion (Mw / Mn) were calculated to be Mw = 33,500 and Mw / Mn = 1.88, respectively. [ka]

[0211] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer (R3) Under a nitrogen atmosphere, 45.1 g of monomer (B13), 34.8 g of monomer (B14), 20.0 g of monomer (B15), 4.70 g of V-601 (2,2'-azobis(isobutyrate)dimethyl, manufactured by Wako Pure Chemical Industries, Ltd.), 1.28 g of SEA (2-mercaptoethanol, manufactured by Tokyo Chemical Industry Co., Ltd.), and 340 g of DAA (diacetone alcohol) were weighed into a 1 L flask, and the mixture was degassed while stirring to prepare a monomer-polymerization initiator solution. 60 g of DAA was weighed into another 1 L flask under a nitrogen atmosphere, degassed while stirring, and then heated until the internal temperature reached 80°C. The monomer-polymerization initiator solution was added dropwise over 4 hours, and the polymerization solution was stirred for 16 hours while maintaining its temperature at 80°C, and then cooled to room temperature. The obtained polymerization solution was added dropwise to 1,500 g of hexane that had been vigorously stirred, and the precipitated polymer was filtered off. Furthermore, the obtained polymer was washed twice with 600 g of hexane and then vacuum-dried at 50°C for 20 hours to obtain a white powdery polymer (R3) (yield 101.5 g, yield 96%). The weight of polymer (R3) was determined by GPC. amount The average molecular weight (Mw) and dispersion (Mw / Mn) were calculated to be Mw = 15,300 and Mw / Mn = 1.98, respectively. [ka]

[0212] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer (R4) Under a nitrogen atmosphere, 34 g of monomer (B18), 66 g of monomer (B20), and 25.1 g of V-601 were weighed into a 1 L flask, and the mixture was degassed while stirring to prepare a monomer-polymerization initiator solution. 300 g of methyl isobutyl ketone was weighed into another 1 L flask under a nitrogen atmosphere, and the mixture was degassed while stirring, then heated until the internal temperature reached 80°C. The monomer-polymerization initiator solution was added dropwise over 3 hours, and the polymerization solution was kept at 80°C while stirring for 6 hours, then cooled to room temperature. The resulting polymerization solution was added dropwise to 1,500 g of vigorously stirred hexane, and the precipitated polymer was filtered off. Furthermore, the obtained polymer was washed twice with 600 g of hexane, and then vacuum-dried at 50°C for 20 hours to obtain a white powdery polymer (R4) (yield 98.7 g, yield 97.2%). The weight of polymer (R4) was determined by GPC. amount The average molecular weight (Mw) and dispersion (Mw / Mn) were calculated to be Mw = 5800 and Mw / Mn = 1.97, respectively. [ka]

[0213] [Comparative Synthesis Example 5] Synthesis of Comparative Polymer (R5) Under a nitrogen atmosphere, 32.1 g of monomer (B1), 49.9 g of monomer (B13), 19.0 g of monomer (B21), 15.4 g of V-601, and 340 g of DAA were weighed into a 1 L flask, and the mixture was degassed while stirring to prepare a monomer-polymerization initiator solution. 60 g of DAA was weighed into another 1 L flask under a nitrogen atmosphere, degassed while stirring, and then heated until the internal temperature reached 80°C. The monomer-polymerization initiator solution was added dropwise over 4 hours, and the polymerization solution was stirred for 16 hours while maintaining the temperature at 80°C, and then cooled to room temperature. The obtained polymerization solution was added dropwise to 1,500 g of vigorously stirred hexane, and the precipitated polymer was filtered off. Furthermore, the obtained polymer was washed twice with 600 g of hexane, and then vacuum-dried at 50°C for 20 hours to obtain a white powdery polymer (R5) (yield 101.3 g, yield 94.5%). GPC determines the weight of the polymer (R5) amount The average molecular weight (Mw) and dispersion (Mw / Mn) were calculated to be Mw = 8,100 and Mw / Mn = 2.11, respectively. [ka]

[0214] Preparation of adhesion film-forming materials (AL-1 to 27, comparative AL-1 to 12) For the preparation of the adhesion film-forming materials and comparative materials, the polymers (A1) to (A16) and comparative polymers (R1) to (R5), (AG1) to (AG2) as thermal acid generators, (AG3) to (AG4) as photoacid generators, and (X1) to (X3) as crosslinking agents were used. The adhesion film-forming materials (AL-1 to 27, comparative AL-1 to 12) were prepared by dissolving them in the proportions shown in Table 2 in an organic solvent containing 0.1% by mass of PF636 (manufactured by OMNOVA), and then filtering through a 0.1 μm fluororesin filter. [ka]

[0215] [Table 2]

[0216] The compositions listed in Table 2 are as follows: Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) DAA (Diacetone Alcohol) EL (Ethyl Lactate)

[0217] Example 1: Adhesion Test (Examples 1-1 to 1-27, Comparative Examples 1-1 to 1-12) The above-mentioned adhesion film-forming materials (AL-1~27, comparative AL-1~12) were applied to an SiO2 wafer substrate and baked in air at 215°C for 60 seconds using a hot plate to form an adhesion film with a thickness of 5 nm (AL-1~19, comparative AL-1~11) or 20 nm (AL-20~27, comparative AL-12). Next, (1) these wafers were exposed to open-frame lithography using a KrF lithography apparatus (Nikon; NSR-206D, NA0.82) with a dose of 25 mJ, and heated at 150°C for 60 seconds. (2) Wafers that were not exposed but only heated at 150°C for 60 seconds were cut into 1 × 1 cm squares. Aluminum pins with epoxy adhesive were attached to the cut wafers using a special jig. After that, the wafers were heated at 150°C for 1 hour using an oven to bond the aluminum pins to the substrate. After cooling to room temperature, the initial adhesion was evaluated by measuring the resistance force using a thin film adhesion strength measuring device (Sebastian Five-A).

[0218] Figure 2 shows an explanatory diagram illustrating the adhesion measurement method. In Figure 2, 8 is the silicon wafer (substrate), 9 is the cured film, 10 is the aluminum pin with adhesive, 11 is the support stand, 12 is the grip, and 13 indicates the tensile direction. The adhesion force is the average value of 12 measurements, and a higher value indicates better adhesion of the adhesive film to the substrate. The adhesion was evaluated by comparing the obtained values. The results are shown in Table 3.

[0219] [Table 3]

[0220] As shown in Table 3, it was confirmed that the adhesion strength of Examples 1-1 to 1-27, which used the adhesion film-forming material (AL-1 to 27) of the present invention, changed significantly depending on whether or not exposure was performed. In particular, Examples 1-1 to 1-6, 1-10 to 1-24, and 1-26 to 1-27, which used polymers containing structural units represented by general formula (2) or (3), tended to show improved adhesion when exposure was performed, and are expected to yield good results when used with negative-type resists. On the other hand, Examples 1-7 to 1-9 and 1-25, which used polymers containing structural units represented by general formula (4), showed improved adhesion when no exposure was performed, and good results can be expected when used in combination with positive-type resists. On the other hand, Comparative Examples 1-1 to 1-7, which did not contain a photoacid generator, and Comparative Examples 1-9 to 1-12, which used polymers not containing structural units represented by general formulas (2) to (4), showed little change in adhesion strength depending on whether or not exposure was performed, suggesting that either the pattern collapse prevention ability or the scum prevention ability in the spaced areas was inferior. Furthermore, in Comparative Examples 1-8, which contain only one type of structural unit represented by general formula (1), the adhesion strength changes significantly depending on whether or not exposure is performed. However, the adhesion strength in the exposed area, where the adhesion strength is improved, is smaller than that of the examples of the present invention, suggesting that the adhesion to the resist is also inferior.

[0221] Example 2: ArF immersion exposure pattern formation test using positive resist (Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-6) A silicon wafer substrate was coated with Shin-Etsu Chemical Co., Ltd.'s spin-on carbon ODL-301 (carbon content 88% by mass) and baked at 350°C for 60 seconds to form a 200 nm thick resist underlayer film. A CVD-SiON hard mask interlayer film was then formed on top of this, and the above-mentioned adhesion film forming materials (AL-7~9, 25, comparative AL-3, comparative AL-6~7, comparative AL-9, comparative AL-11~12) were further coated and baked at 215°C for 60 seconds to form an adhesion film with a thickness of 5 nm (AL-7~9, comparative AL-3, comparative AL-6~7, comparative AL-9, comparative AL-11) or 20 nm (AL-25, comparative AL-12). On top of this, a single-layer resist for ArF, a positive-type resist toplayer film material listed in Table 4, was coated and baked at 105°C for 60 seconds to form a 100 nm thick resist toplayer film. A protective film with a thickness of 50 nm was formed by applying an immersion protective film material (TC-1) onto the resist upper layer and baking it at 90°C for 60 seconds.

[0222] As a positive-type resist upper layer material (single-layer resist for ArF), a polymer (PRP-A1), an acid generator (PAG1), and a basic compound (Amine1) were dissolved in a solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 4, and the mixture was filtered through a 0.1 μm fluororesin filter.

[0223] [Table 4]

[0224] Resist polymer: PRP-A1 Molecular weight (Mw)=8,600 Dispersity (Mw / Mn)=1.88 [ka]

[0225] Acid generator: PAG1 [ka]

[0226] Basic compound: Amine1 [ka]

[0227] The immersion protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent in the proportions shown in Table 5 and filtering it through a 0.1 μm fluororesin filter.

[0228] [Table 5]

[0229] Protective film polymer: PP1 Molecular weight (Mw)=8,800 Dispersion degree (Mw / Mn)=1.69 [ka]

[0230] Next, the material was exposed using an ArF immersion lithography system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s polarized illumination, 6% halftone phase shift mask), baked (PEB) at 100°C for 60 seconds, and developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 40 nm 1:1 line-and-space pattern. The cross-sectional shape and roughness of this pattern were observed using an electron microscope. Furthermore, the minimum dimension at which the lines remained sharp and resolved without collapsing when the line size was reduced by increasing the exposure was determined and defined as the collapsing limit (nm). A smaller value indicates higher resistance to collapsing, which is preferable.

[0231] The obtained pattern cross-sectional shape was evaluated using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the pattern roughness was evaluated using an electron microscope (CG4000) manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 6.

[0232] [Table 6]

[0233] As shown in Table 6, Examples 2-1 to 2-4, which used the adhesion film-forming materials of the present invention (AL-7 to 9, AL-25), showed excellent anti-tilting performance, and at the same time, the pattern shape was vertical. On the other hand, in Comparative Examples 2-1 and 2-2, which did not contain a photoacid generator, there was no difference in the amount of polar groups between the exposed and unexposed areas, indicating that either the adhesion or the pattern shape was deteriorated. Furthermore, in Comparative Examples 2-3, 2-4, and 2-6, which did not have acid-dissociable groups, the pattern shape was a trailing shape, and the adhesion was slightly inferior compared to the examples. On the other hand, in Comparative Example 2-5, which used the composition proposed in Patent Document 6, the pattern shape was good, but the adhesion was deteriorated.

[0234] Example 3: ArF immersion exposure pattern formation test using negative resist (Examples 3-1 to 3-22, Comparative Examples 3-1 to 3-9) Similar to the patterning test using positive resist described above, an organic underlayer film and a CVD-SiON hard mask interlayer film were formed on a silicon wafer, and an adhesion film was then formed on top of them. On top of this, a single-layer ArF resist, which is a negative resist upper layer material as described in Table 7, was applied and baked at 100°C for 60 seconds to form a photoresist layer with a thickness of 100 nm. An immersion protective film (TC-1) was applied on top of the photoresist film and baked at 90°C for 60 seconds to form a protective film with a thickness of 50 nm.

[0235] The negative-type resist upper film material was prepared by dissolving the aforementioned polymer (PRP-A1), acid generator (PAG1), and basic compound (Amine1) in the proportions shown in Table 7 in a solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), and filtering the mixture through a 0.1 μm fluororesin filter.

[0236] [Table 7]

[0237] Next, the image was exposed using an ArF immersion lithography system (Nikon Corporation; NSR-S610C, NA1.30, σ0.98 / 0.65, 35-degree dipole s polarized illumination, 6% halftone phase shift mask), baked (PEB) at 100°C for 60 seconds, butyl acetate was dispensed as developer from the developing nozzle for 3 seconds while rotating at 30 rpm, then the rotation was stopped and paddle development was performed for 27 seconds. After rinsing with diisoamyl ether, the image was spin-dried and baked at 100°C for 20 seconds to evaporate the rinsing solvent. This patterning yielded a 43 nm negative-type line and space pattern. The cross-sectional shape of this pattern was observed using an electron microscope. Furthermore, the minimum dimension at which the lines remained sharp and resolved without collapsing when the line size was reduced by decreasing the exposure was determined and defined as the collapsing limit (nm). A smaller value indicates higher resistance to collapsing, which is preferable.

[0238] The obtained pattern cross-sectional shape was evaluated using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the pattern collapse after development was evaluated using an electron microscope (CG4000) manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 8.

[0239] [Table 8]

[0240] As shown in Table 8, Examples 3-1 to 3-22, which used the adhesion film-forming materials of the present invention (AL-1 to 6, AL-10 to 24, AL-26) in pattern formation tests using negative resists, all exhibited good adhesion and rectangular pattern shape. On the other hand, Comparative Examples 3-1 to 3-5, which lacked a photoacid generator, showed no difference in the amount of polar groups between the exposed and unexposed areas, indicating deterioration in either adhesion or pattern shape. Furthermore, Comparative Example 3-6, which contained only one type of structural unit represented by formula (1), and Comparative Example 3-8, which used the composition proposed in Patent Document 6, had rectangular patterns, but their adhesion was somewhat inferior compared to the adhesion film of the present invention. In addition, Comparative Examples 3-7 and 3-9, which lacked acid-dissociable groups, exhibited excellent adhesion, but their patterns had a trailing shape.

[0241] Example 4: Electron beam pattern formation test (Examples 4-1 to 4-2, Comparative Examples 4-1 to 4-6) The above-mentioned adhesion film forming materials (AL-1, AL-4, comparative AL-1, 4, 7, 8, 10, 11) were applied to a silicon wafer substrate and baked at 215°C for 60 seconds to form an adhesion film with a thickness of 5 nm. A metal-containing resist, which is a resist top layer material, was then applied on top of the adhesion film and baked at 180°C for 60 seconds to form a resist top layer with a thickness of 60 nm.

[0242] As the resist upper layer film material (metal-containing resist), a titanium-containing compound (AM-1) and a metal salt sensitizer (S-1) were dissolved in 4-methyl-2-pentanol (MIBC) containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 9, and the mixture was filtered through a 0.1 μm fluororesin filter.

[0243] [Table 9]

[0244] Synthesis of titanium-containing compound (AM-1) 284 g of titanium tetraisopropoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with 500 g of 2-propanol (IPA) solution. While stirring, 27 g of deionized water in a 500 g IPA solution was added dropwise over 2 hours at room temperature. 180 g of 2,4-dimethyl-2,4-octanediol was added to the resulting solution and stirred at room temperature for 30 minutes. This solution was concentrated under reduced pressure at 30°C, then heated to 60°C, and continued under reduced pressure until no more distillate was observed. Once no distillate was visible, 1,200 g of 4-methyl-2-pentanol (MIBC) was added, and the mixture was heated at 40°C under reduced pressure until no more IPA distilled, yielding 1,000 g of MIBC solution of titanium-containing compound AM-1 (compound concentration 25% by mass). The polystyrene-based molecular weight of this solution was measured to be Mw = 1,200.

[0245] Metal salt sensitizer: S-1 [ka]

[0246] Next, a vacuum chamber drawing was performed using a JBX-9000MV (manufactured by JEOL Ltd.) at an acceleration voltage of 50kV. Immediately after drawing, the image was baked (PEB) at 200°C for 60 seconds, and then paddle developed with butyl acetate for 20 seconds to obtain a negative pattern. The obtained resist patterns were evaluated as follows: The exposure level required to resolve 100 nm line-and-space (LS) lines at a 1:1 ratio was defined as the sensitivity. The minimum dimension at which the lines could be resolved without collapsing at this exposure level was determined and defined as the collapsing limit (nm). A smaller value indicates higher resistance to collapsing, which is preferable. The results are shown in Table 10.

[0247] [Table 10]

[0248] As shown in Table 10, Examples 4-1 to 4-2, which use the adhesion film-forming materials (AL-1, AL-4) of the present invention, exhibit a small tilt limit and good pattern shape. On the other hand, Comparative Examples 4-1 to 4-2, which do not have a photoacid generator, show deterioration in either adhesion or pattern shape because there is no difference in the amount of polar groups between the exposed and unexposed areas. Comparative Example 4-3 has excellent adhesion, but the pattern is tapered. Comparative Examples 4-4 to 4-6, including Comparative Example 4-6 which uses the composition proposed in Patent Document 6, have rectangular patterns, but their adhesion is somewhat inferior compared to the adhesion film of the present invention.

[0249] Example 5: EUV exposure pattern formation test using positive resist (Examples 5-1 to 5-3, Comparative Examples 5-1 to 5-3) A silicon wafer substrate was coated with Shin-Etsu Chemical Co., Ltd.'s spin-on carbon ODL-301 (carbon content 88% by mass) and baked at 350°C for 60 seconds to form a resist underlayer film with a thickness of 100 nm. On top of that, Shin-Etsu Chemical Co., Ltd.'s silicon-containing spin-on hard mask SHB-A940 (silicon content 43% by mass) was coated and baked at 220°C for 60 seconds to form a silicon-containing interlayer film with a thickness of 15 nm. Furthermore, the above-mentioned adhesion film-forming compositions (AL-7~AL-8, AL-25, comparative AL-3, comparative AL-6, comparative AL-11) were coated and baked at 220°C for 60 seconds to form an adhesion film with a thickness of 5 nm (AL-7~AL-8, comparative AL-3, comparative AL-6, comparative AL-11) or 20 nm (AL-25). A positive-type resist top layer film formation composition described in Table 11 was applied thereon, and the mixture was baked at 100°C for 60 seconds to form a resist top layer film with a thickness of 40 nm.

[0250] The composition for forming a positive-type resist upper layer film (single-layer resist for EUV) was prepared by dissolving the polymer compound PRP1 and quencher Q1 in the proportions shown in Table 11 in a solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), and filtering the mixture through a 0.1 μm fluororesin filter.

[0251] [Table 11]

[0252] Resist polymer: PRP1 Molecular weight Mw=9,200 Dispersion degree Mw / Mn=1.8 [ka]

[0253] Quencher: Q1 [ka]

[0254] Next, an 18 nm line-and-space (LS) 1:1 pattern was exposed using an EUV lithography system (ASML EUV scanner NXE3400, NA 0.33, σ 0.9, 90-degree dipole illumination), baked (PEB) at 90°C for 60 seconds, and developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a line-and-space pattern with a space width of 18 nm and a pitch of 36 nm. The cross-sectional shape and roughness of this pattern were observed using an electron microscope. Furthermore, the minimum dimension at which the lines could be resolved without collapsing when the exposure amount was gradually increased from the exposure amount at which the above line-and-space pattern was formed was determined and defined as the collapsing limit (nm). A smaller value indicates higher resistance to collapsing, which is preferable.

[0255] The obtained pattern cross-sectional shape was evaluated using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the pattern roughness was evaluated using an electron microscope (CG6300) manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 12.

[0256] [Table 12]

[0257] As shown in Table 12, Examples 5-1 to 5-3, which used the adhesion film-forming compositions AL-7 to AL-8 and AL-25, showed excellent deformation suppression performance and also produced rectangular patterns. On the other hand, Comparative Examples 5-1 to 5-2, which did not contain a photoacid generator, did not show a difference in the amount of polar groups between the exposed and unexposed areas, indicating that either the adhesion or the pattern shape was deteriorated. Furthermore, Comparative Example 5-3, which used the composition proposed in Patent Document 6, produced a rectangular pattern, but its adhesion was slightly inferior to that of the adhesion film of the present invention, and its pattern roughness was also slightly greater.

[0258] Example 6: Etching Process Evaluation (Examples 6-1 to 6-3, Comparative Examples 6-1 to 6-3) Following the formation of the resist upper layer pattern in Example 5, the silicon-containing interlayer was dry-etched (pattern transferred) using the resist upper layer pattern as a mask with the Telius etching system manufactured by Tokyo Electron. The resulting silicon-containing interlayer pattern was then used as a mask to dry-etch (pattern transferred) the resist lower layer to form the resist lower layer pattern. The etching conditions are as follows.

[0259] (Conditions for transferring the resist upper layer pattern to the silicon-containing interlayer) Chamber pressure 10.0 Pa RF Power 1500W CF4 gas flow rate: 75 mL / min O2 gas flow rate: 15 mL / min Time 15sec

[0260] (Conditions for transferring silicon-containing interlayer patterns to the resist underlying layer) Chamber pressure 2.0 Pa RF Power 500W Ar gas flow rate: 75 mL / min O2 gas flow rate: 45 mL / min Time 90sec

[0261] The feasibility of forming a resist underlayer pattern was confirmed by observing the wafer after pattern transfer (dry etching) to the resist underlayer using a top-down SEM view. The evaluation results are shown in Table 13.

[0262] [Table 13]

[0263] As shown in Table 13, in the pattern formation method of the present invention (Examples 6-1 to 6-3), the resist upper layer pattern was successfully transferred to the resist lower layer even when the adhesion film thickness was 5 nm (Examples 6-1 to 6-2) and 20 nm (Example 6-3), indicating that the adhesion film of the present invention is effective for fine patterning by the multilayer resist method. In contrast, in Comparative Examples 6-1 to 6-3, the resist lower layer pattern could not be formed. This result is due to shape defects occurring in the resist pattern.

[0264] From the above, the adhesion film forming material of the present invention has high adhesion to the resist upper layer film and also has a good scum prevention effect in the space areas, making it extremely useful as an adhesion film material used in the multilayer resist method. Furthermore, the pattern forming method of the present invention using this material can form fine patterns on the workpiece substrate with high precision.

[0265] This specification includes the following embodiments: [1]: An adhesion film forming material for an adhesion film formed directly beneath the resist upper layer film, wherein the adhesion film forming material comprises (A) a resin having structural units containing acid-dissociable groups and at least two types of structural units represented by the following general formula (1), and (C) an organic solvent. Furthermore, an adhesion film forming material characterized by containing (B) a photoacid generator, or the resin (A) having structural units that generate acid in the presence of light, or containing the photoacid generator (B) and the resin (A) having structural units that generate acid in the presence of light. [ka] (In the above general formula (1), R 1 R is a hydrogen atom or a methyl group, 2 (The base is selected from the following equations (1-1) to (1-3).) [ka] (In the above equation, dashed lines indicate connections.) [2]: The adhesive film-forming material of [1], characterized in that the structural unit containing the acid-dissociable group has one of the structures represented by the following general formulas (2) to (4). [ka] (In the formula, R 3 , R 5 , R 10 Each of these is independently either a hydrogen atom or a methyl group. 4 、 R 9 These are each an independently acid-dissociable group. 1 X is a single bond, or a linking group having 1 to 14 carbon atoms that includes a phenylene group, a naphthylene group, an ester bond, an ether bond, or a lactone ring. 2 X is a single bond, an ester bond, or an amide bond. 3 These are single bonds, ether bonds, or ester bonds. 6 R is a single bond or a saturated hydrocarbylene group having 1 to 6 carbon atoms, and some of its carbon atoms may be substituted with ether bonds or ester bonds. 8 a is a fluorine atom, a trifluoromethyl group, a cyano group, or a saturated hydrocarbyl group having 1 to 6 carbon atoms. a is 1 or 2. b is an integer from 0 to 4, where 1 ≤ a + b ≤ 5. 4 This is an alkylene group having 1 to 10 carbon atoms, which may contain an etheric oxygen atom in a single bond or in the middle of the chain. 11 Each of these is independently a hydrogen atom, a halogen atom, a linear, branched, or cyclic acyloxy group having 2 to 8 carbon atoms that may be halogen-substituted, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms that may be halogen-substituted, or a linear, branched, or cyclic alkoxy group having 1 to 6 carbon atoms that may be halogen-substituted. 12 and R 13 Each of these is independently a linear or branched alkyl group having 1 to 15 carbon atoms, which may be substituted with a hydrogen atom, a hydroxyl group, or an alkoxy group, or a monovalent aromatic ring-containing group which may have substituents. 14OR is a linear, branched, or cyclic monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may contain a hydrogen atom, an etheric oxygen atom in the middle of the chain, or a carbonyl group or carbonyloxy group in the middle or at the end of the chain, or a monovalent aromatic ring-containing group which may have substituents. 14 This forms an acid-dissociating group. c is 0 or 1, d is an integer between 0 and 2, and f is an integer between 1 and 3. e is (5 + 2d - f). [3]: The adhesion film-forming material of [1] or [2], characterized in that the resin (A) further has at least one of the structural units represented by the following general formulas (5) to (6). [ka] (In the formula, R 15 , R 17 Each of these is independently either a hydrogen atom or a methyl group. 16 is an alkyl group having 1 to 3 carbon atoms, m is an integer of 1 or 2, n is an integer of 0 to 4, and m+n is an integer between 1 and 5 (inclusive). 5 R represents an alkylene group which may contain a single bond or an oxygen atom with 1 to 10 carbon atoms. 18 This is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -OC(=O)- and Z 21 R is a saturated hydrocarbylene group having 1 to 12 carbon atoms, and may contain a carbonyl group, an ester bond, or an ether bond. 19 ~R 21 Each of these is independently a hydrocarbyl group having 1 to 20 carbon atoms, which may contain heteroatoms. Also, R 19 , R 20 and R 21 Any two of these may bond with each other to form a ring with the sulfur atom to which they are bonded. 1 (This is either a hydrogen atom or a trifluoromethyl group.) [4]: The adhesion film-forming material of [3], characterized in that, when the total number of moles of all structural units in the resin of (A) is set to 1.0, the total number of moles of structural units represented by general formula (1) is 0.10 or more and 0.99 or less, the total number of moles of structural units containing acid-dissociable groups is 0.001 or more and 0.60 or less, and the total number of moles of structural units represented by (5) to (6) is 0 or more and 0.60 or less. [5]: An adhesion film-forming material according to any one of [1] to [4], characterized in that the weight-average molecular weight of the (A) resin is 3,000 to 70,000. [6]: A film-forming material that further contains one or more of (D) surfactants, (E) crosslinking agents, and (F) thermal acid generators, as specified in any one of [1] to [5]. [7]:[2] Adhesion film forming material for negative resist film, characterized in that the structural unit containing the acid-dissociable group has a structure represented by the general formula (2) or (3). [8]:[2] Adhesion film forming material, characterized in that the structural unit containing the acid-dissociable group has a structure represented by the general formula (4). [9]: A coating film for forming an adhesion film, characterized by comprising one of the adhesion film forming materials from [1] to [6], and having a thickness of 2 nm or more and 50 nm or less.

[10] A method for forming a pattern on a substrate to be processed, (I-1) A step of forming an adhesion film by applying one of the adhesion film-forming materials [1] to [6] onto a substrate to be processed, and then heat-treating it. (I-2) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (I-3) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (I-4) A step of transferring the pattern to the adhesion film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of etching the substrate to be processed using the adhesive film on which the pattern is formed as a mask to form a pattern on the substrate. A pattern forming method characterized by having the following features.

[11] A method for forming a pattern on a substrate to be processed, (II-1) A step of forming a resist underlayer film on a substrate to be processed, (II-2) A step of forming a silicon-containing resist interlayer on the resist underlayer, (II-3) A step of forming an adhesion film by applying one of the adhesion film forming materials [1] to [6] onto the silicon-containing resist interlayer and then heat-treating it. (II-4) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (II-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-6) A step of transferring the pattern to the adhesion film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (II-7) Using the contact film on which the pattern is formed as a mask, a step of transferring the pattern to the silicon-containing resist interlayer by dry etching. (II-8) A step of transferring the pattern to the resist underlayer film by dry etching, using the silicon-containing resist interlayer film on which the pattern has been transferred as a mask, and (II-9) A step of etching the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate. A pattern forming method characterized by having the following features.

[12] A method for forming a pattern on a substrate to be processed, (III-1) A step of forming a resist underlayer film on a substrate to be processed. (III-2) A step of forming an inorganic hard mask interlayer film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film. (III-3) A step of forming an adhesion film by applying one of the adhesion film-forming materials [1] to [6] onto the inorganic hard mask interlayer and then heat-treating it. (III-4) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (III-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (III-6) A step of transferring the pattern to the adhesion film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (III-7) Using the adhesive film on which the pattern is formed as a mask, dry etching the above Inorganic hard mask The process of transferring a pattern to an interlayer film, (III-8) The pattern is transferred Inorganic hard mask A step of using the interlayer as a mask to transfer a pattern to the resist underlayer by dry etching, and (III-9) A step of etching the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate to be processed. A pattern forming method characterized by having the following features.

[13] : The pattern formation method of

[12] , characterized in that the inorganic hard mask interlayer is formed by CVD or ALD.

[14] : A pattern formation method from any one of

[10] to

[13] , characterized in that a pattern is formed on the resist upper film using photolithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[15] : A pattern formation method characterized by using alkaline development or development with an organic solvent as the development method, one of the methods described in

[10] to

[14] .

[16] : A pattern formation method according to any one of

[10] to

[15] , characterized in that the substrate to be processed is a semiconductor device substrate, or a semiconductor device substrate on which any of the following films are formed: a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film.

[17] : The pattern forming method of

[16] , characterized in that the metal is 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.

[18] : A pattern forming method from any one of

[10] to

[17] , characterized in that, in the step of forming the adhesion film, the adhesion film forming material is applied to a thickness of 2 nm or more and 50 nm or less.

[19] : A pattern formation method according to any one of

[10] to

[18] , characterized in that the resist upper film is formed using a resist upper film material comprising at least an organometallic compound and a solvent.

[20] : The pattern forming method of

[19] , characterized in that the organometallic compound comprises at least one selected from titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium.

[21] : A method for forming an adhesion film that functions as an adhesion layer used in the manufacturing process of a semiconductor device, characterized in that one of the adhesion film forming materials [1] to [6] is applied by rotation onto a substrate to be processed, and the substrate on which the adhesion film forming material is applied is heat-treated at a temperature of 100°C to 300°C for a range of 10 to 600 seconds to form a cured film.

[22] : A method for forming an adhesion film that functions as an adhesion layer used in the manufacturing process of a semiconductor device, characterized in that one of the adhesion film forming materials from [1] to [6] is rotary coated onto a substrate to be processed, and the substrate coated with the adhesion film forming material is heat-treated in an atmosphere with an oxygen concentration of 0.1% or more and 21% or less to form a cured film.

[23] : A method for forming an adhesion film that functions as an adhesion layer used in the manufacturing process of a semiconductor device, characterized in that one of the adhesion film forming materials [1] to [6] is rotary coated onto a substrate to be processed, and the substrate coated with the adhesion film forming material is heat-treated in an atmosphere with an oxygen concentration of less than 0.1% to form a cured film.

[0266] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0267] 1...Substrate, 2...Workpiece layer, 2a...Pattern (pattern formed on the workpiece layer) 3...Resist underlayer film, 3a...Resist underlayer film pattern, 4...Silicon-containing interlayer, 4a...Silicon-containing interlayer pattern, 5...Adhesion film, 5a...Adhesion film pattern, 6...Resist upper layer film, 6a...Resist upper layer film pattern, 7...Exposed area, 8...Silicon wafer, 9...Cured coating, 10...Adhesive-backed aluminum pin 11...Support base, 12...Grip, 13...Tension direction.

Claims

1. An adhesion film forming material for an adhesion film formed directly beneath a resist upper layer film, wherein the adhesion film forming material comprises (A) a resin having structural units containing acid-dissociable groups and at least two structural units represented by the following general formula (1), wherein R2 is a group selected from at least two types of the following formulas (1-1) to (1-3), and (C) an organic solvent. Furthermore, an adhesion film forming material characterized by containing (B) a photoacid generator, or the resin (A) having structural units that generate acid in the presence of light, or containing the photoacid generator (B) and the resin (A) having structural units that generate acid in the presence of light. 【Chemistry 1】 (In the above general formula (1), R １ R is a hydrogen atom or a methyl group, ２ (The base is selected from the following formulas (1-1) to (1-3).) 【Chemistry 2】 (In the above equation, dashed lines indicate connections.)

2. The adhesive film-forming material according to claim 1, characterized in that the structural unit containing the acid-dissociable group has one of the structures represented by the following general formulas (2) to (4). 【Transformation 3】 (In the formula, R ３ , R ５ , R １０ are each independently a hydrogen atom or a methyl group. R ４ 、 R ９ are each independently an acid dissociable group. X １ is a single bond, or a linking group having 1 to 14 carbon atoms including a phenylene group, a naphthylene group, an ester bond, an ether bond or a lactone ring. X ２ is a single bond, an ester bond or an amide bond. X ３ is a single bond, an ether bond or an ester bond. R ６ is a single bond or a saturated hydrocarbylene group having 1 to 6 carbon atoms, and a part of the carbon atoms thereof may be substituted with an ether bond or an ester bond. R ８ is a fluorine atom, a trifluoromethyl group, a cyano group or a saturated hydrocarbyl group having 1 to 6 carbon atoms. a is 1 or 2. b is an integer of 0 to 4. However, 1 ≦ a + b ≦ 5. X ４ is a single bond, or an alkylene group having 1 to 10 carbon atoms which may contain an ether oxygen atom in the middle of the chain. R １１ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms which may be substituted with a halogen, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen. R １２ and R １３ are each independently a linear or branched alkyl group having 1 to 15 carbon atoms which may be substituted with a hydrogen atom, a hydroxy group or an alkoxy group, or a monovalent aromatic ring-containing group which may have a substituent. R １４ is a hydrogen atom, a linear, branched or cyclic monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may contain an ether oxygen atom in the middle of the chain, a carbonyl group or a carbonyloxy group in the middle or at the end of the chain, or a monovalent aromatic ring-containing group which may have a substituent, and OR １４ This forms an acid-dissociating group. c is 0 or 1, d is an integer between 0 and 2, and f is an integer between 1 and 3. e is (5 + 2d - f).

3. The adhesion film forming material according to claim 1, characterized in that the resin (A) further has at least one of the structural units represented by the following general formulas (5) to (6). 【Chemistry 4】 (In the formula, R １５ , R １７ Each of these is independently either a hydrogen atom or a methyl group. １６ is an alkyl group having 1 to 3 carbon atoms, m is an integer of 1 or 2, n is an integer of 0 to 4, and m+n is an integer between 1 and 5. ５ R represents a single bond or an alkylene group which may contain oxygen atoms having 1 to 10 carbon atoms. １８ This is a single bond, -Z ２１ -C(=O)-O-, -Z ２１ -O- or -Z ２１ -O-C (=O)- and Z ２１ R is a saturated hydrocarbylene group having 1 to 12 carbon atoms, and may contain a carbonyl group, an ester bond, or an ether bond. １９ ~R ２１ Each of these is independently a hydrocarbyl group having 1 to 20 carbon atoms, which may contain heteroatoms. Also, R １９ , R ２０ and R ２１ Any two of these may bond with each other to form a ring with the sulfur atom to which they are bonded. １ (This is either a hydrogen atom or a trifluoromethyl group.)

4. The adhesion film-forming material according to claim 3, characterized in that, when the total number of moles of all structural units in the resin (A) is set to 1.0, the total number of moles of structural units represented by general formula (1) is 0.10 or more and 0.99 or less, the total number of moles of structural units containing acid-dissociable groups is 0.001 or more and 0.60 or less, and the total number of moles of structural units represented by (5) to (6) is 0 or more and 0.60 or less.

5. The adhesion film-forming material according to claim 1, characterized in that the weight-average molecular weight of the resin (A) is 3,000 to 70,000.

6. Furthermore, the adhesive film-forming material according to claim 1 is characterized in that it contains one or more of (D) surfactants, (E) crosslinking agents, and (F) thermal acid generators.

7. An adhesion film forming material for a negative-type resist film, characterized in that the structural unit containing the acid-dissociable group has a structure represented by the general formula (2) or (3).

8. The adhesion film forming material for positive resist films according to claim 2, characterized in that the structural unit containing the acid-dissociable group has a structure represented by the general formula (4).

9. A coating film for forming an adhesive film, characterized by comprising the adhesive film-forming material described in claim 1 and having a thickness of 2 nm or more and 50 nm or less.

10. A method for forming a pattern on a substrate to be processed, (I-1) A step of forming an adhesion film by applying an adhesion film forming material according to any one of claims 1 to 6 onto a substrate to be processed, and then heat-treating it. (I-2) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (I-3) A step of pattern exposure of the resist upper layer film, followed by development with a developer to form a pattern on the resist upper layer film. (I-4) A step of transferring the pattern to the adhesion film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of etching the substrate to be processed using the adhesive film on which the pattern is formed as a mask to form a pattern on the substrate to be processed. A pattern forming method characterized by having the following features.

11. A method for forming a pattern on a substrate to be processed, (II-1) A step of forming a resist underlayer film on the substrate to be processed, (II-2) A step of forming a silicon-containing resist interlayer on the resist underlayer, (II-3) A step of forming an adhesion film by applying an adhesion film forming material according to any one of claims 1 to 6 onto the silicon-containing resist interlayer and then heat-treating it. (II-4) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (II-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-6) A step of transferring the pattern to the adhesion film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (II-7) A step of transferring the pattern to the silicon-containing resist interlayer by dry etching, using the adhesion film on which the pattern is formed as a mask. (II-8) A step of transferring the pattern to the resist underlayer film by dry etching using the silicon-containing resist interlayer film on which the pattern has been transferred as a mask, and (II-9) A step of etching the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate to be processed. A pattern forming method characterized by having the following features.

12. A method for forming a pattern on a substrate to be processed, (III-1) A step of forming a resist underlayer film on a substrate to be processed, (III-2) A step of forming an inorganic hard mask interlayer film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film. (III-3) A step of forming an adhesion film by applying an adhesion film forming material according to any one of claims 1 to 6 onto the inorganic hard mask interlayer and then heat-treating it. (III-4) A step of forming a resist upper layer film on the adhesion film using a photoresist material, (III-5) A step of pattern exposure of the resist upper layer film, followed by development with a developer to form a pattern on the resist upper layer film. (III-6) A step of transferring the pattern to the adhesion film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (III-7) A step of transferring the pattern to the inorganic hard mask interlayer by dry etching, using the adhesion film on which the pattern is formed as a mask. (III-8) A step of transferring the pattern to the resist underlayer film by dry etching using the inorganic hard mask interlayer film on which the pattern has been transferred as a mask, and (III-9) A step of etching the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate to be processed. A pattern forming method characterized by having the following features.

13. The pattern forming method according to claim 12, characterized in that the inorganic hard mask interlayer is formed by CVD or ALD.

14. The pattern formation method according to claim 10, characterized in that the method for forming a pattern on the resist upper layer film is to use photolithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

15. The pattern forming method according to claim 10, characterized in that alkaline development or development with an organic solvent is used as the development method.

16. The pattern forming method according to claim 10, characterized in that the substrate to be processed is a semiconductor device substrate, or a semiconductor device substrate on which any of the following films is formed: a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film.

17. The pattern forming method according to claim 16, characterized in that silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof are used as the aforementioned metal.

18. The pattern forming method according to claim 10, characterized in that, in the step of forming the adhesion film, the adhesion film forming material is applied to a thickness of 2 nm or more and 50 nm or less.

19. The pattern forming method according to claim 10, characterized in that the resist upper film is formed using a resist upper film material comprising at least an organometallic compound and a solvent.

20. The pattern forming method according to claim 19, characterized in that the organometallic compound comprises at least one selected from titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium.

21. A method for forming an adhesion film that functions as an adhesion layer used in the manufacturing process of a semiconductor device, characterized by rotatingly coating an adhesion film forming material described in any one of claims 1 to 6 onto a substrate to be processed, and then heat-treating the substrate coated with the adhesion film forming material at a temperature of 100°C to 300°C for a range of 10 to 600 seconds to form a cured film.

22. A method for forming an adhesion film that functions as an adhesion layer used in the manufacturing process of a semiconductor device, characterized by rotatingly coating an adhesion film forming material according to any one of claims 1 to 6 onto a substrate to be processed, and then heat-treating the substrate coated with the adhesion film forming material in an atmosphere with an oxygen concentration of 0.1% or more and 21% or less to form a cured film.

23. A method for forming an adhesion film that functions as an adhesion layer used in the manufacturing process of a semiconductor device, characterized by rotatingly coating an adhesion film forming material according to any one of claims 1 to 6 onto a substrate to be processed, and then heat-treating the substrate coated with the adhesion film forming material in an atmosphere with an oxygen concentration of less than 0.1% to form a cured film.

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