Pattern Formation Method

Abstract

To provide a pattern forming method using an adhesion film which can obtain a good pattern shape, has high adhesiveness with a resist upper layer film and prevents the collapse of a fine pattern in a fine patterning process in a semiconductor device manufacturing process.SOLUTION: There is provided a pattern forming method using a composition for forming an adhesion film comprising (A) a polymer compound, (B) a thermal acid generator and (C) an organic solvent, which comprises: (I-1) a step of forming an adhesion film by applying the composition for forming an adhesion film on a substrate to be processed, followed by heat treatment; (I-2) a step of forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (I-3) a step of forming a circuit pattern on the resist upper layer film by developing the resist upper layer film with a developer after pattern exposure of the resist upper layer film; and (I-4) a step of using the resist upper layer film on which the circuit pattern is formed as a mask and transferring the pattern to the adhesion film and the substrate to be processed by dry etching.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a pattern forming method. [Background technology]

[0002] As LSIs become more highly integrated and faster, pattern dimensions are becoming increasingly miniaturized. Lithography technology has achieved this miniaturization by shortening the wavelength of light sources and selecting appropriate resist compositions to match. The key to this is positive photoresist compositions used in single layers. These single-layer positive photoresist compositions incorporate a backbone that is resistant to dry etching with chlorine- or fluorine-based gas plasma, and also incorporate a switching mechanism that dissolves exposed areas. This allows the exposed areas to be dissolved to form a pattern, and the remaining resist pattern is then used as an etching mask to dry etch a substrate coated with the photoresist composition.

[0003] However, if the thickness of the photoresist film used is kept the same and the pattern width is made smaller, the resolution of the photoresist film will decrease, and in the case of a line-and-space pattern, the aspect ratio of the line pattern will become too large, causing the pattern to collapse when the photoresist film is developed with a chemical solution. For this reason, photoresist films have been made thinner as the pattern becomes smaller.

[0004] On the other hand, processing of substrates typically involves dry etching using a patterned photoresist film as an etching mask. However, as photoresist films become thinner, etching selectivity between the photoresist film and the substrate cannot be ensured. This means that the photoresist film is damaged during processing of the substrate, resulting in the photoresist film collapsing during processing, resulting in inaccurate transfer of the resist pattern to the substrate. Therefore, as patterns become finer, photoresist compositions are required to have higher dry etching resistance. Meanwhile, resins used in photoresist compositions are required to have low light absorption at the exposure wavelength. As wavelengths become shorter (i.e., from i-line to KrF and ArF), their structures change to novolac resins, polyhydroxystyrenes, and resins with aliphatic polycyclic skeletons, which means that the etching rate increases under the above dry etching conditions. In other words, recent photoresist compositions with high resolution tend to have poor etching resistance.

[0005] This means that the substrate to be processed must be dry etched using a thinner photoresist film with weaker etching resistance, and there is a demand for materials and processes for this processing step.

[0006] One method for solving these problems is the multilayer resist method, in which a resist intermediate film having etching selectivity different from that of a photoresist film (i.e., a resist top layer film) is interposed between the resist top layer film and the substrate to be processed, a pattern is formed on the resist top layer film, and then the pattern is transferred to the resist intermediate film by dry etching using the resist top layer film pattern as a dry etching mask, and the pattern is then transferred to the substrate to be processed by dry etching using the resist intermediate film as a dry etching mask.

[0007] An example of a multilayer resist method is a three-layer resist method, which can be performed using a common resist composition used in a single-layer resist method. In this three-layer resist method, for example, an organic film such as novolak is formed on a substrate to be processed as a resist underlayer, a silicon-containing film is formed on top of that as a silicon-containing resist intermediate film, and a conventional organic photoresist film is formed on top of that as a resist upper layer. When dry etching is performed using fluorine-based gas plasma, the organic resist upper layer has a good etching selectivity relative to the silicon-containing resist intermediate film, so the resist upper layer pattern is transferred to the silicon-containing resist intermediate film by dry etching using fluorine-based gas plasma. Furthermore, when etching using oxygen gas or hydrogen gas, the silicon-containing resist intermediate film has a good etching selectivity relative to the resist underlayer film, so the silicon-containing resist intermediate film pattern is transferred to the resist lower layer by etching using oxygen gas or hydrogen gas. According to this method, even if a photoresist composition is used that is difficult to form a pattern with a sufficient film thickness for directly processing a substrate to be processed, or a photoresist composition that does not have sufficient dry etching resistance for processing a substrate, as long as the pattern can be transferred to the silicon-containing film (silicon-containing resist intermediate film), it is possible to obtain a pattern in an organic film (resist underlayer film) made of novolak 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 been attracting attention as a promising alternative to the combined use of ArF immersion lithography and multiple exposure processes. Using this technology, it has become 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 resist materials to compensate for the insufficient output of the light source. However, the increase in shot noise that accompanies high sensitivity leads to an increase in line edge roughness (LER, LWR) of the line pattern, and achieving both high sensitivity and low edge roughness has been cited as one of the important challenges in EUV lithography.

[0010] In recent years, the use of metallic materials in resist materials has been investigated as an attempt to increase resist sensitivity and reduce the effects of shot noise. Compounds containing metal elements such as barium, titanium, hafnium, zirconium, and tin have higher absorbance of EUV light than metal-free organic materials, which is expected to improve resist photosensitivity and suppress the effects of shot noise. Furthermore, metal-containing resist patterns are expected to be etched with high selectivity when combined with an underlayer made of a non-metallic material.

[0011] For example, resist materials using metal salts, organometallic complexes, and metal clusters have been investigated (Patent Documents 1 to 5, Non-Patent Document 1). However, the resolution of these metal-containing resists has not yet reached the level required for practical use, and further improvement in resolution is required.

[0012] Furthermore, with the advent of ArF immersion lithography, EUV lithography, and the like, it is becoming possible to form finer patterns. However, ultrafine patterns have a small contact area, making them extremely susceptible to collapse, and preventing pattern collapse is a major challenge. To prevent pattern collapse, materials have been reported that use resist underlayer films containing polar functional groups such as lactone structures or urea structures to improve adhesion to resist overlayer films (Patent Documents 6 and 7). However, given the current demand for finer pattern formation, these materials are not sufficient in preventing pattern collapse.

[0013] Recently, it has been reported that the interaction at the interface between the resist top layer film and the resist bottom layer film in a fine pattern affects the resist sensitivity, the pattern shape (rectangularity and space residues), etc., and improvements in the performance of the resist bottom layer film are required from these perspectives as well (Non-Patent Document 2). For these reasons, in cutting-edge microfabrication, there is a demand for an adhesive film that does not generate residues in the space portions of the pattern (portions where the resist top layer film has been removed by development), enables patterning with high rectangularity, and also suppresses pattern collapse. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] Patent No. 5708521 [Patent Document 2] Patent No. 5708522 [Patent Document 3] Japanese Patent Publication No. 2021-033090 [Patent Document 4] Japanese Patent Publication No. 2021-039171 [Patent Document 5] U.S. Patent No. 9,310,684 [Patent Document 6] International Publication No. 2003 / 017002 [Patent Document 7] International Publication No. 2018 / 143359 [Patent Document 8] Patent No. 6404757 [Non-patent literature]

[0015] [Non-Patent Document 1] Proc. SPIE Vol. 7969,796915(2011) [Non-patent document 2] Proc. SPIE Vol. 7273,72731J(2009) Summary of the Invention [Problem to be solved by the invention]

[0016] The present invention has been made in view of the above circumstances, and aims to provide a pattern formation method using an adhesive film that can obtain a good pattern shape in a fine patterning process in a semiconductor device manufacturing process, and that has high adhesion to a resist overlying film and prevents the fine pattern from collapsing. [Means for solving the problem]

[0017] In order to solve the above problems, the present invention provides a method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, the method comprising: (I-1) a step of applying the composition for forming an adhesion film onto a substrate to be processed and then heat-treating the composition to form an adhesion film; (I-2) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (I-4) a step of transferring a pattern to the adhesion film and the substrate to be processed by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; The present invention provides a pattern forming method comprising the steps of: [ka] (In the formula, R 01 , R 03 are each independently a hydrogen atom or a methyl group, and R 02 is expressed by the following formula (R 02 -1)~(R 02 R is an organic group selected from 04 is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R 05is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. [ka] (In the formula, dashed lines indicate bonds.)

[0018] The present invention also provides a method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, the method comprising: (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) forming a silicon-containing resist intermediate film on the resist underlayer film; (II-3) a step of applying the composition for forming an adhesion film onto the silicon-containing resist intermediate film, followed by heat treatment to form an adhesion film; (II-4) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (II-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (II-6) a step of transferring a pattern to the adhesion film and the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (II-7) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-8) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; The present invention provides a pattern forming method comprising the steps of: [ka] (In the formula, R 01 , R03 are each independently a hydrogen atom or a methyl group, and R 02 is expressed by the following formula (R 02 -1)~(R 02 R is an organic group selected from 04 is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R 05 is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. [ka] (In the formula, dashed lines indicate bonds.)

[0019] The present invention also provides a method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, the method comprising: (III-1) forming a resist underlayer film on a substrate to be processed; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; (III-3) applying the composition for forming an adhesion film onto the inorganic hard mask intermediate film, and then performing a heat treatment to form an adhesion film; (III-4) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (III-6) a step of transferring a pattern to the adhesion film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (III-7) transferring a pattern to the resist underlayer film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; The present invention provides a pattern forming method comprising the steps of: [ka] (In the formula, R 01 , R 03 are each independently a hydrogen atom or a methyl group, and R 02 is expressed by the following formula (R 02 -1)~(R 02 R is an organic group selected from 04 is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R 05 is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. [ka] (In the formula, dashed lines indicate bonds.)

[0020] Thus, the pattern formation method of the present invention can be realized by various pattern formation methods, such as a two-layer resist process or a four-layer resist process in which the above-mentioned adhesion film is formed on a silicon-containing intermediate film (silicon-containing resist intermediate film, inorganic hard mask intermediate film). These pattern formation methods can effectively suppress pattern collapse by the adhesion film, and are suitable for photolithography of the resist upper layer film.

[0021] In this case, it is preferable that the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

[0022] In the present invention, by using the pattern formation method as described above, pattern formation can be carried out well and efficiently.

[0023] In the pattern forming method of the present invention, it is preferable that the adhesion film immediately below the resist top layer film has a film thickness of 15 nm or less.

[0024] Such a film thickness is preferable because it can reduce the load on the resist pattern in the etching step.

[0025] The resist upper layer film used in the present invention may be formed using a composition for forming a resist upper layer film, which contains at least a metal atom-containing compound and an organic solvent.

[0026] In this case, the metal atom-containing compound preferably contains at least one selected from titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium.

[0027] By using such a resist top layer film in the pattern forming method of the present invention, collapse of a fine pattern can be suppressed, and a good pattern shape can be obtained, while at the same time contamination of the substrate to be processed by metal compounds can be prevented.

[0028] In the present invention, the method for forming a circuit pattern on the resist upper layer film is preferably photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0029] In the present invention, it is preferable to use alkaline development or development with an organic solvent as the development method.

[0030] In the present invention, the pattern formation can be carried out satisfactorily and efficiently by using the pattern formation method as described above.

[0031] In addition, in the present invention, it is preferable to use, as the substrate to be processed, a semiconductor device substrate or a semiconductor device substrate having any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal carbide oxide film, and a metal oxynitride film formed thereon.

[0032] 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 an alloy thereof as the metal.

[0033] According to the pattern forming method of the present invention, a pattern can be formed by processing the above-described substrate to be processed in the above-described manner.

[0034] In addition, in the pattern forming method of the present invention, the adhesion film can be formed by spin-coating the composition for forming an adhesion film and heat-treating the substrate to which the composition for forming an adhesion film has been applied at a temperature of 100°C or higher and 300°C or lower for 10 to 600 seconds.

[0035] In addition, in the pattern forming method of the present invention, an adhesion film can be formed by spin-coating the composition for forming an adhesion film and heat-treating the substrate to which the composition for forming an adhesion film has been applied in an atmosphere having an oxygen concentration of 0.1% or more and 21% or less.

[0036] By using such a method, the crosslinking reaction during the formation of the adhesive film can be promoted, and mixing with the resist upper layer film can be further prevented. Furthermore, by adjusting the heat treatment temperature, time, or oxygen concentration within the above ranges, the resist pattern collapse suppression effect of the adhesive film and the pattern shape can be adjusted.

[0037] In addition, in the pattern forming method of the present invention, an adhesion film can be formed by spin-coating the composition for forming an adhesion film and heat-treating the substrate to which the composition for forming an adhesion film has been applied in an atmosphere with an oxygen concentration of less than 0.1%.

[0038] This method is useful because it can promote the crosslinking reaction during the formation of the adhesive film and prevent intermixing with the overlying film without causing deterioration of the substrate to be processed, even if the substrate to be processed contains a material that is unstable when heated in an oxygen atmosphere. [Effects of the Invention]

[0039] As described above, the present invention enables the formation of a highly rectangular resist upper layer film pattern without collapse by introducing an adhesive film, and enables the formation of a fine pattern on a substrate to be processed with high precision by a multilayer resist process, such as a four-layer resist process in which the adhesive film is formed on a silicon-containing intermediate film or an inorganic hard mask intermediate film. [Brief explanation of the drawings]

[0040] [Figure 1] 1A to 1C are explanatory diagrams illustrating an example of a pattern formation method using a four-layer resist process according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0041] As used herein, 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 present. 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 present, and when an element is said to be "on" another element, there may be intervening elements between them.

[0042] As described above, there has been a need for the development of a pattern formation method using an adhesive film that can obtain a good pattern shape in the fine patterning process in the semiconductor device manufacturing process, and that has high adhesion to the resist overlying film and prevents the fine pattern from collapsing.

[0043] As a result of extensive research into the above-mentioned problems, the inventors have discovered that the above-mentioned problems can be solved by a pattern formation method using an adhesion film formed from the following adhesion film-forming composition, and have thus completed the present invention.

[0044] That is, the present invention provides a method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, (I-1) a step of applying the composition for forming an adhesion film onto a substrate to be processed and then heat-treating the composition to form an adhesion film; (I-2) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (I-4) a step of transferring a pattern to the adhesion film and the substrate to be processed by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; The pattern forming method includes the steps of: [ka] (In the formula, R 01 , R 03 are each independently a hydrogen atom or a methyl group, and R 02 is expressed by the following formula (R 02 -1)~(R 02 R is an organic group selected from 04 is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R 05 is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. [ka] (In the formula, dashed lines indicate bonds.)

[0045] The present invention also provides a method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, the method comprising: (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) forming a silicon-containing resist intermediate film on the resist underlayer film; (II-3) a step of applying the composition for forming an adhesion film onto the silicon-containing resist intermediate film, followed by heat treatment to form an adhesion film; (II-4) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (II-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (II-6) a step of transferring a pattern to the adhesion film and the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (II-7) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-8) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; The pattern forming method includes the steps of: [ka] (In the formula, R 01 , R 03 are each independently a hydrogen atom or a methyl group, and R 02 is expressed by the following formula (R 02 -1)~(R 02 R is an organic group selected from 04 is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R 05is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. [ka] (In the formula, dashed lines indicate bonds.)

[0046] Furthermore, the present invention provides a method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, the method comprising: (III-1) forming a resist underlayer film on a substrate to be processed; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; (III-3) applying the composition for forming an adhesion film onto the inorganic hard mask intermediate film, and then performing a heat treatment to form an adhesion film; (III-4) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (III-6) a step of transferring a pattern to the adhesion film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (III-7) transferring a pattern to the resist underlayer film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; The pattern forming method includes the steps of: [ka] (In the formula, R 01 , R 03 are each independently a hydrogen atom or a methyl group, and R 02 is expressed by the following formula (R 02 -1)~(R 02 R is an organic group selected from 04 is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R 05 is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. [ka] (In the formula, dashed lines indicate bonds.)

[0047] The present invention will be described in detail below, but the present invention is not limited thereto.

[0048] [Adhesion film forming composition] The composition for forming an adhesion film for forming an adhesion film directly below a resist upper layer film contains (A) a polymeric compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent. [ka] (In the formula, R 01 , R 03 are each independently a hydrogen atom or a methyl group, and R 02 is expressed by the following formula (R 02 -1)~(R 02 R is an organic group selected from 04 is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R 05 is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. [ka] (In the above formula, the dashed lines represent bonds.)

[0049] In the composition for forming an adhesion film used in the present invention, the polymer compound (A) may be used alone or in combination of two or more. Furthermore, the composition for forming an adhesion film may contain components other than the components (A) to (C). Each component will be described below.

[0050] [(A) Polymer compound] The polymer compound (A) contained in the composition for forming an adhesion film contains a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). [ka] (In the formula, R 01 , R 03 are each independently a hydrogen atom or a methyl group, and R 02 is expressed by the following formula (R 02 -1)~(R 02 R is an organic group selected from 04 is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R 05 is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. [ka] (In the formula, dashed lines indicate bonds.)

[0051] Preferred examples of the repeating unit represented by the general formula (1) include the following structures: 01 are each independently a hydrogen atom or a methyl group. [ka]

[0052] The repeating unit represented by the general formula (1) functions as a crosslinking unit, and the epoxy or oxetane structure undergoes a ring-opening reaction during thermal film formation, resulting in film hardening. As mentioned above, the use of the general formula (1) in a polymer compound is effective for film hardening and enables the formation of a dense film. In addition, the hydroxyl group generated by this ring-opening reaction also contributes to improved adhesion with the resist overlying film.

[0053] In the repeating unit represented by the general formula (2), R 03 are each independently a hydrogen atom or a methyl group.

[0054] R 04 is a single bond or a divalent linking group containing 2 to 10 carbon atoms and containing an ester group. Specific examples include a single bond, -CO2CH2-, -CO2CH2CH2-, -CO2CH2CH2CH2-, -CO2CH(CH3)-, -CO2CH2CH2CH2CH2-, -CO2CH2CH2CH2CH2CH2-, -CO2CH2CH2CH2CH2CH2CH2-, -CO2CH2CH2O-, -CO2CH2CH2OCH2CH2OCH2CH2O-, etc. Among these, -CO2CH2-, -CO2CH2CH2-, -CO2CH2CH2-, -CO2CH2CH2CH2-, -CO2CH2CH2CH2CH2-, -CO2CH2CH2CH2CH2-, and -CO2CH2CH2CH2CH2CH2- are particularly preferred.

[0055] R 05 R is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, and may contain an oxygen functional group. 05 Examples of the structure include, but are not limited to, the following structures:

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] When an adhesive film is formed from a polymer compound containing a repeating unit represented by the general formula (2), the tertiary alkyl group R 05 The elimination and decomposition reaction of the carboxylic acid proceeds to generate a carboxylic acid. The polarity of this carboxylic acid can improve adhesion to the resist pattern, improve the rectangularity of the pattern, and prevent residues from being generated in the spaces of the pattern.

[0060] In addition, the generated carboxylic acid may undergo a ring-opening addition reaction with the repeating unit of general formula (1) to form a hydroxy ester crosslinked structure. A typical example of this reaction is shown below. In the following formula, R in the repeating unit (2) 05 The state in which (3) is formed as a carboxylic acid after being eliminated, and the state in which (4) is formed as a hydroxy ester crosslinked structure after a ring-opening addition reaction with (1"), which is an example of the general formula (1) above. The area enclosed by the dotted line is the hydroxy ester crosslinked structure formed by this reaction. [ka] (In the formula, R 01 , R 03 , R 04 , R 05 is the same as above.)

[0061] The formation of this hydroxyester crosslinking structure is a crosslinking reaction that accelerates the hardening of the adhesive film, resulting in the formation of a dense film and preventing intermixing between the adhesive film and the resist top layer, thereby preventing residues in the spaces of the pattern and enabling the production of highly rectangular patterns.

[0062] Furthermore, the hydroxy ester crosslinked structure is a polar group and interacts with the resist pattern, so the presence of repeating unit (2) also contributes to preventing the resist pattern from collapsing.

[0063] The repeating unit represented by the general formula (2) may be contained in the polymer compound (A) either alone or in combination of two or more kinds.

[0064] Furthermore, it is preferable that the content of the repeating unit represented by the general formula (1) is 10 mol % or more and 90 mol % or less of all repeating units in the (A) polymer compound, and that the content of the repeating unit represented by the general formula (2) is 10 mol % or more and 90 mol % or less of all repeating units.

[0065] By adjusting the content ratio of the general formula (1) and the general formula (2), the polarity of the (A) polymer compound is adjusted, resulting in good adhesion to the resist pattern. Furthermore, during thermal film formation, a dense adhesive film can be formed by the reaction of the carboxylic acid generated from the general formula (2) with the general formula (1), as described above, preventing intermixing between the adhesive film and the resist overcoat film. This prevents residues from forming in the spaces of the pattern, allowing for a highly rectangular pattern. Therefore, the (A) polymer compound preferably contains 10 mol% to 90 mol%, particularly 20 mol% to 80 mol%, of the repeating units represented by the general formula (1) relative to all repeating units, and 10 mol% to 90 mol%, particularly 20 mol% to 80 mol%, of the repeating units represented by the general formula (2).

[0066] The polymer compound (A) preferably further contains a repeating unit represented by the following general formula (5). [ka] (In the formula, R 06 is a hydrogen atom or a methyl group, and R 07 R is a single bond, an ester group, or a divalent linking group containing an ester group and having 2 to 10 carbon atoms. 08 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

[0067] In the above general formula (5), R06 is a hydrogen atom or a methyl group. 07 is a single bond, an ester group (-CO2-), or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and specific examples include a single bond, -CO2-, -CO2CH2-, -CO2CH2CH2-, -CO2CH2CH2-, -CO2CH2CH2CH2-, -CO2CH(CH3)-, -CO2CH2CH2CH2CH2-, -CO2CH2CH2CH2CH2CH2CH2CH2-, -CO2CH2CH2O-, -CO2CH2CH2OCH2CH2OCH2CH2O-, and the like, but are not limited to these.

[0068] R 08 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Specific examples include a phenyl group, a tolyl group, a xylyl group, a methoxyphenyl group, a tert-butoxyphenyl group, a hydroxyphenyl group, an acetylphenyl group, a naphthyl group, a methylnaphthyl group, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group, and particularly preferred are a phenyl group and a tert-butoxyphenyl group, but are not limited to these.

[0069] When the (A) polymer compound contains the repeating unit (5), the repeating unit (5) may be of one type or two or more types. When the repeating unit (5) is contained, its content is preferably 5 mol % to 50 mol % and more preferably 5 mol % to 40 mol % of the total repeating units. A content of the repeating unit (5) of 5 mol % or more is preferable because the resolution of the resist upper layer film during lithography is good, and a content of 50 mol % or less is preferable because the etching characteristics are good.

[0070] The weight average molecular weight of the (A) polymer compound is preferably 8,000 to 50,000, and the dispersity, expressed as weight average molecular weight / number average molecular weight, is preferably 3.0 or less.

[0071] The "weight-average molecular weight" referred to here is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as the solvent and polystyrene as the standard. By ensuring that the weight-average molecular weight and dispersity of the (A) polymer compound contained in the adhesion film-forming composition are within these ranges, excellent film-forming properties can be achieved during spin coating, and the generation of sublimation during heat curing is suppressed, thereby preventing equipment contamination. In particular, when forming thin films of 15 nm or less, the presence of low-molecular-weight, volatile components in the composition can easily cause variations in the film thickness distribution within the wafer surface. However, by controlling the amount of low-molecular-weight components in the composition by setting the molecular weight and dispersity of the polymer compound used as described above, the film thickness distribution within the wafer surface can be minimized. Therefore, the weight-average molecular weight of the (A) polymer compound is preferably 8,000 to 50,000. The dispersity is preferably 3.0 or less.

[0072] (A) A method for synthesizing a polymer compound includes, for example, mixing monomers having polymerizable unsaturated bonds corresponding to each repeating unit, adding a radical polymerization initiator in a solvent, and carrying out thermal polymerization. Polymerization conditions can be selected in a variety of ways depending on the monomers used, the target molecular weight, etc., and are not particularly limited. Specific examples of solvents used during polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, 2-butanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, cyclohexanone, γ-butyrolactone, ethyl acetate, butyl acetate, and diacetone alcohol. Examples of radical polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. Furthermore, thiols such as octanethiol and 2-mercaptoethanol may be added as chain transfer agents during polymerization. The polymerization reaction can be carried out by heating, preferably at 40°C to the boiling point of the reaction solvent. The reaction time is preferably 0.5 to 100 hours, more preferably 1 to 48 hours.

[0073] For example, by using compounds having polymerizable double bonds represented by the following general formulas (1'), (2'), and (5') as monomers and carrying out the polymerization as described above, polymer compounds containing repeating units represented by the above general formulas (1), (2), and (5) can be synthesized. [ka] (In the formula, R 01 ~R 08 is the same as above.)

[0074] During polymerization, all the raw materials may be mixed and then heated, or the remaining raw materials may be added all at once or gradually to a portion of the raw materials that have been heated in advance, either individually or as a mixture. For example, a polymerization method in which only the polymerization solvent is heated and the monomer solution and the polymerization initiator solution are added thereto separately and gradually is particularly preferred, since it can produce a relatively homogeneous polymer compound and can prevent abnormal reactions such as runaway reactions.

[0075] The polymer compound solution obtained as described above may be blended directly into the composition for forming an adhesion film, or may be purified, if necessary, using conventional methods such as crystallization, separation, filtration, and concentration to remove residual monomers, residual solvents, reaction by-products, and other impurities. (A) When purifying the polymer compound, a crystallization method in which a poor solvent such as water, an aqueous alcohol, or a saturated hydrocarbon is added to a solution of the polymer compound and the resulting precipitate is collected by filtration, or a separation method in which a poor solvent layer is separated and removed, is preferred, with the separation method being particularly preferred. When the polymer compound is purified by the separation method, low-molecular-weight components in the polymer compound solution can be efficiently removed, thereby reducing the generation of sublimates when an adhesion film is formed from a composition for forming an adhesion film containing the polymer compound, and as a result, contamination of the film-forming apparatus can be prevented.

[0076] [(B) Thermal acid generator] In the adhesive film-forming composition used in the present invention, a thermal acid generator (B) is added to promote the crosslinking reaction by heat.

[0077] Examples of the thermal acid generator (B) that can be used in the composition for forming an adhesion film used in the present invention include those represented by the following general formula (6). [ka] (In the formula, X - represents a non-nucleophilic counter ion. 10 , R 11 , R 12 and R 13 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 in these groups may be substituted with an alkoxy group or the like. 10 and R 11 , R 10 and R 11 and R 12 may form a ring, and when a ring is formed, R 10 and R 11 , and R 10 and R 11 and R 12 represents an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring having a nitrogen atom in the ring.

[0078] Above, R 10 , R 11 , R 12 and R 13 may be the same or different, and specific examples of alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, and an adamantyl group.

[0079] Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group.

[0080] Examples of the oxoalkyl group include a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, a 2-oxopropyl group, a 2-cyclopentyl-2-oxoethyl group, a 2-cyclohexyl-2-oxoethyl group, and a 2-(4-methylcyclohexyl)-2-oxoethyl group.

[0081] Examples of the oxoalkenyl group include a 2-oxo-4-cyclohexenyl group and a 2-oxo-4-propenyl group.

[0082] Examples of the aryl group include a phenyl group, a naphthyl group, and the like; alkoxyphenyl groups such as a p-methoxyphenyl group, a m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and a m-tert-butoxyphenyl group; alkylphenyl groups such as a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group; alkylnaphthyl groups such as a methylnaphthyl group and an ethylnaphthyl group; alkoxynaphthyl groups such as a methoxynaphthyl group and an ethoxynaphthyl group; dialkylnaphthyl groups such as a dimethylnaphthyl group and a diethylnaphthyl group; and dialkoxynaphthyl groups such as a dimethoxynaphthyl group and a diethoxynaphthyl group.

[0083] Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group.

[0084] Examples of the aryloxoalkyl group include 2-aryl-2-oxoethyl groups such as a 2-phenyl-2-oxoethyl group, a 2-(1-naphthyl)-2-oxoethyl group, and a 2-(2-naphthyl)-2-oxoethyl group.

[0085] Also, R 10 , R 11 , R 12 and R 13When the nitrogen atom in the formula forms a heteroaromatic ring in the ring, 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-pyrrolidone, etc.) are preferred. Examples of the pyridine derivative include pyridine derivatives such as 1H-indazole, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, and dimethylaminopyridine, pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline, 3-quinolinecarbonitrile, and the like), isoquinoline derivatives, cinnoline 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, and uridine derivatives.

[0086] Above, X -Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; 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; methide acids such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide; and sulfonates substituted with fluoro at the α-position as shown in the following general formula (7) and sulfonates substituted with fluoro at the α- and β-positions as shown in the following general formula (8). [ka] [ka]

[0087] In the above general formula (7), R 14 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 23 carbon atoms, an acyl group, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group. 15 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0088] Specific examples of the thermal acid generator include, but are not limited to, the following. [ka]

[0089] The thermal acid generator (B) contained in the composition for forming an adhesion film can be used alone or in combination of two or more. The amount of the thermal acid generator added is not particularly limited as long as it is contained in the composition for forming an adhesion film, and is preferably 0.05 to 30 parts, more preferably 0.1 to 10 parts, per 100 parts of the polymer compound (A). If the thermal acid generator is not contained, the amount of acid generated and the crosslinking reaction will be insufficient. Furthermore, if the amount is 0.05 parts or more, the amount of acid generated and the crosslinking reaction will be sufficient, and if it is 30 parts or less, there is little risk of the mixing phenomenon occurring due to the acid migrating to the upper layer resist.

[0090] [(C) Organic solvent] The adhesive film-forming composition used in the present invention contains (C) an organic solvent. There are no particular limitations on the organic solvent as long as it can dissolve the (A) polymer compound and (B) thermal acid generator. When the additives described below ((D) photoacid generator, (E) crosslinking agent, (F) surfactant) are added, it is preferable that the organic solvent can also dissolve these additives. Specifically, examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether, as described in paragraphs

[0144] and

[0145] of JP-A-2008-111103. Examples include ethers such as glycol dimethyl ether and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate and propylene glycol mono-tert-butyl ether acetate; and lactones such as γ-butyrolactone, and one or a mixture of two or more of these is preferably used.

[0091] The amount of organic solvent added is not particularly limited as long as it is contained in the composition for forming an adhesion film, and is preferably 5,000 parts or more, more preferably 8,000 parts or more, per 100 parts of the polymer compound (A).

[0092] The adhesive film-forming composition used in the present invention may also contain the following (D) photoacid generator, (E) crosslinking agent, and (F) surfactant.

[0093] [(D) Photoacid generator] A photoacid generator (D) can be added to the adhesion film-forming composition used in the present invention to appropriately adjust the pattern shape, exposure sensitivity, etc. of the resist upper layer film. The photoacid generators can be used alone or in combination of two or more. Examples of photoacid generators that can be used include those described in paragraphs

[0160] to

[0179] of JP-A No. 2009-126940. The amount of photoacid generator added is preferably 0.05 to 30 parts, more preferably 0.1 to 10 parts, per 100 parts of the polymer compound (A). When the amount of photoacid generator added is within the above range, the resolution is good and there is no risk of problems with foreign matter occurring after resist development or during peeling.

[0094] [(E) Crosslinking agent] Furthermore, a crosslinking agent (E) can be added to the adhesion film-forming composition used in the present invention to enhance curability and further suppress intermixing with the resist upper layer film. The crosslinking agent is not particularly limited, and a wide variety of known crosslinking agents can be used. Examples include melamine-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, epoxy-based crosslinking agents, and phenol-based crosslinking agents. The crosslinking agents (E) can be used alone or in combination of two or more. 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 polymer compound (A). Addition of 5 parts or more ensures sufficient curability and suppresses intermixing with the resist upper layer film. On the other hand, if the amount added is 50 parts or less, there is no risk of deterioration in adhesion due to a decrease in the ratio of the polymer compound (A) in the composition for forming an adhesion film.

[0095] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof.

[0096] Specific examples of glycoluril crosslinking agents include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and / or hydroxy substituted products thereof, and partial self-condensates thereof.

[0097] Specific examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof.

[0098] Specific examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethylene urea, its alkoxy and / or hydroxy substituted derivatives, and partial self-condensates thereof.

[0099] A specific example of the β-hydroxyalkylamide crosslinking agent is N,N,N',N'-tetra(2-hydroxyethyl)adipamide.

[0100] Specific examples of the isocyanurate crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate.

[0101] Specific examples of the aziridine crosslinking agent include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0102] Specific examples of oxazoline crosslinking agents include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline) and 2,2'-isopropylidenebis(4-phenyl-2-oxazoline). 、2 Examples include 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 copolymer.

[0103] Specific examples of epoxy-based 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.

[0104] Specific examples of phenol-based crosslinking agents include compounds represented by the following general formula (9). [ka] (In the formula, Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. R 16 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and q is an integer of 1 to 5.

[0105] Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. q is an integer of 1 to 5, and 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.

[0106] R 16 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an octyl group, an ethylhexyl group, a decyl group, and an eicosanyl group, and a hydrogen atom or a methyl group is preferred.

[0107] Specific examples of the compound represented by the general formula (9) include the following compounds: Among these, hexamethoxymethylated triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the viewpoint of improving the curability and film thickness uniformity of the adhesive film.

[0108] [ka]

[0109] [ka]

[0110] The (E) crosslinking agent can be used alone or in combination of two or more. The amount of the (E) crosslinking agent added is preferably 10% by mass to 50% by mass, more preferably 15% by mass to 30% by mass, based on 100 parts of the (A) polymer compound. If the amount added is 10% by mass or more, sufficient curability is obtained 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 ratio of the (A) polymer compound in the composition for forming an adhesion film is not reduced, and there is no risk of deterioration in adhesion.

[0111] [(F) Surfactant] A surfactant (F) can be added to the adhesive film-forming composition used in the present invention to improve the coatability in spin coating. The surfactant can be used alone or in combination of two or more. Examples of surfactants that can be used include those described in paragraphs

[0142] to

[0147] of JP-A No. 2009-269953. When a surfactant is added, the amount added is preferably 0.001 to 20 parts, more preferably 0.01 to 10 parts, per 100 parts of the polymer compound (A). Within this range, coatability is reliably improved, and a thin, uniform adhesive film can be formed.

[0112] A plasticizer can also be added to the adhesion film-forming composition used in the present invention. The plasticizer is not particularly limited, and various known plasticizers can be widely used. Examples include low-molecular-weight compounds such as phthalates, adipic esters, phosphate esters, trimellitates, and citrate esters, as well as polymers such as polyethers, polyesters, and polyacetal polymers described in JP-A-2013-253227. The amount of plasticizer added is preferably 5% to 500% by mass relative to 100 parts of the polymer compound (A). An amount within this range results in excellent pattern filling and leveling.

[0113] Furthermore, the above-mentioned composition for forming an adhesion film can be used in a multilayer resist process such as a two-layer resist process or a four-layer resist process using a resist underlayer film and a silicon-containing intermediate film to realize fine pattern processing.

[0114] The silicon-containing intermediate film can be a silicon-containing resist intermediate film or an inorganic hard mask intermediate film depending on the pattern formation method described below. The inorganic hard mask intermediate film is preferably selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film.

[0115] [Pattern formation method] The present invention provides a pattern forming method that uses the above-mentioned adhesion film-forming composition to form an adhesion film that has high adhesion to an overlying resist film and has the effect of preventing the collapse of a fine pattern in a fine patterning process using a multilayer resist method in a semiconductor device manufacturing process.

[0116] The adhesion film is formed by coating the adhesion film-forming composition onto a substrate to be processed by spin coating or the like. After spin coating, the organic solvent is evaporated, and baking (heat treatment) is performed to promote the crosslinking reaction and prevent intermixing with the resist upper layer film or the silicon-containing intermediate film. Baking is preferably performed at 100°C or higher and 300°C or lower for 10 to 600 seconds, more preferably 200°C or higher and 250°C or lower for 10 to 300 seconds. Considering damage to the adhesion film and the effect on wafer deformation, the upper limit of the heating temperature in the lithography wafer process is preferably 300°C or lower, more preferably 250°C or lower.

[0117] That is, the present invention provides a pattern forming method for forming an adhesion film by spin-coating the composition for forming an adhesion film and heat-treating the substrate coated with the composition for forming an adhesion film at a temperature of 100°C or higher and 300°C or lower for 10 to 600 seconds.

[0118] The adhesion film used in the present invention can also be formed by coating the adhesion film-forming composition on a substrate to be processed by spin coating or the like, as described above, and then baking the adhesion film-forming composition in an atmosphere with an oxygen concentration of 0.1% to 21% to harden it. By baking the adhesion film-forming composition in such an oxygen atmosphere, a sufficiently hardened film can be obtained.

[0119] That is, the present invention provides a pattern forming method for forming an adhesion film by spin-coating the composition for forming an adhesion film and heat-treating the substrate coated with the composition for forming an adhesion film in an atmosphere having an oxygen concentration of 0.1% or more and 21% or less.

[0120] The atmosphere during baking may be air or may contain an inert gas such as N2, Ar, or He. In this case, the atmosphere may have an oxygen concentration of less than 0.1%. The baking temperature and other conditions may be the same as those described above. Even if the substrate to be processed contains a material that is unstable when heated in an oxygen atmosphere, the crosslinking reaction during adhesion film formation can be promoted without causing deterioration of the substrate to be processed.

[0121] That is, the present invention provides a pattern forming method for forming an adhesion film by spin-coating the composition for forming an adhesion film and heat-treating the substrate coated with the composition for forming an adhesion film in an atmosphere having an oxygen concentration of less than 0.1%.

[0122] In the present invention, there is provided a method for forming a pattern on a substrate to be processed, comprising the steps of: (I-1) a step of applying the composition for forming an adhesion film onto a substrate to be processed, followed by heat treatment to form an adhesion film; (I-2) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (I-4) a step of transferring a pattern to the adhesion film and the substrate to be processed by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; The present invention provides a pattern forming method comprising the steps of:

[0123] The pattern forming method of the present invention will be described below using a four-layer resist process as an example, but is not limited to this process. First, a method for forming a pattern on a workpiece substrate is provided, which includes at least forming a resist underlayer film on the workpiece substrate using an organic film-forming composition, forming a silicon-containing intermediate film (silicon-containing resist intermediate film) on the resist underlayer film using a silicon-containing resist intermediate film-forming composition, forming an adhesion film on the silicon-containing resist intermediate film using the above-mentioned adhesion film-forming composition, and forming a resist upper layer film on the adhesion film using a resist upper layer film-forming composition to form a multi-layer resist film, exposing the pattern circuit area of the resist upper layer film and developing it with a developer to form a pattern of the resist upper layer film, etching the adhesion film and the silicon-containing resist intermediate film using the obtained resist upper layer film pattern as an etching mask to form a silicon-containing resist intermediate film pattern, etching the resist underlayer film using the obtained silicon-containing resist intermediate film pattern as an etching mask to form a resist underlayer film pattern, and further etching the workpiece substrate using the obtained resist underlayer film pattern as an etching mask to form a pattern on the workpiece substrate.

[0124] That is, a method for forming a pattern on a substrate to be processed, (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) forming a silicon-containing resist intermediate film on the resist underlayer film; (II-3) a step of applying the composition for forming an adhesion film onto the silicon-containing resist intermediate film, followed by heat treatment to form an adhesion film; (II-4) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (II-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (II-6) a step of transferring a pattern to the adhesion film and the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (II-7) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-8) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; The present invention provides a pattern forming method comprising the steps of:

[0125] Polysilsesquioxane-based interlayers are also preferred as the silicon-containing resist interlayer in the four-layer resist process. By imparting anti-reflection properties to the silicon-containing resist interlayer, reflection can be suppressed. For 193 nm exposure, in particular, using a resist underlayer containing a material with a high aromatic group content and high substrate etching resistance increases the k value and substrate reflection, but using a silicon-containing resist interlayer can reduce substrate reflection to 0.5% or less. Preferred silicon-containing resist interlayers with anti-reflection properties are anthracene for 248 nm and 157 nm exposure, and polysilsesquioxanes with pendant light-absorbing groups containing phenyl groups or silicon-silicon bonds and crosslinked by acid or heat for 193 nm exposure.

[0126] In this case, forming the silicon-containing resist intermediate film by spin coating is easier and more cost-effective than forming it by CVD.

[0127] Alternatively, an inorganic hard mask intermediate film may be formed as the silicon-containing intermediate film. In this case, at least a resist underlayer film may be formed on a substrate to be processed using a composition for forming an organic film, an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film may be formed on the resist underlayer film, an adhesion film may be formed on the inorganic hard mask intermediate film using the composition for forming an adhesion film, a resist upper layer film may be formed on the adhesion film using a composition for forming a photoresist upper layer film, a pattern circuit region of the resist upper layer film may be exposed to light and then developed with a developer to form a resist upper layer film pattern in the resist upper layer film, the adhesion film and the inorganic hard mask intermediate film may be etched using the resist upper layer film pattern obtained as an etching mask to form an inorganic hard mask intermediate film pattern, the resist underlayer film may be etched using the inorganic hard mask intermediate film pattern obtained as an etching mask to form a resist underlayer film pattern, and the substrate to be processed may be etched using the resist underlayer film pattern obtained as an etching mask to form a pattern on the substrate to be processed.

[0128] That is, a method for forming a pattern on a substrate to be processed, (III-1) forming a resist underlayer film on a substrate to be processed; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; (III-3) applying the composition for forming an adhesion film onto the inorganic hard mask intermediate film, and then performing a heat treatment to form an adhesion film; (III-4) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (III-6) a step of transferring a pattern to the adhesion film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (III-7) transferring a pattern to the resist underlayer film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; The present invention provides a pattern forming method comprising the steps of:

[0129] As described above, when forming an inorganic hard mask intermediate film on a resist underlayer film, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. It is particularly preferable to form the inorganic hard mask intermediate film by a CVD method or an ALD method. For example, methods for forming a silicon nitride film are described in JP 2002-334869 A and WO 2004 / 066377 A. The thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, more preferably 10 to 100 nm. Furthermore, a SiON film, which is highly effective as an anti-reflective coating, is most preferably used as the inorganic hard mask intermediate film. Since the substrate temperature during SiON film formation is 300 to 500°C, the resist underlayer film must be able to withstand temperatures of 300 to 500°C.

[0130] The adhesive film used in the present invention preferably has a thickness of 15 nm or less directly below the resist top layer film.

[0131] As miniaturization advances, resist top layer films become thinner, and designs that reduce dry etching resistance are inevitably adopted from the standpoint of resolution. Therefore, in order to reduce the load on the resist pattern during etching, it is necessary to make the adhesion film directly below the resist as thin as possible. Therefore, the thickness of the adhesion film used in the present invention is preferably 15 nm or less, and particularly preferably 10 nm or less. The adhesion film-forming composition used in the present invention contains the same polymer compound as the resist underlayer film reported in Patent Document 8. The polymer compound has a higher etching rate than the resist top layer film and is therefore suitable for etching.

[0132] When forming an adhesion film having a thickness of 15 nm or less from the adhesion film-forming composition used in the present invention, a spin coating method is preferably used. The film can be formed by appropriately setting the concentration of the polymer compound (A) contained in the adhesion film-forming composition and / or the rotation speed during spin coating.

[0133] The resist upper layer film in the four-layer process may be either positive or negative. The resist upper layer film is preferably formed using a resist upper layer film-forming composition containing at least a metal atom-containing compound and an organic solvent. The metal atom-containing compound preferably contains at least one selected from titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium. After spin-coating the resist upper layer film-forming composition, pre-baking is performed, preferably at 60 to 180°C for 10 to 300 seconds. Thereafter, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain a resist upper layer film pattern. The thickness of the resist upper layer film is not particularly limited, but is preferably 20 to 300 nm, and more preferably 25 to 250 nm.

[0134] A circuit pattern (resist upper layer film pattern) is formed on the resist upper layer film. In forming the circuit pattern, it is preferable to form the circuit pattern by photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination of these.

[0135] Examples of exposure light include high-energy rays with a wavelength of 300 nm or less, specifically far ultraviolet rays, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 laser light (157 nm), Kr2 laser light (146 nm), Ar2 laser light (126 nm), soft X-rays (EUV) of 3 to 20 nm, electron beams (EB), ion beams, X-rays, and the like.

[0136] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali development method or development using an organic solvent.

[0137] Next, etching is performed using the obtained resist top layer film pattern as a mask. The adhesion film used in the present invention has a high etching rate and can be used at a thin film thickness of 15 nm or less, thereby reducing the etching load on the resist pattern that serves as a mask. Therefore, the adhesion film and the film immediately below it, such as a silicon-containing resist intermediate film or an inorganic hard mask intermediate film, can be etched based on the resist top layer film pattern. These silicon-containing resist intermediate films and inorganic hard mask intermediate films are etched using a fluorocarbon-based gas. This forms a silicon-containing resist intermediate film pattern or an inorganic hard mask intermediate film pattern.

[0138] Next, the resist underlayer film is etched using the resulting silicon-containing resist intermediate film pattern or inorganic hard mask intermediate film pattern as a mask.

[0139] The next step, etching of the substrate to be processed, can also be performed using standard methods. For example, if the substrate to be processed is an SiO2, SiN, or silica-based low-dielectric-constant insulating film, etching is performed primarily with fluorocarbon-based gases, while for p-Si, Al, or W, etching is performed primarily with chlorine- or bromine-based gases. When etching the substrate with fluorocarbon-based gases, the silicon-containing intermediate film pattern is removed at the same time as the substrate is processed. When etching the substrate with chlorine- or bromine-based gases, the silicon-containing intermediate film pattern must be removed by separate dry etching using fluorocarbon-based gases after substrate processing.

[0140] The substrate to be processed is not particularly limited, and may be a semiconductor device substrate or a semiconductor device substrate having a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal carbide oxide film, or a metal oxynitride film formed thereon. Examples of the metal that can be used include silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, and alloys thereof.

[0141] Specifically, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, and substrates with a work layer formed thereon, are used. The work layer may be a variety of 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, and can be formed to a thickness of typically 50 to 10,000 nm, and particularly 100 to 5,000 nm. When forming a work layer, the substrate and work layer are made of different materials.

[0142] An example of a four-layer resist process is specifically shown below with reference to Figure 1. In the four-layer resist process, as shown in Figure 1(A), a resist underlayer film 3 is formed using an organic film material on a processable layer 2 laminated on a substrate 1, and then a silicon-containing intermediate film 4 is formed thereon, and an adhesion film 5 is formed thereon using the adhesion film-forming composition of the present invention, and a resist upper layer film 6 is formed thereon.

[0143] Next, as shown in FIG. 1(B), the exposed portion 7 of the resist top layer film is exposed, followed by PEB and development to form a resist top layer film pattern 6a (FIG. 1(C)). Using the resulting resist top layer film pattern 6a as a mask, the adhesion film 5 is etched to form an adhesion film pattern 5a (FIG. 1(D)). Furthermore, the silicon-containing intermediate film 4 is also etched using a CF-based gas to form a silicon-containing intermediate film pattern 4a (FIG. 1(E)). Using the resulting silicon-containing intermediate film pattern 4a as a mask, the resist underlayer film 3 is etched using an O-based gas to form a resist underlayer film pattern 3a (FIG. 1(F)). Furthermore, after removing the silicon-containing intermediate film pattern 4a, the workpiece layer 2 is etched using the resist underlayer film pattern 3a as a mask to form a pattern 2a (FIG. 1(G)).

[0144] As described above, the pattern forming method of the present invention makes it possible to form a fine pattern on a substrate to be processed with high precision in a multi-layer resist process. [Example]

[0145] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. The molecular weight was measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent, and the polydispersity (Mw / Mn) was calculated from the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene.

[0146] [Synthesis Example 1] Synthesis of polymer compound (A1) 38.9 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C under a nitrogen atmosphere. To this was added 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, simultaneously and separately, over a period of 4 hours. After heating and stirring for an additional 20 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer compound (A1). Analysis revealed that the weight-average molecular weight (Mw) of polymer compound (A1) was 12,000 and the polydispersity (Mw / Mn) was 2.4.

[0147] [Synthesis Example 2] Synthesis of polymer compound (A2) 38.9 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this mixture, 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 heating and stirring for an additional 20 hours, the mixture was cooled to 60°C, 200 g of heptane was added, cooled to room temperature, and allowed to stand for 2 hours. The upper layer was separated and removed, and 100 g of PGMEA was added. The heptane was then distilled off under reduced pressure to obtain a PGMEA solution of the desired polymer compound (A2). Analysis revealed that the weight-average molecular weight (Mw) of polymer compound (A2) was 13,000 and the polydispersity (Mw / Mn) was 2.2.

[0148] [Synthesis Examples 3 to 7] Synthesis of polymer compounds (A3) to (A7) Except for changing the types and molar ratios of the raw material monomers used according to the structure of each polymer compound, PGMEA solutions of polymer compounds (A3) to (A7) were obtained in the same manner as in Synthesis Example 1. The weight average molecular weights (Mw) and dispersities (Mw / Mn) of polymer compounds (A3) to (A7) were as follows:

[0149] The polymer compounds (A1) to (A7) synthesized in the synthesis examples are shown below. [ka]

[0150] Preparation of adhesive film-forming compositions (AL1 to 16, comparative AL1) The polymer compounds (A1) to (A7), the thermal acid generators (AG1) to (AG3), the photoacid generators (AG4) to (AG5), and the crosslinkers (X1) to (X2) were used to prepare the adhesion film-forming compositions. The compositions were dissolved in an organic solvent containing 0.001% by mass of PF636 (manufactured by OMNOVA) in the proportions shown in Table 1, and then filtered through a 0.1 μm fluororesin filter to prepare the adhesion film-forming compositions (AL1 to 16, comparative AL1).

[0151] [ka]

[0152] [Table 1] PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

[0153] Example 1 Evaluation of film thickness uniformity and solvent resistance (Examples 1-1 to 16, Comparative Example 1-1) The adhesive film-forming compositions (AL1-16, comparative AL1) prepared above were applied to a 300 mm silicon substrate and baked at 220°C for 60 seconds, after which the film thickness was measured. The film thickness was measured at 225 locations across the entire wafer, and the difference between the maximum and minimum values of these measurements was calculated as a parameter indicating the in-plane film thickness uniformity. A small value indicates high film thickness uniformity on the wafer, which is preferable. The average film thickness of these 225 locations was used as the film thickness after deposition. PGMEA solvent was dispensed onto the resulting adhesive film, which was then left to stand for 30 seconds, spin-dried, and baked at 100°C for 60 seconds to evaporate the PGMEA solvent. The film thickness was then measured again to determine the difference in film thickness before and after PGMEA treatment, thereby evaluating solvent resistance. The results are shown in Table 2.

[0154] [Table 2]

[0155] As shown in Table 2, Examples 1-1 to 16 using adhesion film-forming compositions AL1 to 16 and Comparative Example 1-1 using comparative AL1 showed almost no reduction in film thickness due to solvent treatment, and produced adhesion films with good solvent resistance.

[0156] Example 2 EUV exposure pattern formation test using positive resist (Examples 2-1 to 2-16, Comparative Example 2-1) A silicon wafer substrate was coated with spin-on carbon ODL-301 (carbon content: 88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. and baked at 350°C for 60 seconds to form a 100 nm thick resist underlayer film. A silicon-containing spin-on hard mask SHB-A940 (silicon content: 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was then coated thereon and baked at 220°C for 60 seconds to form a 15 nm thick silicon-containing intermediate film. The above-mentioned adhesion film-forming compositions (AL1-16, Comparative AL1) were then coated thereon and baked at 220°C for 60 seconds to form adhesion films with thicknesses of 5 nm (AL1-11, 13-15, Comparative AL1) or 15 nm (AL12, 16). A positive resist top layer film-forming composition listed in Table 3 was then coated thereon and baked at 100°C for 60 seconds to form a 40 nm thick resist top layer film.

[0157] A composition for forming a positive resist top layer film (EUV single-layer resist) was prepared by dissolving polymer compound PRP1 and quencher Q1 in a solvent containing 0.1 mass% of FC-4430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 3 and filtering the solution through a 0.1 μm fluororesin filter.

[0158] [Table 3]

[0159] Resist polymer: PRP1 Molecular weight Mw=9,200 Dispersion degree Mw / Mn=1.8 [ka]

[0160] Quencher: Q1 [ka]

[0161] Next, an 18 nm line and space (LS) 1:1 pattern was exposed using an EUV exposure system (ASML EUV Scanner NXE3400, NA 0.33, σ 0.9, 90-degree dipole illumination), baked at 90°C for 60 seconds (PEB), and developed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds, yielding 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. In addition, the exposure dose required to form the line and space pattern was gradually increased to narrow the line dimensions, and the minimum dimension at which the lines could be resolved without collapsing was determined, and this was taken as the collapse limit (nm). The smaller the value, the higher the collapse resistance, making it preferable.

[0162] The cross-sectional shape of the obtained pattern 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 Corp. The results are shown in Table 4.

[0163] [Table 4]

[0164] As shown in Table 4, Examples 2-1 to 2-16, which used adhesion film-forming compositions AL1 to 16, produced rectangular patterns and exhibited excellent collapse suppression performance. On the other hand, Comparative Example 2-1, which used comparative AL1, produced a tapered pattern and was highly rough. This demonstrates the effectiveness of using repeating units represented by the above general formulas (1) and (2) in combination in the polymer compound that constitutes the adhesion film.

[0165] Example 3 Etching Process Evaluation (Examples 3-1 to 3-16, Comparative Example 3-1) Following the formation of the resist top layer film pattern in Example 2, the silicon-containing intermediate film was dry-etched (pattern transferred) using the resist top layer film pattern as a mask using a Telius etching system manufactured by Tokyo Electron, and the resulting silicon-containing intermediate film pattern was used as a mask to dry-etch (pattern transferred) the resist underlayer film to form a resist underlayer film pattern. The etching conditions were as follows:

[0166] (Conditions for transferring the resist top layer pattern to the silicon-containing intermediate film) Chamber pressure 10.0Pa RF power 1500W CF4 gas flow rate: 75mL / min O2 gas flow rate 15mL / min Time 15sec

[0167] (Conditions for transferring silicon-containing intermediate film pattern to resist underlayer film) Chamber pressure 2.0Pa RF power 500W Ar gas flow rate: 75 mL / min O2 gas flow rate: 45mL / min Time 90sec

[0168] The success of resist underlayer film pattern formation was confirmed by top-down SEM observation of the wafer after pattern transfer (dry etching) to the resist underlayer film. The evaluation results are shown in Table 5.

[0169] [Table 5]

[0170] As shown in Table 5, in the pattern forming method of the present invention (Examples 3-1 to 16), even when the thickness of the adhesive film was 5 nm (Examples 3-1 to 11, 13 to 15) or 15 nm (Examples 3-12, 16), the resist upper layer film pattern was transferred well to the resist lower layer film, demonstrating that the adhesive films AL1 to 16 are effective for fine patterning using the multilayer resist method.

[0171] In contrast, in Comparative Example 3-1, a resist underlayer film pattern could not be formed, which was due to the occurrence of a defective shape in the resist pattern.

[0172] Example 4 Electron beam pattern formation test (Examples 4-1 to 4-16, Comparative Example 4-1) A silicon wafer substrate was coated with spin-on carbon ODL-301 (carbon content: 88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. and baked at 350°C for 60 seconds to form a 100 nm thick resist underlayer film. A silicon-containing spin-on hard mask SHB-A940 (silicon content: 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was then coated thereon and baked at 220°C for 60 seconds to form a 20 nm thick silicon-containing intermediate film. The adhesion film-forming compositions AL1 to 16 and Comparative AL1 were then coated thereon and baked at 220°C for 60 seconds to form a 5 nm thick adhesion film. A metal-containing resist upper layer film-forming composition was then coated thereon and baked at 180°C for 60 seconds to form a 60 nm thick resist upper layer film.

[0173] The composition for forming the metal-containing resist upper layer film was prepared by dissolving the titanium-containing compound MPRP1 and the metal salt sensitizer S1 in 4-methyl-2-pentanol (MIBC) containing 0.1 mass % of FC-4430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 6, and filtering the resultant solution through a 0.1 μm fluororesin filter.

[0174] [Table 6]

[0175] Synthesis of titanium-containing compound MPRP1 A solution of 284 g of titanium tetraisopropoxide (Tokyo Chemical Industry Co., Ltd.) in 500 g of 2-propanol (IPA) was added dropwise to the resulting solution over 2 hours at room temperature while stirring. 180 g of 2,4-dimethyl-2,4-octanediol was added to the resulting solution, which was then stirred at room temperature for 30 minutes. The solution was concentrated under reduced pressure at 30°C, then heated to 60°C and continued to be heated under reduced pressure until no more distillate was produced. When no more distillate was observed, 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 was produced, yielding a titanium-containing compound. MPRP1 1,000 g of the MIBC solution (compound concentration: 25% by mass) was obtained. When the molecular weight of this solution was measured in terms of polystyrene, it was found to be Mw=1,200.

[0176] Metal salt sensitizer: S1 [ka]

[0177] Next, writing was performed in a vacuum chamber using an ELS-F125 (manufactured by Elionix Co., Ltd.) at an accelerating voltage of 125 kV. Immediately after writing, the wafer was baked (PEB) at 200°C for 60 seconds, and then puddle developed with butyl acetate for 20 seconds to obtain a negative pattern.

[0178] The resulting resist patterns were evaluated as follows. The exposure dose required to resolve a 50 nm line-and-space 1:1 pattern was taken as sensitivity, and the minimum dimension at which the lines could be resolved without collapsing when the exposure dose was reduced to narrow the line dimensions was determined, and this was taken as the collapse limit (nm). The smaller the value, the higher the collapse resistance, and thus the more preferable it is. The results are shown in Table 7.

[0179] [Table 7]

[0180] As shown in Table 7, Examples 4-1 to 16, which used adhesion film-forming compositions AL1 to 16, had smaller collapse limit values than Comparative Example 4-1, which used Comparative AL1, and it can be seen that the present invention has excellent adhesion even with metal-containing resists and is effective for fine patterning.

[0181] From the above, it can be seen that an adhesion film obtained from a composition for forming an adhesion film using a polymeric compound containing a specific repeating unit has the effect of preventing collapse of a fine resist pattern, and is therefore extremely useful as an adhesion film to be used in a multilayer resist method.Furthermore, the pattern forming method of the present invention using this can transfer a fine pattern to a substrate to be processed with high precision.

[0182] The present specification includes the following aspects. [1]: A method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, (I-1) a step of applying the composition for forming an adhesion film onto a substrate to be processed and then heat-treating the composition to form an adhesion film; (I-2) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (I-4) a step of transferring a pattern to the adhesive film and the substrate to be processed by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; A pattern forming method comprising the steps of: [ka] (In the formula, R 01 , R 03 are each independently a hydrogen atom or a methyl group, and R 02 is expressed by the following formula (R 02-1)~(R 02 R is an organic group selected from 04 is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R 05 is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. [ka] (In the formula, dashed lines indicate bonds.) [2]: A method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) forming a silicon-containing resist intermediate film on the resist underlayer film; (II-3) a step of applying the composition for forming an adhesion film onto the silicon-containing resist intermediate film, followed by heat treatment to form an adhesion film; (II-4) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (II-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (II-6) a step of transferring a pattern to the adhesion film and the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (II-7) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-8) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; A pattern forming method comprising the steps of: [ka] (In the formula, R 01 , R 03 are each independently a hydrogen atom or a methyl group, and R 02 is expressed by the following formula (R 02 -1)~(R 02 R is an organic group selected from 04 is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R 05 is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. [ka] (In the formula, dashed lines indicate bonds.) [3]: A method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, (III-1) forming a resist underlayer film on a substrate to be processed; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; (III-3) applying the composition for forming an adhesion film onto the inorganic hard mask intermediate film, and then performing a heat treatment to form an adhesion film; (III-4) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (III-6) a step of transferring a pattern to the adhesion film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (III-7) transferring a pattern to the resist underlayer film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; A pattern forming method comprising the steps of: [ka] (In the formula, R 01 , R 03 are each independently a hydrogen atom or a methyl group, and R 02 is expressed by the following formula (R 02 -1)~(R 02 R is an organic group selected from 04 is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R 05 is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. [ka] (In the formula, dashed lines indicate bonds.) [4]: The pattern forming method according to [3] above, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method. [5]: The pattern forming method according to [1], [2], [3] or [4] above, wherein the thickness of the adhesive film directly below the resist top layer film is 15 nm or less. [6]: The pattern forming method according to [1], [2], [3], [4] or [5], wherein the resist upper layer film is formed using a composition for forming a resist upper layer film, the composition containing at least a metal atom-containing compound and an organic solvent. [7]: The pattern formation method according to [6], wherein the metal atom-containing compound contains at least one selected from titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium. [8]: The pattern forming method according to [1], [2], [3], [4], [5], [6] or [7], characterized in that a circuit pattern is formed on the resist upper layer film by photolithography having a wavelength of 10 nm or more and 300 nm or less, direct writing using an electron beam, nanoimprinting, or a combination thereof. [9]: The pattern forming method according to any one of [1], [2], [3], [4], [5], [6], [7], and [8], characterized in that alkaline development or development with an organic solvent is used as the development method.

[10] : The pattern forming method according to [1], [2], [3], [4], [5], [6], [7], [8] or [9], characterized in that the substrate to be processed is a semiconductor device substrate, or a semiconductor device substrate having any of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film and a metal oxide nitride film formed thereon.

[11] : The pattern formation method according to

[10] , characterized in that the metal used 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.

[12] : The pattern forming method according to any one of [1], [2], [3], [4], [5], [6], [7], [8], [9],

[10] ,

[11] ,

[12] ,

[13] ,

[14] ,

[15] ,

[16] ,

[17] ,

[18] ,

[19] ,

[20] ,

[21] ,

[22] ,

[23] ,

[24] ,

[25] ,

[26] ,

[27] ,

[28] ,

[29] ,

[30] ,

[31] ,

[32] ,

[33] ,

[34] ,

[35] ,

[36] ,

[37] ,

[38] ,

[39] ,

[40] ,

[41] ,

[42] ,

[43] ,

[44] ,

[45] ,

[46] ,

[47] ,

[48] ,

[49] ,

[50] ,

[51] ,

[52] ,

[53] ,

[54] ,

[55] ,

[56] ,

[57] ,

[58] ,

[59] ,

[60] ,

[54] ,

[55] ,

[56] ,

[57] ,

[58] ,

[59] ,

[61] ,

[59] ,

[62] ,

[63] ,

[64] ,

[65] ,

[66] ,

[67] ,

[68] ,

[70] ,

[71] ,

[72] ,

[73] ,

[74] ,

[75] ,

[76] ,

[77] ,

[78] ,

[79] ,

[80] ,

[81] ,

[82] ,

[83] ,

[84] ,

[85] ,

[86] ,

[87] ,

[88] ,

[89] ,

[89] ,

[90] ,

[91] ,

[92] ,

[93] ,

[94] , [

[13] : The pattern forming method according to any one of [1], [2], [3], [4], [5], [6], [7], [8], [9],

[10] ,

[11] ,

[12] ,

[13] ,

[14] ,

[14] ,

[15] ,

[16] ,

[17] ,

[18] ,

[19] ,

[20] ,

[21] ,

[22] ,

[23] ,

[24] ,

[25] ,

[26] ,

[27] ,

[28] ,

[29] ,

[30] ,

[31] ,

[32] ,

[33] ,

[34] ,

[35] ,

[36] ,

[37] ,

[38] ,

[39] ,

[40] ,

[41] ,

[42] ,

[43] ,

[44] ,

[45] ,

[46] ,

[47] ,

[48] ,

[49] ,

[50] ,

[51] ,

[52] ,

[53] ,

[54] ,

[55] ,

[56] ,

[57] ,

[58] ,

[59] ,

[51] ,

[52] ,

[53] ,

[54] ,

[55] ,

[56] ,

[57] ,

[58] ,

[59] ,

[69] ,

[69] ,

[69] ,

[69] ,

[69] ,

[70] ,

[71] ,

[72] ,

[73] ,

[74] ,

[75] ,

[76] ,

[77] ,

[78] ,

[79] ,

[80] ,

[81] ,

[82] ,

[83] ,

[84] ,

[85] ,

[86] ,

[87] ,

[88] ,

[89] ,

[89] ,

[90] ,

[91] ,

[92] ,

[93] ,

[94] ,

[95] , [

[14] : The pattern forming method according to any one of [1], [2], [3], [4], [5], [6], [7], [8], [9],

[10] ,

[11] ,

[12] ,

[13] ,

[14] ,

[15] ,

[16] ,

[17] ,

[18] ,

[19] ,

[20] ,

[21] ,

[22] ,

[23] ,

[24] ,

[25] ,

[26] ,

[27] ,

[28] ,

[29] ,

[30] ,

[31] ,

[32] ,

[33] ,

[34] ,

[35] ,

[36] ,

[37] ,

[38] ,

[39] ,

[40] ,

[41] ,

[42] ,

[43] ,

[44] ,

[45] ,

[46] ,

[47] ,

[48] ,

[49] ,

[50] ,

[51] ,

[52] ,

[53] ,

[54] ,

[55] ,

[56] ,

[57] ,

[58] ,

[59] ,

[69] ,

[69] ,

[69] ,

[70] ,

[71] ,

[72] ,

[73] ,

[74] ,

[75] ,

[76] ,

[77] ,

[78] ,

[79] ,

[80] ,

[81] ,

[82] ,

[83] ,

[84] ,

[85] ,

[86] ,

[87] ,

[88] ,

[89] ,

[89] ,

[90] ,

[91] ,

[92] ,

[93] ,

[94] ,

[95] ,

[96] ,

[97] ,

[98] ,

[99] ,

[99] ,

[99] ,

[99] ,

[90] ,

[91] ,

[92] ,

[93] ,

[94] , [

[0183] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0184] 1...substrate, 2...processed layer, 2a...pattern (pattern formed on the processed layer), 3...resist underlayer film, 3a...resist underlayer film pattern, 4...silicon-containing interlayer film, 4a...silicon-containing interlayer film pattern, 5...adhesive film, 5a...adhesive film pattern, 6...resist upper layer film, 6a...resist upper layer film pattern, 7...exposed portion.

Claims

1. A method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, (I-1) A step of applying the composition for forming an adhesion film onto a substrate to be processed, followed by heat treatment to form an adhesion film; (I-2) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (I-4) a step of transferring a pattern to the adhesive film and the substrate to be processed by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; wherein the thickness of an adhesive film directly below the resist top layer film is 15 nm or less, and the repeating unit represented by general formula (2) undergoes an elimination and decomposition reaction of R 05 by the action of an acid to generate a carboxylic acid. 【Chemical 1】 (In the formula, R ０１ , R ０３ are each independently a hydrogen atom or a methyl group, and R ０２ is expressed by the following formula (R ０２ -1) to (R ０２ R is an organic group selected from the group consisting of ０４ is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R ０５ is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. 【Chemistry 2】 (In the formula, dashed lines indicate bonds.)

2. A method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) forming a silicon-containing resist intermediate film on the resist underlayer film; (II-3) A step of applying the composition for forming an adhesion film onto the silicon-containing resist intermediate film, followed by heat treatment to form an adhesion film; (II-4) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (II-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (II-6) A step of transferring a pattern to the adhesion film and the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (II-7) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-8) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; wherein the repeating unit represented by general formula (2) undergoes an elimination and decomposition reaction of R 05 under the action of an acid to generate a carboxylic acid. 【Chemistry 3】 (In the formula, R ０１ , R ０３ are each independently a hydrogen atom or a methyl group, and R ０２ is expressed by the following formula (R ０２ -1) to (R ０２ R is an organic group selected from the group consisting of ０４ is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R ０５ is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. 【Chemistry 4】 (In the formula, dashed lines indicate bonds.)

3. A method for forming a pattern on a substrate to be processed, using a composition for forming an adhesion film for forming an adhesion film immediately below a resist upper layer film, the composition containing (A) a polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), (B) a thermal acid generator, and (C) an organic solvent, (III-1) forming a resist underlayer film on a substrate to be processed; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; (III-3) A step of forming an adhesion film by applying the composition for forming an adhesion film onto the inorganic hard mask intermediate film and then heat-treating the composition; (III-4) forming a resist upper layer film on the adhesion film using a composition for forming a resist upper layer film; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (III-6) a step of transferring a pattern to the adhesion film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (III-7) transferring the pattern to the resist underlayer film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; wherein the repeating unit represented by general formula (2) undergoes an elimination and decomposition reaction of R 05 under the action of an acid to generate a carboxylic acid. 【Chemistry 5】 (In the formula, R ０１ , R ０３ are each independently a hydrogen atom or a methyl group, and R ０２ is expressed by the following formula (R ０２ -1) to (R ０２ R is an organic group selected from the group consisting of ０４ is a single bond or a divalent linking group containing an ester group and having 2 to 10 carbon atoms, and R ０５ is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms, which may contain an oxygen functional group. 【Chemistry 6】 (In the formula, dashed lines indicate bonds.)

4. 4. The pattern forming method according to claim 3, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

5. 5. The pattern forming method according to claim 2, wherein the thickness of the adhesive film directly below the resist top layer film is 15 nm or less.

6. 5. The pattern forming method according to claim 1, wherein the resist upper layer film is formed using a composition for forming a resist upper layer film, the composition comprising at least a metal atom-containing compound and an organic solvent.

7. 7. The pattern formation method according to claim 6, wherein the metal atom-containing compound contains at least one selected from the group consisting of titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium.

8. 5. The pattern forming method according to claim 1, wherein a method for forming a circuit pattern on the resist upper layer film is performed by photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing using an electron beam, nanoimprinting, or a combination thereof.

9. 5. The pattern forming method according to claim 1, wherein the development is carried out using an alkali development or an organic solvent.

10. 5. The pattern forming method according to claim 1, wherein the workpiece substrate is a semiconductor device substrate, or a semiconductor device substrate having any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film formed thereon.

11. 11. The pattern formation method according to claim 10, wherein 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.

12. The pattern forming method according to any one of claims 1 to 4, characterized in that the adhesion film is formed by spin-coating the composition for forming an adhesion film, and heat-treating the substrate coated with the composition for forming an adhesion film at a temperature of 100 ° C. or higher and 300 ° C. or lower for 10 to 600 seconds.

13. 5. The pattern forming method according to claim 1, wherein the composition for forming an adhesion film is spin-coated, and the substrate to which the composition for forming an adhesion film is coated is heat-treated in an atmosphere with an oxygen concentration of 0.1% or more and 21% or less, thereby forming an adhesion film.

14. 5. The pattern forming method according to claim 1, wherein the composition for forming an adhesion film is spin-coated, and the substrate to which the composition for forming an adhesion film is coated is heat-treated in an atmosphere with an oxygen concentration of less than 0.1%, thereby forming an adhesion film.

Images