Metal-containing film forming composition and pattern forming method

Abstract

The invention relates to a metal-containing film forming composition and a pattern forming method. The invention provides a composition for forming a metal-containing film, which can obtain a good pattern shape and can inhibit the collapse of a fine pattern. A metal-containing film-forming composition containing (A) a metal compound, (B) a surface modifier, and (C) a solvent, the metal compound containing at least one metal atom selected from the group consisting of Ti, Zr, and Hf; the surface modifier (B) is a polymer compound containing a repeating unit represented by general formula (1) and / or a repeating unit represented by general formula (2), and the polymer compound does not contain a repeating unit containing a hydroxyl group. In the formula 1 # imgabs0, R1 is a hydrogen atom or a methyl group, R2 is a monovalent organic group having 2-20 carbon atoms and containing a heterocyclic structure, and R3 is a hydrogen atom or a linear or branched alkyl group having 1-3 carbon atoms.

Description

Technical Field

[0001] The present invention relates to a metal-containing film-forming composition that can be used for fine patterning by a multilayer resist method in a semiconductor device manufacturing process, and a pattern forming method using the composition. Background Art

[0002] With the high integration and high speed of LSI, the miniaturization of pattern size is progressing rapidly. As the miniaturization progresses, the photolithography technology has achieved the formation of fine patterns by shortening the wavelength of the light source and appropriately selecting the resist composition for it. The center is a positive photoresist composition used in a single layer. This single-layer positive photoresist composition is made by making the resist resin have a skeleton that is etch-resistant to dry etching using chlorine-based or fluorine-based gas plasma, and has a switching mechanism that dissolves the exposed part, so that the exposed part is dissolved to form a pattern, and the substrate to be processed is dry-etched using the remaining resist pattern as an etching mask.

[0003] However, if the thickness of the photoresist film used is maintained and miniaturized, even if the pattern width is reduced, the resolution performance of the photoresist film is reduced, and if the photoresist film is to be patterned using a developer, the so-called aspect ratio becomes too large, resulting in a problem of pattern collapse. Therefore, as the pattern is miniaturized, the photoresist film is gradually thinned.

[0004] On the other hand, the processing of the processed substrate usually uses a method of processing the substrate by dry etching using a photoresist film formed with a pattern as an etching mask, but in reality there is no dry etching method that can obtain complete etching selectivity between the photoresist film and the processed substrate. Therefore, there will be a problem that the resist film is also damaged and collapsed during the processing of the substrate, and the resist pattern becomes unable to be correctly transferred to the processed substrate. Therefore, with the miniaturization of the pattern, the resist composition is also gradually seeking higher dry etching resistance. However, on the other hand, in order to improve the resolution, the resin used in the photoresist composition has gradually sought a resin with small light absorption at the exposure wavelength. Therefore, as the exposure light is shortened to i-rays, KrF, and ArF, the resin is gradually changed to novolac resin, polyhydroxystyrene, and resins with aliphatic polycyclic skeletons, but in reality, the etching speed under dry etching conditions during substrate processing gradually becomes faster, and the recent photoresist composition with high resolution tends to weaken etching resistance.

[0005] In view of this situation, it becomes necessary to perform dry etching processing on the substrate to be processed using a thinner photoresist film with weaker etching resistance, and it is urgent to ensure the materials and processes in this processing step.

[0006] As one of the methods for solving such a problem, there is a multilayer resist method, in which an intermediate film having an etching selectivity different from that of a photoresist film (i.e., a resist upper film) is inserted between the resist upper film and a substrate to be processed, and after the resist upper film has a pattern, the resist upper film pattern is used as a dry etching mask to transfer the pattern to the intermediate film by dry etching, and further, the intermediate film is used as a dry etching mask to transfer the pattern to the substrate to be processed by dry etching.

[0007] As one of the multilayer resist methods, there is a three-layer resist method that can be implemented using a general resist composition used in the single-layer resist method. In the three-layer resist method, for example, an organic film composed of a novolac resin or the like is formed on a substrate to be processed as a resist lower film, a silicon-containing film is formed thereon as a resist intermediate film, and then a normal organic photoresist film is formed thereon as a resist upper film. When dry etching using fluorine-based gas plasma is performed, the organic resist upper film can achieve a good etching selectivity ratio relative to the silicon-containing resist intermediate film, so the resist upper film pattern can be transferred to the silicon-containing resist intermediate film using dry etching using fluorine-based gas plasma. According to this method, even if a resist composition that is difficult to form a pattern having a sufficient film thickness required for directly processing a substrate to be processed is used, or a resist composition that does not have sufficient dry etching resistance required for processing a substrate is used, the pattern can be transferred to a silicon-containing resist intermediate film (resist intermediate film), and then the pattern transfer is performed by dry etching performed by oxygen-based or hydrogen-based gas plasma, so that a pattern of an organic film (resist underlayer film) composed of a novolac resin or the like having sufficient dry etching resistance required for processing a substrate can be obtained. As for the above-mentioned resist underlayer film, many are already known, such as those described in Patent Document 1.

[0008] As the silicon-containing resist intermediate film used in the above-mentioned three-layer resist method, a silicon-containing inorganic film obtained by CVD, such as SiO 2 As a film obtained by spin coating, a SOG (spin-on-glass) film (for example, Patent Document 4 and Non-Patent Document 1), a cross-linked silsesquioxane film (for example, Patent Document 5), etc., or a polysilane film (for example, Patent Document 6) can be used. Among these, SiO 2 SiO2 films and SiON films have high performance as dry etching masks when dry etching the underlying organic film, but special equipment is required for film formation. On the other hand, SOG films, cross-linked silsesquioxane films, and polysilane films can be formed by only spin coating and heating, and are considered to have higher processing efficiency.

[0009] There are some problems with silicon-containing films used in such multilayer resist methods. For example, when a resist pattern is to be formed by optical lithography, it is known that the exposure light will be reflected on the substrate and interfere with the incident light to cause the so-called standing wave problem. In order to obtain a fine pattern without edge roughness of the resist film under the most advanced ArF immersion and high NA exposure conditions, the intermediate film needs to have an anti-reflection effect. In addition, in the most advanced semiconductor processing as mentioned above, the photoresist thin film is further advanced, so the intermediate film is also required to be thinner. In the next generation of exposure processing, it is required to have an anti-reflection effect with a film thickness of less than 30nm. In addition, when processing the resist lower film, the dry etching speed of the oxygen plasma generally used is preferably smaller in order to improve the etching selectivity ratio between the intermediate film and the lower film. Due to the trend of thin film, the dry etching resistance of the intermediate film is required to be improved.

[0010] As a resist intermediate film that meets the requirements for such antireflection effect and dry etching characteristics, metal-containing films (metal hard mask films) containing Ti and Zr have attracted attention instead of the known silicon-containing films. 2 、ZrO 2 Since the film contains these materials with a high refractive index, the antireflection effect under high NA exposure conditions can be improved. In addition, since the film contains metal-oxygen bonds, excellent dry etching resistance to oxygen can be expected.

[0011] Furthermore, since the metal-containing film has excellent dry etching resistance not only to oxygen but also to fluorine gas, a two-layer resist method can be expected in which a metal-containing film is formed on a processed substrate as a resist lower layer film and a resist upper layer film is formed thereon.

[0012] On the other hand, when such a metal-containing film is used directly under the resist upper film, the improvement of the adhesion with the resist pattern becomes a problem. The hardened metal-containing film has a relatively much higher surface energy (or a smaller water contact angle) than the photoresist used subsequently. This mismatch in surface energy will cause poor adhesion between the metal-containing film and the photoresist used subsequently, and will also cause pattern collapse.

[0013] In order to suppress the collapse of the photoresist pattern on the metal-containing film, it is necessary to modify the surface of the metal-containing film. For example, Patent Document 7 reports a metal hard mask containing a surface-modified organic polymer. By using the difference in free energy between the organic polymer and the metal compound, the organic polymer is concentrated on the surface layer, and it is reported that the adhesion with the resist pattern will be improved. In order to suppress the collapse of the pattern, an organic polymer containing a surface-treated portion of a hydroxyl group, a protected hydroxyl group, a protected carboxyl group, and a mixture thereof is used. However, in the current situation where it is required to form a finer pattern, these materials cannot be said to have sufficient performance in suppressing the collapse of the pattern.

[0014] It has recently been discovered that in fine patterns, the interaction between the interface between the resist upper film and the lower film directly below the resist upper film can also affect the sensitivity of the resist, the shape of the pattern (rectangularity and residue in the spacing portion), etc. From these viewpoints, the performance of the lower film directly below the resist upper film is also required to be improved (Non-Patent Document 2).

[0015] Prior art literature

[0016] Patent Literature

[0017] [Patent Document 1] Japanese Patent Application Publication No. 2004-205685

[0018] [Patent Document 2] Japanese Patent Application Laid-Open No. 7-183194

[0019] [Patent Document 3] Japanese Patent Application Laid-Open No. 7-181688

[0020] [Patent Document 4] Japanese Patent Application Laid-Open No. 5-291208

[0021] [Patent Document 5] Japanese Patent Publication No. 2005-520354

[0022] [Patent Document 6] Japanese Patent Application Laid-Open No. 11-60735

[0023] [Patent Document 7] Japanese Patent No. 6463600

[0024] Non-patent literature

[0025] [Non-patent document 1] J. Appl. Polym. Sci., Vol. 88, 636-640 (2003)

[0026] [Non-patent document 2] Proc. SPIE Vol. 7273, 72731J (2009) Summary of the invention

[0027] [Problems to be solved by the invention]

[0028] In view of the above situation, the present invention aims to provide a metal-containing film forming composition that can obtain a good pattern shape and has high adhesion with the upper film of the resist and can inhibit the collapse of the fine pattern in the fine patterning process of the semiconductor device manufacturing step, and a pattern forming method using the composition.

[0029] [Methods for solving problems]

[0030] In order to solve the above problems, the present invention provides a metal-containing film-forming composition, which is characterized by containing (A) a metal compound, (B) a surface modifier, and (C) a solvent.

[0031] The metal compound contains at least one metal atom selected from the group consisting of Ti, Zr and Hf,

[0032] The surface modifier (B) is a polymer compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and the polymer compound does not contain a repeating unit containing a hydroxyl group.

[0033] [Chemistry 1]

[0034]

[0035] In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R 3 It is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

[0036] Such a metal-containing film-forming composition can form a metal-containing film that has high adhesion to the resist upper layer film, has the effect of preventing fine pattern collapse, and can provide a good pattern shape. In addition, the obtained metal-containing film shows a high refractive index, so it can exert a high anti-reflection effect under ArF immersion and high NA exposure conditions.

[0037] Furthermore, the aforementioned heterocyclic structure is preferably a heterocyclic structure containing an oxygen atom.

[0038] The metal-containing film-forming composition having such a structure can achieve higher adhesion with the resist upper layer film, and is more effective in preventing collapse of fine patterns.

[0039] In the above general formulas (1) and (2), R 2 , is a compound selected from the following formula (R 2 -1)~(R 2 -3) is preferably a monovalent organic group.

[0040] [Chemistry 2]

[0041]

[0042] In the formula, R 4 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the chain represents an atomic bond.

[0043] By containing the (B) surface modifier having such a structure, the metal-containing film-forming composition can obtain higher adhesion with the resist upper layer film, and is more effective in preventing the collapse of fine patterns.

[0044] Furthermore, the surface modifier (B) is preferably a polymer compound further comprising any of the repeating units represented by the following formula (3a) or formula (3b).

[0045] [Chemistry 3]

[0046]

[0047] In the above formula, R F1 is a monovalent organic group having 1 to 20 carbon atoms and containing at least one F atom, R F2 is a F atom or a monovalent organic group having 1 to 10 carbon atoms and containing one or more F atoms, R 1 is a hydrogen atom or a methyl group, and n represents 1 to 5.

[0048] By using such a surface modifier, the surface modifier is more likely to be concentrated on the surface layer of the metal-containing film, which is more preferable.

[0049] Furthermore, the weight average molecular weight of the polymer compound used as the surface modifier (B) is preferably 6,000 to 50,000.

[0050] Furthermore, the polymer compound used in the surface modifier (B) preferably has a dispersity expressed by weight average molecular weight / number average molecular weight of 3.0 or less.

[0051] When the weight average molecular weight and / or dispersion degree of the polymer compound contained in the metal-containing film-forming composition is within such a range, excellent film-forming properties can be obtained, and generation of sublimates during heat curing can be suppressed to prevent device contamination.

[0052] The content of the surface modifier (B) in the metal-containing film-forming composition is preferably 1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the metal compound.

[0053] By containing the surface modifier at such a ratio, higher adhesion with the resist upper layer film can be obtained without deteriorating the dry etching resistance and refractive index of the metal-containing film-forming composition, and the collapse of fine patterns can be prevented more effectively.

[0054] Furthermore, it contains

[0055] (D) Thermal acid generator,

[0056] (E) photoacid generator,

[0057] (F) a cross-linking agent, and

[0058] (G) Surfactant

[0059] At least one of the above is preferred.

[0060] By the presence or absence and selection of these various additives, fine adjustment of the performance in accordance with customer requirements can be performed in terms of film forming properties, reduction of sublimates, and further various properties of resist patterning, which is practically ideal.

[0061] Furthermore, the aforementioned (C) solvent contains (C-1) a high boiling point solvent,

[0062] The high boiling point solvent (C-1) is preferably one or more organic solvents having a boiling point of 180 degrees or higher.

[0063] By containing such a high boiling point solvent, sufficient thermal fluidity can be obtained during film formation, so when a metal-containing film is formed, the etching selectivity of (A) the metal compound and the pattern adhesion of (B) the surface modifier can be achieved at a high level without forming a sea-island structure.

[0064] Furthermore, the metal compound (A) is preferably a metal compound represented by the following general formula (4).

[0065] [Chemistry 4]

[0066] L a Mx b (4)

[0067] In the formula, M is any one of Ti, Zr or Hf. L is a monodentate ligand or a polydentate ligand having 1 to 30 carbon atoms, and X is selected from a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR a R b Hydrolyzable group. a and R b Each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a+b=4, and a and b are integers of 0-4.

[0068] By using such a metal compound, a metal-containing film having better dry etching resistance with respect to oxygen gas can be formed.

[0069] In this case, the aforementioned (A) metal compound is preferably a reaction product of a compound derived from the metal compound represented by the aforementioned general formula (4) and an organic compound having 1 to 30 carbon atoms and containing at least one cross-linking group represented by any of the following general formulas (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3).

[0070] [Chemistry 5]

[0071]

[0072] In the above general formulas (a-1) to (a-4), R a It is hydrogen or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding part.

[0073] [Chemistry 6]

[0074]

[0075] In the above general formula, R b is a hydrogen atom or a methyl group, which may be the same as or different from each other in the same formula, and R c It is hydrogen or a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; * represents a bonding portion.

[0076] [Chemistry 7]

[0077]

[0078] In the above general formulas (c-1) to (c-3), Y 1 is a divalent organic group having 1 to 20 carbon atoms, R is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, R d It is an organic group represented by the following general formula (c-4), in which the protective group is released by the action of either or both of acid and heat to generate one or more hydroxyl groups or carboxyl groups, and * represents a bonding part.

[0079] [Chemistry 8]

[0080]

[0081] In the above general formula (c-4), R e is an organic group from which the protective group is released by the action of either acid or heat or both, and * indicates 1 The bonding portion.

[0082] If the (A) metal compound contains such an organic group, sufficient thermal fluidity can be obtained during film formation, so when a metal-containing film is formed, the etching selectivity of the (A) metal compound and the pattern adhesion of the (B) surface modifier can be achieved to a higher degree without forming a sea-island structure.

[0083] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0084] (I-1) After applying the metal-containing film-forming composition of the present invention on a substrate to be processed, a metal-containing film is formed by heat treatment,

[0085] (I-2) forming a resist upper layer film on the aforementioned metal-containing film using a photoresist material,

[0086] (I-3) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0087] (I-4) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching, and

[0088] (I-5) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0089] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0090] (II-1) forming a resist underlayer film on a substrate to be processed,

[0091] (II-2) After applying the metal-containing film-forming composition of the present invention on the resist underlayer film, a metal-containing film is formed by heat treatment,

[0092] (II-3) forming a resist upper layer film on the aforementioned metal-containing film using a photoresist material,

[0093] (II-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0094] (II-5) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching,

[0095] (II-6) using the metal-containing film to which the pattern has been transferred as a mask, transferring the pattern to the resist underlayer film by dry etching,

[0096] (II-7) The substrate to be processed is processed using the patterned resist underlayer film as a mask to form a pattern on the substrate to be processed.

[0097] Thus, the metal-containing film-forming composition of the present invention is suitable for use in various pattern forming methods such as two-layer resist processing and three-layer resist processing. In these pattern forming methods, the metal-containing film provided by the present invention can be used to effectively suppress pattern collapse, is suitable for optical lithography of the resist upper film, and can transfer the resist upper film pattern to the processed substrate with high precision.

[0098] [Effects of the Invention]

[0099] As described above, the present invention provides a metal-containing film-forming composition having high adhesion to a resist upper film and having an effect of suppressing collapse of a fine pattern. Furthermore, this metal-containing film-forming composition has high adhesion and an effect of suppressing collapse of a fine pattern, and can provide a pattern shape of a resist upper film with high rectangularity to a processed substrate, so it is very useful in multilayer resist processing. Furthermore, the metal-containing film-forming composition of the present invention has excellent resistance to dry etching using oxygen and fluorine gas, respectively, so in various pattern forming methods such as two-layer resist processing and three-layer resist processing, a fine pattern can be formed on a processed substrate with high precision. BRIEF DESCRIPTION OF THE DRAWINGS

[0100] Figure 1 (A) to (F) are explanatory diagrams of an example (three-layer resist process) of the pattern forming method of the present invention.

[0101] Figure 2 (G) to (K) are explanatory diagrams of an example of the pattern forming method of the present invention (two-layer resist processing).

[0102] Figure 3 This is a diagram for explaining the calculation of reflectance in the pattern forming method. DETAILED DESCRIPTION

[0103] As mentioned above, it is desired to develop a metal-containing film forming composition and a pattern forming method using the composition, which can provide a metal-containing film with a good pattern shape, high adhesion with the upper film of the resist, and suppress the collapse of the fine pattern in the fine patterning process of the semiconductor device manufacturing step.

[0104] The inventors of the present application have made great efforts to study the above-mentioned problems and have found that a metal-containing film-forming composition containing a polymer compound of a specific structure and a pattern forming method using the metal-containing film-forming composition can solve the above-mentioned problems, thereby completing the present invention.

[0105] That is, the present invention is a metal-containing film-forming composition, which is characterized by containing:

[0106] (A) Metal compounds,

[0107] (B) surface modifiers, and

[0108] (C) a solvent,

[0109] The metal compound contains at least one metal atom selected from the group consisting of Ti, Zr and Hf,

[0110] The surface modifier (B) is a polymer compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and the polymer compound does not contain a repeating unit containing a hydroxyl group.

[0111] [Chemistry 9]

[0112]

[0113] In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R 3 It is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

[0114] Furthermore, the present invention is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0115] (I-1) After applying the metal-containing film-forming composition of the present invention on a substrate to be processed, a metal-containing film is formed by heat treatment,

[0116] (I-2) forming a resist upper layer film on the aforementioned metal-containing film using a photoresist material,

[0117] (I-3) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0118] (I-4) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching, and

[0119] (I-5) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0120] Furthermore, the present invention is a pattern forming method, which is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0121] (II-1) forming a resist underlayer film on a substrate to be processed,

[0122] (II-2) After applying the metal-containing film-forming composition of the present invention on the resist underlayer film, a metal-containing film is formed by heat treatment,

[0123] (II-3) forming a resist upper layer film on the aforementioned metal-containing film using a photoresist material,

[0124] (II-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0125] (II-5) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching,

[0126] (II-6) using the metal-containing film to which the pattern has been transferred as a mask, transferring the pattern to the resist underlayer film by dry etching,

[0127] (II-7) The substrate to be processed is processed using the patterned resist underlayer film as a mask to form a pattern on the substrate to be processed.

[0128] The present invention is described in detail below, but the present invention is not limited thereto.

[0129] <Metal-Containing Film-Forming Composition>

[0130] The present invention is a metal-containing film-forming composition, characterized in that it contains

[0131] (A) Metal compounds,

[0132] (B) surface modifiers, and

[0133] (C) a solvent,

[0134] The metal compound contains at least one metal atom selected from the group consisting of Ti, Zr and Hf,

[0135] The surface modifier (B) is a polymer compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and the polymer compound does not contain a repeating unit containing a hydroxyl group.

[0136] [Chemistry 10]

[0137]

[0138] In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R 3 It is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

[0139] In the metal-containing film-forming composition of the present invention, (A) the metal compound, (B) the surface modifier, and (C) the solvent may be used alone or in combination of two or more components. Furthermore, the metal-containing film-forming composition may contain components other than the above-mentioned components (A), (B), and (C). Each component is described below.

[0140] <(A) Metal Compound>

[0141] The (A) metal compound contained in the metal-containing film-forming composition of the present invention contains at least one metal atom selected from the group consisting of Ti, Zr and Hf.

[0142] By including such a metal, the refractive index of the metal-containing film after heat treatment can be increased, and a metal-containing film having excellent dry etching resistance using oxygen gas and fluorine gas can be formed.

[0143] (A) In the metal compound, the lower limit of the atomic content of the metal element is preferably 10 mass %, more preferably 20 mass %, and even more preferably 30 mass %. The upper limit of the above content is preferably 50 mass %. The atomic content of the metal element can be determined by measurement using a differential thermometer (TG / DTA).

[0144] If the ratio of the metal element is such, the refractive index of the metal-containing film-forming composition and the dry etching resistance to oxygen gas and fluorine gas can be further improved.

[0145] The metal atoms contained in the above-mentioned metal compound may be composed of atoms of one element or of two or more elements. Considering that the etching rate during the inorganic film etching transfer process after the formation of a fine pattern is desired to be uniform within the surface at the nanoscale, it is preferred that the metal compound be composed of atoms of one element.

[0146] (A) The metal compound is preferably a compound having a metal-oxygen covalent bond.

[0147] The metal compound contains metal-oxygen atoms, so that the metal-containing film formed by the metal-containing film-forming composition has better etching selectivity. The oxygen atom may be bonded to one metal atom or to multiple metal atom, but a structure mainly containing two oxygen atoms bonded to the metal atom is preferred. By mainly containing a structure in which a metal atom is bonded to two oxygen atoms, the metal compound will have a more linear structure such as -MOMO- (M is at least one metal atom selected from the group consisting of Ti, Zr and Hf), which can improve solvent solubility.

[0148] In order to form a two-layer structure by coating two substances of different properties at once, the difference in free energy between (A) the metal compound and (B) the surface modifier must be appropriate. If the difference in free energy is inappropriate, a so-called sea-island structure in which microdomains of one layer are dotted in the matrix of the other layer often occurs, and the combination of (A) the metal compound and (B) the surface modifier becomes important.

[0149] The (A) metal compound of the present invention may also use a commercially available metal compound, for example, a metal-containing compound having a hydrolyzable group (hereinafter referred to as (a) metal-containing compound). Alternatively, the metal compound may be synthesized by a method of performing a hydrolysis-condensation reaction of the (a) metal-containing compound. That is, the (A) metal compound may be derived from the (a) metal-containing compound. Here, the "hydrolysis-condensation reaction" refers to a reaction in which the hydrolyzable group possessed by the (a) metal-containing compound is hydrolyzed and converted to -OH, and the two obtained -OH are dehydrated and condensed to form -O-.

[0150] The (A) metal compound of the present invention is preferably a compound obtained by reacting the above-mentioned (a) metal-containing compound, a hydrolysis-condensation reaction product of a (a) metal-containing compound, or a compound obtained by reacting these compounds with a substance capable of forming a monodentate ligand or a multi-seat ligand. It is even more preferred to use a compound obtained by reacting the hydrolysis-condensation reaction product of a (a) metal-containing compound or a compound obtained by reacting the hydrolysis-condensation reaction product of a (a) metal-containing compound with a substance capable of forming a monodentate ligand or a multi-seat ligand.

[0151] Since the surface energy of the metal compound (A) is higher than that of the surface modifier (B), the etching selectivity of the metal compound (A) and the pattern adhesion of the surface modifier (B) can be achieved at a high level without forming a sea-island structure when forming a resist underlayer film.

[0152] [(a) Metal-containing compounds]

[0153] The metal-containing compound (a) is a metal compound (I) having a hydrolyzable group, a hydrolyzate of the metal compound (I), a hydrolysis condensate of the metal compound (I), or a combination thereof. In other words, the metal-containing compound (a) is derived from the metal compound (I). The metal compound (I) may be used alone or in combination of two or more.

[0154] The metal compound (I) is, for example, a compound (I-1) represented by the following formula (4). By using such a metal compound (I-1), a stable compound (A) can be formed, and dry etching resistance can be improved.

[0155] [Chemistry 11]

[0156] L a MX b (4)

[0157] In the formula, M is any one of Ti, Zr or Hf. L is a monodentate ligand or a polydentate ligand having 1 to 30 carbon atoms, and X is selected from a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR a R b The hydrolyzable group in R a and R bEach independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a+b=4, and a and b are integers of 0-4.

[0158] [Hydrolyzable Group]

[0159] The hydrolyzable group X is, for example, a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, and -NR a R b . R a and R b Each independently is preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0160] The above-mentioned halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

[0161] The above-mentioned alkoxy group includes, for example, methoxy, ethoxy, n-butoxy, isopropoxy, n-butoxy, tert-butoxy and the like.

[0162] The carboxylate group includes, for example, acetate, propionate, butyrate, hexanoate, octanoate, and the like.

[0163] Examples of the acyloxy group include acetyloxy, acetyloxy, propionyloxy, butyryloxy, tert-butyryloxy, tert-valeryloxy, n-hexanecarbonyloxy and n-octanecarbonyloxy groups.

[0164] Above-NR a R b , such as unsubstituted amino, methylamino, dimethylamino, diethylamino, dipropylamino and the like.

[0165] The hydrolyzable group X is preferably an alkoxy group, more preferably an isopropoxy group, an n-butoxy group, or a tert-butoxy group.

[0166] [Monodentate ligand]

[0167] The above-mentioned monodentate ligands include, for example, hydroxyl ligands, carboxyl ligands, amide ligands, amine ligands, amino ligands, olefin ligands, and the like.

[0168] The above amide ligands, for example, unsubstituted amide ligands (NH 2 ), methylamide ligand (NHMe), dimethylamide ligand (NMe 2 ), diethylamide ligand (NEt 2 ), dipropylamide ligand (NPr 2 )wait.

[0169] The above-mentioned amine ligands include, for example, pyridine, trimethylamine ligands, piperidine ligands, and the like.

[0170] Olefin ligands, for example: chain olefins such as ethylene and propylene, cyclic olefins such as cyclopentene, cyclohexene, and norbornene, etc.

[0171] [Multidentate ligand]

[0172] The above-mentioned multidentate ligands include, for example, ligands derived from hydroxy acid esters, ligands derived from β-diketones, ligands derived from β-ketoesters, ligands derived from α,α-dicarboxylates, hydrocarbons having π bonds, biphosphines, and the like.

[0173] The above-mentioned hydroxy acid esters include glycolic acid esters, lactic acid esters, 2-hydroxycyclohexane-1-carboxylic acid esters, salicylic acid esters and the like.

[0174] Examples of the β-diketone include acetoacetate, α-alkyl-substituted acetoacetate, β-ketovalerate, benzoyl acetate, and 1,3-acetone dicarboxylate.

[0175] The above-mentioned α,α-dicarboxylic acid esters include, for example, malonic acid diesters, α-alkyl-substituted malonic acid diesters, α-cycloalkyl-substituted malonic acid diesters, α-aryl-substituted malonic acid diesters, and the like.

[0176] The above-mentioned hydrocarbons having a π bond include, for example, chain dienes such as butadiene and isoprene, cyclic dienes such as cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, cyclohexadiene, and norbornadiene, and aromatic hydrocarbons such as benzene, toluene, xylene, hexamethylbenzene, naphthalene, and indene.

[0177] The above-mentioned biphosphine is, for example, 1,1-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 1,1'-bis(diphenylphosphino)ferrocene, and the like.

[0178] In the above general formula (4), a+b=4, and a and b are integers of 0 to 4. a is preferably 0 to 3, more preferably 0 to 2, more preferably 1 to 2, and particularly preferably 2. b is preferably 2 to 4, more preferably 2 or 3, and even more preferably 2. By setting a and b within the above ranges, the stability of the metal compound (A) can be improved.

[0179] The (a) metal-containing compound is preferably a metal alkoxide which is neither hydrolyzed nor hydrolytically condensed, or a metal alkoxide which has a ligand and is not hydrolytically condensed.

[0180] (a) Metal-containing compounds, for example: titanium-containing compounds include diisopropoxybis(2,4-pentanedionato)titanium(IV), tetra-n-butoxytitanium(IV), tetra-n-propoxytitanium(IV), tri-n-butoxymonostearatetitanium(IV), butoxytitanium(IV) oligomer, aminopropyltrimethoxytitanium(IV), triethoxymono(2,4-pentanedionato)titanium(IV), tri-n-propoxymono(2,4-pentanedionato)titanium(IV), triisopropoxymono(2,4-pentanedionato)titanium, di-n-butoxybis(2,4-pentanedionato)titanium(IV), etc.; zirconium-containing compounds include dibutoxybis(ethylacetoacetate)zirconium(IV), di-n-butoxybis(2,4-pentanedionato)zirconium(IV), tetra-n-butoxyzirconium(IV), tetra-n-propoxyzirconium(IV), tetraisopropyl trimethoxy zirconium (IV), tri-(3-propoxy)-1-nitro ...

[0181] During the synthesis reaction of the metal compound (A), in addition to the metal-containing compound (a), a compound capable of forming a monodentate ligand or a polydentate ligand on the metal compound (hereinafter referred to as (b) ligand-forming compound) may be added.

[0182] The above-mentioned (b) ligand-forming compound may include organic compounds derived from hydroxyl ligands, carboxyl ligands, amide ligands, amine ligands, amino ligands, olefin ligands, etc. exemplified for L in the above formula (4), organic compounds derived from ligands derived from hydroxy acid esters, ligands derived from β-diketones, ligands derived from β-ketoesters, ligands derived from α,α-dicarboxylates, etc., and in addition, compounds having multiple hydroxyl groups may be included.

[0183] Furthermore, the (b) ligand-forming compound may be an organic compound having 1 to 30 carbon atoms and containing at least one crosslinking group represented by any of the following general formulae (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3).

[0184] [Chemistry 12]

[0185]

[0186] In the above general formulas (a-1) to (a-4), R a It is hydrogen or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding part.

[0187] [Chemistry 13]

[0188]

[0189] In the above general formula, R b is a hydrogen atom or a methyl group, which may be the same as or different from each other in the same formula, and R c It is hydrogen or a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; * represents a bonding portion.

[0190] [Chemistry 14]

[0191]

[0192] In the above general formulas (c-1) to (c-3), Y 1 is a divalent organic group having 1 to 20 carbon atoms, R is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, R d It is an organic group represented by the following general formula (c-4) in which the protective group is released by the action of either or both of acid and heat to generate one or more hydroxyl groups or carboxyl groups, and * represents a bonding part.

[0193] [Chemistry 15]

[0194]

[0195] In the above general formula (c-4), R e is an organic group from which the protecting group is released by the action of either acid or heat or both, and * is 1 The bonding portion.

[0196] (b) The ligand-forming compound contains at least one cross-linking group represented by any of the above (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3), so that sufficient thermal fluidity can be obtained during film formation. Therefore, when a metal-containing film is formed, it is believed that an island structure will not be formed, and both (A) the etching selectivity of the metal compound and (B) the pattern adhesion of the surface modifier can be taken into account to a higher degree.

[0197] From the viewpoint of productivity and stability of the (A) metal compound, the (b) ligand-forming compound is preferably a compound derived from a carboxyl ligand, a compound derived from a ligand derived from β-diketone, or a compound having a plurality of hydroxyl groups. These can be used alone or in combination of two or more.

[0198] The compound derived from the carboxyl ligand is, for example, a compound represented by the following formula (5).

[0199] [Chemistry 16]

[0200]

[0201] In the above general formula (5), p is 0 or 1. When p is 1, X 1 is a divalent organic group having 2 to 20 carbon atoms, W is an alkoxy group having 1 to 10 carbon atoms, the following general formula (5-A), or any of the general formulas (b-1) to (b-4). When p is 0, X 1 It is a monovalent organic group having 8 to 30 carbon atoms and a crosslinking group of any of the structures represented by the above general formulae (a-2) and (a-3) and an aromatic ring.

[0202] [Chemistry 17]

[0203]

[0204] In the above general formula (5-A), Y is a saturated or unsaturated divalent organic group having 1 to 20 carbon atoms, and R A Any one of the structures represented by the above general formulae (a-1) to (a-4), h represents 1 to 6, and * represents a bond to the carbon atom of the carbonyl group.

[0205] When the compound is derived from a carboxyl ligand having such a structure, the heat curing property of the metal compound (A) is improved, and a metal-containing film having excellent mixing resistance of the resist upper layer film can be formed.

[0206] In the above general formula (5), p is 1 and W is preferably a structure represented by the following general formula (5-B).

[0207] [Chemistry 18]

[0208]

[0209] In the above general formula (5-B), R A1 is the structure represented by the above general formula (a-1), R A2 is any one of the structures represented by the above general formula (a-2) or (a-3), Z is an oxygen atom or a secondary amine, L is a divalent hydrocarbon group having 1 to 10 carbon atoms, and RA3 It is a saturated or unsaturated divalent organic group having 1 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 to 6, r is 1 to 10, u is 0 or 1, m is 0 or 1, and * represents a bond to the carbon atom of the carbonyl group.

[0210] When the compound is derived from a carboxyl ligand having such a structure, the heat resistance of the metal compound (A) is improved, so that the formed metal-containing film exhibits excellent film-forming properties, and the generation of sublimates during heat curing can be suppressed to prevent equipment contamination.

[0211] In the above general formula (5), p is 1, W is an alkoxy group having 1 to 10 carbon atoms, and X 1 Any of the structures represented by the following general formula (5-C) is preferred.

[0212] [Chemistry 19]

[0213]

[0214] When the compound is derived from a carboxyl ligand having such a structure, the heat resistance of the metal compound (A) is improved, the formed metal-containing film exhibits excellent film-forming properties, and the generation of sublimates during heat curing can be suppressed to prevent equipment contamination.

[0215] Or in the above general formula (5), p is 0, X 1 Any of the structures represented by the following general formula (5-D) is preferred.

[0216] [Chemistry 20]

[0217]

[0218] In the above general formula (5-D), R f Similarly to the above-mentioned general formula (a-2) or (a-3), * represents a bonding portion to the carbon atom of the carbonyl group.

[0219] The compound derived from the carboxyl ligand is, for example, a compound represented by the following formula (6).

[0220] [Chemistry 21]

[0221]

[0222] In the above general formula (6), X 2 is a divalent organic group having 1 to 31 carbon atoms, R 6A It is any of the above-mentioned general formulae (c-1) to (c-3).

[0223] In the above general formula (6), X 2It is a divalent organic group having 1 to 31 carbon atoms, and is more preferably a saturated hydrocarbon having 1 to 20 carbon atoms or an unsaturated hydrocarbon having 2 to 20 carbon atoms from the viewpoint of thermosetting properties.

[0224] In the above general formulas (c-1) to (c-3), Y 1 is a substituted or unsubstituted saturated or unsaturated divalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, Y 1 It is preferably a saturated hydrocarbon having 1 to 20 carbon atoms or an unsaturated hydrocarbon having 2 to 20 carbon atoms.

[0225] In the above general formulas (c-1) to (c-3), if Y 1 A saturated hydrocarbon having 1 to 20 carbon atoms or an unsaturated hydrocarbon having 2 to 20 carbon atoms can further improve the heat curability of the metal compound (A). This is also preferred from the viewpoint of raw material availability.

[0226] Y 1 Examples include, but are not limited to, the following structures.

[0227] [Chemistry 22]

[0228]

[0229] * 1 is the bond portion with an oxygen atom or a nitrogen atom, 2 Representation and R d The bonding portion.

[0230] In the above general formula (c-4), R e The organic group from which the thermally acid-labile group is separated by the action of either acid or heat or both is preferably a tertiary hydrocarbon group or a group that forms an acetal structure together with an adjacent oxygen atom, and a tertiary hydrocarbon group is particularly preferred. The tertiary hydrocarbon group is preferably one having 4 to 20 carbon atoms, and more preferably one having fewer carbon atoms.

[0231] A compound derived from a ligand derived from β-diketone, for example, a compound represented by formula (7).

[0232] [Chemistry 23]

[0233]

[0234] In the above general formula, R 7A ~R 7c It is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a crosslinking group represented by any of the general formulae (a-1) to (a-4) and (b-1) to (b-4).

[0235] The compound of the general formula (7) preferably contains at least one crosslinking group represented by any of the general formulae (a-1) to (a-4) and (b-1) to (b-4). Such a compound is preferred because it can further improve the thermal curability of the metal compound (A).

[0236] Examples of the compound having a plurality of hydroxyl groups include divalent alcohols represented by any of the formulae (7-A) to (7-C).

[0237] [Chemistry 24]

[0238]

[0239] In the above general formula, R 7a ~R 7b is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a crosslinking group represented by any of the general formulae (a-1) to (a-4), R 7c ~R 7f is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a crosslinking group represented by any of the following general formulae (a-1) to (a-4) and (b-1) to (b-4), 2 is a divalent organic group having 1 to 10 carbon atoms. 7a With R 7b Bond to each other and form an unsaturated or saturated ring structure.

[0240] The compounds of the general formulae (7-A) to (7-C) preferably contain at least one crosslinking group represented by any of the general formulae (a-1) to (a-4) and (b-1) to (b-4). Such compounds are ideal because they can further enhance the thermal curability of the metal compound (A).

[0241] In the (A) metal compound, the content of the ligand derived from the (b) ligand-forming compound is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol%, of the total ligands coordinated to the metal atom. The content of the ligand other than the (b) ligand-forming compound, for example, the ligand derived from an alkoxy group having 1 to 10 carbon atoms, is preferably 0 mol% to 50 mol%, more preferably 0 mol% to 20 mol%, of the total ligands coordinated to the metal atom.

[0242] In addition, during the synthesis reaction of the metal compound (A), in addition to the (a) metal-containing compound and the (b) ligand-forming compound, the (c) silicon-containing compound may be added.

[0243] By substituting the hydrolyzable group of the (a) metal-containing compound with the (c) silicon-containing compound, the stability of the (A) metal compound in the metal-containing film-forming composition can be improved.

[0244] (c) Silicon-containing compounds, such as the following structure (s).

[0245] [Chemistry 25]

[0246]

[0247] In the above (s), R s1 , R s2 and R s3 , is any organic group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 1 to 20 carbon atoms, which is selected from any cross-linking group in the structures represented by the following general formulae (s-1) to (s-3).

[0248] [Chemistry 26]

[0249]

[0250] In the above general formulas (s-1) to (s-3), R s4 It is hydrogen or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding part.

[0251] The (c) silicon-containing compound is preferably a compound represented by any of the following formulae, and trimethylsilanol is more preferred from the viewpoint of productivity.

[0252] [Chemistry 27]

[0253]

[0254] When the (A) metal compound contains a ligand derived from the (b) ligand-forming compound and a ligand derived from the (c) silicon-containing compound, the content of the ligand derived from the (b) ligand-forming compound in the (A) metal compound is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol%, of the total ligands coordinated to the metal atom. The content of the ligand derived from the (c) silicon-containing compound is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol%, of the total ligands coordinated to the metal atom. The content of the ligand other than the (b) ligand-forming compound and the (c) silicon-containing compound, such as the ligand derived from an alkoxy group having 1 to 10 carbon atoms, is preferably 0 mol% to 50 mol%, more preferably 0 mol% to 20 mol%, of the total ligands coordinated to the metal atom.

[0255] When synthesizing a (A) metal compound containing a ligand from a (b) ligand-forming compound, the (A) metal compound only needs to contain a ligand from a (b) ligand-forming compound, and the synthesis method is not particularly limited. For example, the (a) metal-containing compound can use a metal alkoxide or a metal acetylacetonate (acac), which can be obtained by reacting an alkoxy or acac metal with a compound (b). After the (a) metal-containing compound is hydrolyzed and condensed, it can also be reacted with the (b) ligand-forming compound, or the (a) metal-containing compound can be reacted with the compound (b) and then hydrolyzed and condensed. When the hydrolysis and condensation are difficult to control, it can also be reacted with the compound (b) in a non-aqueous environment. They can be appropriately adjusted according to the necessary properties of the (A) metal compound and the metal-containing film. When (c) a silicon-containing compound and (b) a ligand-forming compound are used as ligands, it is preferred to react (a) a metal-containing compound with (c) a silicon-containing compound and then react with (b) a ligand-forming compound.

[0256] A method for hydrolysis-condensation reaction using (a) metal-containing compound, for example, a method for hydrolysis-condensation reaction of (a) metal-containing compound in a water-containing solvent. In this case, other compounds with hydrolyzable groups may be added as needed. In addition, acids such as acetic acid may be added as catalysts for hydrolysis-condensation reaction. As for the lower limit of the amount of water used in this hydrolysis-condensation reaction, 0.2 times mole is more ideal, 1 times mole is more preferred, and 3 times mole is more preferred relative to the hydrolyzable groups possessed by (a) metal-containing compound, etc. The upper limit of the amount of the above water is 20 times mole is more ideal, 15 times mole is more preferred, and 10 times mole is more preferred.

[0257] (A) The solvent used in the synthesis reaction of the metal compound is not particularly limited, and for example, the same solvent as the solvent exemplified for the (C) solvent described later can be used. Typical solvents and solvent mixtures contain ester, ether or alcohol functional groups, for example: a mixture of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) of 70 / 30 by volume. Examples of other solvents that can be used include butanediol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, 1-butanol, 2-butanol, 2-methyl-1-propanol, 4-methyl-2-pentanol Alcohol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diamyl ether, isoamyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0258] [(B) Surface modifier]

[0259] The surface modifier contained in the metal-containing film-forming composition of the present invention is a polymer compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). The polymer compound does not contain a repeating unit containing a hydroxyl group.

[0260] [Chemistry 28]

[0261]

[0262] In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R 3 It is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

[0263] Such a surface modifier (B) has a lower surface energy than the metal compound (A), so when a metal-containing film is formed, no sea-island structure is formed, and both the etching selectivity of the metal compound (A) and the pattern adhesion of the surface modifier (B) can be achieved to a high degree.

[0264] The above R 3 It is preferably a hydrogen atom.

[0265] R of the polymer compound containing any of the repeating units represented by the above general formula (1) or formula (2) 2The heterocyclic structure contained is preferably a heterocyclic structure containing an oxygen atom.

[0266] By including such a heterocyclic structure, higher adhesion with the resist pattern can be obtained, and collapse of the fine resist pattern can be prevented more effectively.

[0267] The aforementioned R 2 is a compound selected from the following formula (R 2 -1)~(R 2 -3) is preferably a monovalent organic group.

[0268] [Chemistry 29]

[0269]

[0270] In the formula, R 4 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the chain represents an atomic bond.

[0271] By containing such a heterocyclic structure, when the epoxy or oxetane structure is heated to form a film, a ring-opening reaction is induced and the film is hardened. In addition, the hydroxyl group generated by this ring-opening reaction also helps to improve the adhesion with the resist upper layer film.

[0272] The above (R 2 -3) in R 4 It is preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably an ethyl group.

[0273] Specific examples of the repeating units represented by the above formulae (1) and (2) include the following structures.

[0274] [Chemistry 30]

[0275]

[0276] R 1 and R 4 Same as above.

[0277] The polymer compound of the surface modifier (B) may contain only one kind of the repeating unit represented by the general formula (1) or the general formula (2), or may contain two or more kinds of the repeating unit.

[0278] In the polymer compound contained in the surface modifier (B), the content of any of the repeating units represented by the general formula (1) and the general formula (2) is preferably 30 mol % or more, more preferably 50 mol % or more, based on all the repeating units.

[0279] In the polymer compound contained in the surface modifier (B), the content of any of the repeating units represented by the general formula (1) and the formula (2) is preferably 95 mol% or less, more preferably 90 mol% or less, relative to all repeating units.

[0280] By having such a content ratio of any of the repeating units represented by the general formula (1) and the general formula (2), the polarity of the polymer compound can be adjusted, and the adhesion of the resist pattern becomes good. In addition, the epoxy or oxetane structure of the general formula (1) and (2) will induce a ring-opening reaction and the film will harden when heated to form a film, so a dense and tight film can be formed, and cross-mixing of the tight film and the resist upper film can be prevented. Thereby, the occurrence of residues in the spacing part of the pattern can be prevented, and a pattern with high rectangularity can be obtained. Therefore, in the above-mentioned (B) surface modifier, the content of any of the repeating units represented by the general formula (1) and the general formula (2) relative to all repeating units is 30 mol% or more and 95 mol% or less, and especially 50 mol% or more and 90 mol% or less is preferred.

[0281] The surface modifier is preferably a polymer compound further comprising any of the repeating units represented by the following formula (3a) or formula (3b).

[0282] [Chemistry 31]

[0283]

[0284] In the above formula, R F1 is a monovalent organic group having 1 to 20 carbon atoms and containing at least one F atom, R F2 is a F atom or a monovalent organic group having 1 to 10 carbon atoms and containing one or more F atoms, R 1 is a hydrogen atom or a methyl group, and n represents 1 to 5.

[0285] It is preferred that the polymer compound contains any of the repeating units represented by formula (3a) and formula (3b) because the surface modifier (B) is easily concentrated on the surface layer of the metal-containing film.

[0286] Specific examples of the repeating units represented by formula (3a) and formula (3b) include the following structures.

[0287] [Chemistry 32]

[0288]

[0289] R 1 Same as above.

[0290] The polymer compound (B) may contain only one type of the repeating units represented by the general formula (3a) and the general formula (3b), or may contain two or more types.

[0291] In the polymer compound of the surface modifier (B), the content of the repeating unit represented by the general formula (1) or (2) is preferably 30 mol% to 95 mol%, or 50 mol% to 90 mol%, relative to all repeating units. The content of the repeating unit represented by the general formula (3a) and (3b) is preferably 5 mol% to 70 mol%, or 10 mol% to 50 mol%.

[0292] Furthermore, the surface modifier (B) mentioned above preferably has a repeating unit represented by the following general formula (B-1).

[0293] [Chemistry 33]

[0294]

[0295] In the formula, R 1 ' is a hydrogen atom or a methyl group, R 5 is a single bond or a divalent linking group having 2 to 10 carbon atoms and containing an ester group, R 6 It is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms.

[0296] In the above general formula (B-1), R 5 R is a single bond or a divalent linking group having 2 to 10 carbon atoms and containing an ester group. 5 Specifically, for example, a single bond, -CO 2 CH 2 -、-CO 2 CH 2 CH 2 -、-CO 2 CH 2 CH 2 CH 2 -、-CO 2 CH(CH 3 )-、-CO 2 CH 2 CH 2 CH 2 CH 2 -、-CO 2 CH 2 CH 2 CH 2 CH 2 CH 2 -、-CO 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH2 -、-CO 2 CH 2 CH 2 O-、-CO 2 CH 2 CH 2 OCH 2 CH 2 O-、-CO 2 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 O-, etc. Among them, especially -CO 2 CH 2 -、-CO 2 CH 2 CH 2 -、-CO 2 CH 2 CH 2 CH 2 -、-CO 2 CH 2 CH 2 CH 2 CH 2 -、-CO 2 CH 2 CH 2 CH 2 CH 2 CH 2 - is better.

[0297] In the repeating unit represented by the above general formula (B-1), R 6 Specifically, the following structures are provided, but the present invention is not limited thereto. Chain lines represent atomic bonds.

[0298] [Chemistry 34]

[0299]

[0300] [Chemistry 35]

[0301]

[0302] [Chemistry 36]

[0303]

[0304] When a metal-containing film is formed from a metal-containing film-forming composition containing a polymer compound containing a repeating unit represented by the general formula (B-1), the tertiary alkyl group R 6The decomposition reaction of the ions proceeds and carboxylic acid is generated. Due to the polarity of the carboxylic acid, the adhesion with the resist pattern can be improved, the rectangularity of the pattern can be improved, or the residue of the spacing part of the pattern can be prevented.

[0305] In addition, the carboxylic acid produced may sometimes initiate a ring-opening addition reaction with the repeating units represented by the above general formulae (1) and (2) to form a hydroxyester crosslinking structure. The following is a typical example of the reaction. In the following formula, R in the repeating unit (B-1) is 6 The state in which the carboxylic acid is separated is (B-2), and the state in which the hydroxyester crosslinking structure is formed by the ring-opening addition reaction with one example (1") of the general formula (1) and (2) is (B-3). The portion surrounded by the dotted line is the hydroxyester crosslinking structure formed by this reaction.

[0306] [Chemistry 37]

[0307]

[0308] In the formula, R 1 , R 5 , R 6 , R 1’ Same as above.

[0309] The formation of the hydroxyester crosslinking structure is a crosslinking reaction, which promotes the hardening of the adhesive film. Due to sufficient hardening, a dense film is formed, which prevents the cross-mixing of the adhesive film and the resist upper film, thereby preventing the residue of the spacing part of the pattern and obtaining a highly rectangular pattern.

[0310] Furthermore, the hydroxyester crosslinking structure is a polar group and interacts with the resist pattern, so the presence of the repeating unit (B-1) also contributes to preventing the collapse of the resist pattern.

[0311] The polymer compound (B) may contain only one type of the repeating unit represented by the general formula (B-1), or may contain two or more types.

[0312] When the above-mentioned (B) polymer compound contains the repeating unit represented by the above formula (B-1), the content of the repeating unit represented by the formula (B-1) relative to all the repeating units of the above-mentioned (B) polymer compound is preferably from 1 mol % to 30 mol %, and more preferably from 5 mol % to 15 mol %.

[0313] Furthermore, in the present invention, the (B) polymer compound does not contain a hydroxyl group-containing structural unit.

[0314] When the polymer compound contains a hydroxyl group, there is a risk of damaging the stability of the metal compound, which is less desirable.

[0315] The (B) polymer compound preferably has a weight average molecular weight of 6,000 to 50,000, and preferably has a dispersion degree represented by weight average molecular weight / number average molecular weight of 3.0 or less.

[0316] Furthermore, the "weight average molecular weight" referred to herein is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and polystyrene as a standard substance. By setting the weight average molecular weight and dispersity of the polymer compound used as the surface modifier (B) contained in the metal-containing film-forming composition to such a range, excellent film-forming properties can be obtained during spin coating, and the generation of sublimates during heat curing is suppressed, so that device contamination can be prevented. In particular, when forming a metal-containing film as an intermediate film of an anti-etching agent, if the composition contains a low-molecular-weight and volatile component, the film thickness distribution within the surface of the processed substrate is prone to variation. However, by setting the molecular weight and dispersity of the polymer compound used as described above and managing the amount of low-molecular-weight components in the composition, the film thickness distribution within the surface of the processed substrate can be suppressed to be small. Therefore, the weight average molecular weight of the polymer compound contained in the surface modifier (B) used in the metal-containing film-forming composition of the present invention is preferably 6,000 to 50,000, and particularly preferably 8,000 to 40,000, and the dispersion degree is preferably 3.0 or less.

[0317] The content of the (B) surface modifier in the metal-containing film-forming composition is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, based on 100 parts by mass of the (A) metal compound.

[0318] With such a content, it is possible to achieve both the etching selectivity of the (A) metal compound and the pattern adhesion of the (B) surface modifier at a higher level.

[0319] The method for synthesizing the polymer compound for the surface modifier (B) is, for example, a method of mixing monomers having polymerizable unsaturated bonds corresponding to the respective repeating units, adding a free radical polymerization initiator to a solvent, and heating and polymerizing. The polymerization conditions can be selected in various ways depending on the monomers used, the target molecular weight, etc., and are not particularly limited. Specifically, the solvent used in the polymerization is, for example, toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, 2-butanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, cyclohexanone, γ-butyrolactone, ethyl acetate, butyl acetate, diacetone alcohol, etc. The free radical polymerization initiator is, for example, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-methylpropionic acid) dimethyl ester, benzoyl peroxide, lauroyl peroxide, etc. Moreover, thiols such as octanethiol and 2-mercaptoethanol may be added as chain transfer agents during the polymerization. The polymerization reaction is preferably carried out by heating to 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.

[0320] For example, by using compounds having polymerizable double bonds represented by the following general formulae (1'), (2'), and (B-1') as monomers and carrying out polymerization as described above, a polymer compound containing repeating units represented by the above general formulae (1), (2), and (B-1) can be synthesized.

[0321] [Chemistry 38]

[0322]

[0323] In the formula, R 1 ~R 3 , R 5 ~R 6 , R 1 'Same as above.

[0324] During polymerization, all raw materials may be mixed and then heated, or the remaining raw materials may be added individually or mixed in a portion of the preheated raw materials and added all at once or slowly. For example, a polymerization method in which only the polymerization solvent is heated first and the monomer solution and the polymerization initiator solution are added thereto one by one can obtain a relatively homogeneous polymer compound and can prevent abnormal reactions such as runaway reactions, which is particularly ideal.

[0325] The polymer compound solution obtained above can be directly blended into the metal-containing film-forming composition, and can also be refined by conventional methods such as crystallization, liquid separation, filtration, and concentration as needed, and residual monomers, residual solvents, reaction by-products, and other impurities can be removed. When refining the polymer compound, a crystallization method in which a poor solvent such as water, aqueous alcohol, or saturated hydrocarbon is added to the polymer compound solution and the resulting precipitate is filtered out, or a liquid separation method in which the poor solvent layer is separated and removed is appropriate, among which the liquid separation method is particularly good. If the liquid separation method is used to purify the polymer compound, the low molecular weight components in the polymer compound solution can be removed with good efficiency. Therefore, when the metal-containing film-forming composition containing the polymer compound is formed into a metal-containing film, the generation of sublimates is reduced, and as a result, the contamination of the film-forming device can be prevented.

[0326] <(C) Solvent>

[0327] The (C) solvent that can be used in the metal-containing film-forming composition of the present invention is not particularly limited as long as it can dissolve the above-mentioned (A) metal compound and (B) surface modifier, and the (D) thermal acid generator, (E) photoacid generator, (F) cross-linking agent, (G) surfactant, and other additives that are optionally contained therein.

[0328] Specifically, for example, the organic solvents listed in paragraphs

[0091] to

[0092] of Japanese Patent Application Laid-Open No. 2007-199653 may be added. More specifically, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, cyclopentanone, cyclohexanone and γ-butyrolactone, or a mixture containing one or more of these is preferred.

[0329] The amount of the organic solvent to be added is preferably in the range of 200 to 10,000 parts, more preferably 250 to 5,000 parts, based on 100 parts by mass of the (A) metal compound.

[0330] <(C-1) High Boiling Point Solvent>

[0331] In the metal-containing film-forming composition of the present invention, the solvent (C) may contain a high-boiling-point organic solvent (C-1).

[0332] (C-1) The high boiling point organic solvent may be one or more organic solvents having a boiling point of 180 degrees (° C.) or higher.

[0333] For example, the solvent (C) may be a mixture of one or more organic solvents having a boiling point of less than 180° C. and one or more organic solvents having a boiling point of 180° C. or higher ((C-1) high boiling point solvent).

[0334] (C-1) The high boiling point solvent may be any solvent capable of dissolving the components of the metal-containing film-forming composition of the present invention, and may be any hydrocarbon, alcohol, ketone, ester, ether, chlorine-based solvent, etc., without particular limitation. Specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2- Ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, nonyl acetate, monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol Glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol Alcohol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc., which can be used alone or in combination.

[0335] (C-1) A high boiling point solvent, which is appropriately selected from the above-mentioned solvents in accordance with the temperature at which the metal-containing film-forming composition of the present invention is subjected to heat treatment, etc. The boiling point of the high boiling point solvent is preferably 180°C to 300°C, and 200°C to 300°C is more ideal. If the boiling point is such, there is no risk of volatilization becoming too fast during baking (heat treatment), so sufficient thermal fluidity can be obtained during film formation. It is believed that when the resist lower layer film is formed, an island structure may not be formed, and (A) the etching selectivity of the metal compound and B) the pattern adhesion of the surface modifier can be taken into account to a higher degree. In addition, if the boiling point is such, there will be no situation where the solvent does not volatilize after baking and remains in the film, and there is no risk of adverse effects on the film properties such as etching resistance.

[0336] When the high boiling point solvent (C-1) is used, the blending amount is preferably 1 to 30 parts by mass relative to 100 parts by mass of the organic solvent having a boiling point of less than 180° C. Such a blending amount is desirable because it can provide sufficient thermal fluidity during baking and will not remain in the film, thereby not causing deterioration of film properties such as etching resistance.

[0337] <Other ingredients>

[0338] When the metal-containing film-forming composition is a metal-containing film-forming composition that can be used as a resist underlayer film used in a multilayer resist method, it may contain one or more of the above-mentioned (A) metal compound, (B) surface modifier and (C) solvent, and may also contain at least one of (D) thermal acid generator, (E) photoacid generator, (F) cross-linking agent, and (G) surfactant as needed.

[0339] Components that may be contained in the resist underlayer film forming composition of the present invention other than the above-mentioned (A) metal compound, (B) surface modifier, and (C) organic solvent will be described below.

[0340] [(D) Thermal acid generator]

[0341] In order to promote the heat-induced crosslinking reaction, it is preferred to add (D) a thermal acid generator to the metal-containing film-forming composition of the present invention.

[0342] The thermal acid generator (D) that can be used in the metal-containing film-forming composition of the present invention is, for example, represented by the following general formula (7).

[0343] [Chemistry 39]

[0344]

[0345] Where, X A - Represents a non-nucleophilic counter ion. 70 , R 71 , R 72 , and R 73 Each of them represents a hydrogen atom, or a linear, branched, or cyclic alkyl, alkenyl, oxoalkyl, or oxoalkenyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group, and some or all of the hydrogen atoms in these groups may be substituted by an alkoxy group or the like. 70 and R 71 , or R 70 , R 71 and R 72 It can also form a ring. When it forms a ring, R 70 and R 71 , or R 70 , R 71and R 72 It represents an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring having a nitrogen atom in the ring.

[0346] Above, R 70 , R 71 , R 72 , and R 73 The alkyl groups may be the same as or different from each other. Specifically, the alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl and adamantyl.

[0347] Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl.

[0348] Oxoalkyl, for example, 2-oxocyclopentyl, 2-oxocyclohexyl, 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, 2-(4-methylcyclohexyl)-2-oxoethyl and the like.

[0349] Oxoalkenyl, for example, 2-oxo-4-cyclohexenyl, 2-oxo-4-propenyl, and the like.

[0350] Aryl groups include phenyl, naphthyl, alkoxyphenyl such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, m-tert-butoxyphenyl, alkylphenyl such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, alkylnaphthyl such as methylnaphthyl and ethylnaphthyl, alkoxynaphthyl such as methoxynaphthyl and ethoxynaphthyl, dialkylnaphthyl such as dimethylnaphthyl and diethylnaphthyl, and dialkoxynaphthyl such as dimethoxynaphthyl and diethoxynaphthyl.

[0351] Examples of the aralkyl group include benzyl, phenylethyl, and phenethyl.

[0352] Aryloxoalkyl groups include, for example, 2-aryl-2-oxoethyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl and 2-(2-naphthyl)-2-oxoethyl.

[0353] Again, R 70 and R 71 , or R 70 , R 71 and R 72When a heteroaromatic ring having a nitrogen atom in the formula is formed in the ring, for example, imidazole derivatives (for example, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazol derivatives, pyrroline derivatives (for example, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (for example, pyrrolidine, N-methylpyrrolidine, pyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolinidine derivatives, pyridine derivatives (for example, 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-pyridine

[0063] The invention also includes but is not limited to oxadiazole derivatives, anthracene derivatives, pyrrolidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolinidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoleline derivatives, quinoline derivatives (e.g., quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, urea derivatives, etc.

[0354] Above, X A - The non-nucleophilic counter ion may be a halide ion such as chloride ion and bromide ion, a fluoroalkyl sulfonate such as trifluoromethanesulfonate, 1,1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate, an aryl sulfonate such as toluenesulfonate, benzenesulfonate, 4-fluorobenzenesulfonate and 1,2,3,4,5-pentafluorobenzenesulfonate, an alkyl sulfonate such as methanesulfonate and butanesulfonate, an imide acid such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide and bis(perfluorobutylsulfonyl)imide, a methylated acid such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide, and further examples thereof include a sulfonate substituted with fluorine at the α-position as represented by the following general formula (8), and a sulfonate substituted with fluorine at the α- and β-positions as represented by the following general formula (9).

[0355] [Chemistry 40]

[0356]

[0357] In the above general formula (8), R 81is 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. 91 It 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.

[0358] The thermal acid generator may be specifically listed below, but is not limited to these.

[0359] [Chemistry 41]

[0360]

[0361] The (D) thermal acid generator contained in the metal-containing film-forming composition of the present invention can be used alone or in combination of two or more. The amount of the thermal acid generator added is preferably 0.05 to 30 parts, more preferably 0.1 to 10 parts, relative to 100 parts of the above-mentioned (B) surface modifier. If it is 0.05 parts or more, the acid generation amount and cross-linking reaction are sufficient, and if it is 30 parts or less, there is little risk of mixing due to acid migration to the upper layer resist.

[0362] [(E) Photoacid generator]

[0363] In the metal-containing film-forming composition of the present invention, in order to appropriately adjust the pattern shape, exposure sensitivity, etc. of the resist upper film, (E) a photoacid generator may be added. One type of photoacid generator may be used alone or two or more types may be used in combination. As the photoacid generator, for example, the photoacid generators in paragraphs

[0160] to

[0179] of Japanese Patent Gazette No. 2009-126940 may be used. The amount of the photoacid generator added is preferably 0.05 to 30 parts, more preferably 0.1 to 10 parts, relative to 100 parts of the above-mentioned (B) surface modifier. If the amount of the photoacid generator added is within the above range, the resolution is good, and there is no risk of foreign matter after the resist is developed or peeled off.

[0364] [(F) Cross-linking agent]

[0365] In addition, in the metal-containing film-forming composition of the present invention, in order to improve the curability and further suppress the cross-mixing with the upper film of the resist, a (F) cross-linking agent may also be added. There is no particular limitation on the cross-linking agent, and various well-known systems of cross-linking agents can be widely used. For example, melamine-based cross-linking agents, glycoluril-based cross-linking agents, benzoguanamine-based cross-linking agents, urea-based cross-linking agents, β-hydroxyalkylamide-based cross-linking agents, isocyanurate-based cross-linking agents, aziridine-based cross-linking agents, oxazoline-based cross-linking agents, epoxy-based cross-linking agents, and phenol-based cross-linking agents. The above-mentioned (F) cross-linking agent can be used alone or in combination of two or more. The amount added when the cross-linking agent is added is preferably 5 to 50 parts, and more preferably 10 to 40 parts, relative to 100 parts of the above-mentioned (B) surface modifier. If the added amount is 5 parts or more, sufficient curability will be exhibited and cross-mixing with the upper film of the resist can be suppressed. On the other hand, when the added amount is 50 parts or less, there is no concern that the adhesion will be deteriorated due to a decrease in the ratio of the (B) surface modifier in the composition, and that the dry etching resistance will be deteriorated due to a decrease in the ratio of the (A) metal compound.

[0366] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy and / or hydroxyl-substituted melamines thereof, and partially self-condensed products thereof.

[0367] Specific examples of the glycoluril-based crosslinking agent include tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensation products thereof.

[0368] Specific examples of the benzoguanamine-based crosslinking agent include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensation products thereof.

[0369] Specific examples of the urea crosslinking agent include dimethoxymethylated dimethoxyethylene urea, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensates thereof.

[0370] Specific examples of the β-hydroxyalkylamide crosslinking agent include N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide.

[0371] Specific examples of the isocyanurate crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate.

[0372] Specific examples of the aziridine crosslinking agent include 4,4′-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0373] Oxazoline crosslinking agents include, for example, 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tert-butyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymers.

[0374] Specific examples of the epoxy crosslinking agent include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0375] The phenol-based crosslinking agent is specifically, for example, a compound represented by the following general formula (10).

[0376] [Chemistry 42]

[0377]

[0378] In the formula, Q is a single bond or a q having 1 to 20 carbon atoms. 1 Valence hydrocarbon group. 16 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 1 It is an integer from 1 to 5.

[0379] Q is a single bond, or a carbon number of 1 to 20 1 Hydroxyl. 1 is an integer of 1 to 5. More preferably, it is 2 or 3. Specifically, Q includes, for example, methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R 16 It is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specifically, the alkyl group having 1 to 20 carbon atoms includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosyl, and is preferably a hydrogen atom or a methyl group.

[0380] Examples of the compound represented by the general formula (10) include the following compounds. Among them, from the viewpoint of improving the curability and film thickness uniformity of the adhesive film, hexamethoxymethylated products of trisphenolmethane, trisphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred.

[0381] [Chemistry 43]

[0382]

[0383] [Chemistry 44]

[0384]

[0385] The above-mentioned (F) cross-linking agent can be used alone or in combination of two or more. The amount of the added (F) cross-linking agent is preferably 10% to 50% by mass, and more preferably 15% to 30% by mass, relative to 100 parts of the above-mentioned (B) surface modifier. If the added amount is more than 10% by mass, it has sufficient hardening properties and can suppress cross-mixing with the upper film of the resist. On the other hand, if the added amount is less than 50% by mass, there is no risk of deterioration of adhesion due to a decrease in the ratio of the (B) surface modifier in the metal-containing film-forming composition and deterioration of dry etching resistance due to a decrease in the ratio of the (A) metal compound.

[0386] [(G) Surfactant]

[0387] In the metal-containing film-forming composition of the present invention, in order to improve the coating property of spin coating, a (G) surfactant may be added. The surfactant may be used alone or in combination of two or more. The surfactant, for example, is the surfactant in paragraphs

[0142] to

[0147] in Japanese Patent Gazette No. 2009-269953. The amount of the surfactant added is preferably 0.001 to 20 parts, more preferably 0.01 to 10 parts, relative to 100 parts of the above-mentioned (A) metal compound. If it is within such a range, the coating property will be indeed improved, and a thin and uniform close-fitting film can be formed.

[0388] [Plasticizer]

[0389] In addition, a plasticizer may be added to the metal-containing film-forming composition of the present invention. There is no particular limitation on the plasticizer, and plasticizers of various known systems can be widely used. For example, low molecular weight compounds such as phthalates, adipic acid esters, phosphates, trimellitic acid esters, and citrates, polyethers, polyesters, and polymers such as polyacetal polymers of Japanese Patent Publication No. 2013-253227. The amount of the added plasticizer is preferably 1% to 500% by mass relative to 100 parts of the above-mentioned (A) metal compound. If the amount added is within such a range, the pattern is excellent in embedding and averaging.

[0390] <Method for Forming Metal-Containing Film>

[0391] The present invention uses the metal-containing film-forming composition to form a metal-containing film as, for example, a resist underlayer film of a multilayer resist film used in photolithography.

[0392] The method for forming a resist lower film using the metal-containing film-forming composition of the present invention comprises applying the metal-containing film-forming composition on a substrate to be processed by spin coating or the like. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to prevent mixing with the resist upper film and to promote a cross-linking reaction. The baking is preferably performed under conditions in the range of 100°C to 450°C for 10 to 600 seconds, and more preferably under conditions in the range of 200°C to 300°C for 10 to 300 seconds. Considering the effects of device damage and wafer deformation, the upper limit of the heating temperature for photolithography in wafer processing is preferably set to be below 450°C, and more preferably below 300°C.

[0393] Furthermore, the method for forming an anti-etching underlayer film using the metal-containing film-forming composition of the present invention can also be carried out by coating the metal-containing film-forming composition of the present invention on a processed substrate by a spin coating method or the like in the same manner as described above, and firing the above-mentioned metal-containing film-forming composition in a gas environment with an oxygen concentration of not less than 0.1 volume % and not more than 21 volume % to harden it, thereby forming a metal-containing film.

[0394] The metal-containing film-forming composition of the present invention can be fired in such an oxygen atmosphere to obtain a sufficiently hardened film. The gas atmosphere during baking may be air, but in order to reduce oxygen, N 2 Inert gases such as Ar, He, etc. are ideal for preventing oxidation of the metal-containing film. In order to prevent oxidation, the oxygen concentration must be controlled, preferably below 1000ppm, more preferably below 100ppm (volume basis). If the metal-containing film is prevented from oxidizing during baking, there will be no increase in absorption or reduction in etching resistance, so it is ideal.

[0395] Alternatively, the metal-containing film-forming composition may be used to form a metal-containing film as an intermediate film of a multilayer resist film used in photolithography, for example.

[0396] <Pattern Formation Method Using Resist Underlayer Film Forming Composition>

[0397] The present invention also provides a pattern forming method, as a pattern forming method using the metal-containing film-forming composition of the present invention and using a two-layer resist process, which is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0398] (I-1) After applying the metal-containing film-forming composition of the present invention on a substrate to be processed, a metal-containing film is formed by heat treatment,

[0399] (I-2) forming a resist upper layer film on the aforementioned metal-containing film using a photoresist material,

[0400] (I-3) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0401] (I-4) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching, and

[0402] (I-5) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0403] The resist upper film in the above two-layer resist treatment is resistant to etching by chlorine-based gas, so in the above two-layer resist treatment, the dry etching of the metal-containing film using the resist upper film as a mask is preferably performed using an etching gas mainly containing chlorine-based gas. The metal-containing film is resistant to etching by fluorine-based gas, so the dry etching of the processed substrate using the metal-containing film as a mask is preferably performed using an etching gas mainly containing fluorine-based gas.

[0404] The present invention also provides a pattern forming method, which is a pattern forming method using the metal-containing film-forming composition of the present invention and is formed by three-layer resist processing, and is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0405] (II-1) forming a resist underlayer film on a substrate to be processed,

[0406] (II-2) After applying the metal-containing film-forming composition of the present invention on the resist underlayer film, a metal-containing film is formed by heat treatment,

[0407] (II-3) forming a resist upper layer film on the aforementioned metal-containing film using a photoresist material,

[0408] (II-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0409] (II-5) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching,

[0410] (II-6) using the metal-containing film to which the pattern has been transferred as a mask, transferring the pattern to the resist underlayer film by dry etching,

[0411] (II-7) The substrate to be processed is processed using the patterned resist underlayer film as a mask to form a pattern on the substrate to be processed.

[0412] The metal-containing film formed from the metal-containing film-forming composition of the present invention used as the intermediate film in the above three-layer resist treatment exhibits resistance to etching by oxygen-based gases, so in the above three-layer resist treatment, dry etching of the organic resist lower film using the metal-containing film as a mask is preferably performed using an etching gas mainly containing oxygen-based gases. The organic lower film exhibits resistance to etching by fluorine-based gases, so dry etching of the substrate to be processed using the organic lower film as a mask is preferably performed using an etching gas mainly containing fluorine-based gases.

[0413] In the above pattern forming method, the resist upper layer film can be either positive or negative, and can use the same photoresist composition as commonly used. When the resist upper layer film is formed using the above photoresist composition, spin coating is preferred.

[0414] When the photoresist composition is used to form the resist upper film by spin coating, the resist is pre-baked after coating, preferably at 60 to 180°C and 10 to 300 seconds. After that, exposure is performed according to the usual method, and post-exposure baking (PEB) and development are performed to obtain a resist pattern. In addition, the thickness of the resist upper film is not particularly limited, and 10 to 500 nm, especially 20 to 400 nm is preferred.

[0415] The exposure light may be, for example, high energy radiation having a wavelength of 300 nm or less, specifically, deep ultraviolet light, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 Laser (157nm), Kr 2 Laser (146nm), Ar 2 Laser (126nm), 3~20nm soft X-ray (EUV), electron beam (EB), ion beam, X-ray, etc.

[0416] The patterning method of the resist upper layer film is preferably to form the pattern by optical lithography with a wavelength of 5 nm to 300 nm, direct writing using an electron beam, nanoimprinting, or a combination thereof.

[0417] In addition, the development method of the above-mentioned pattern forming method is preferably alkali development or organic solvent development.

[0418] Then, the obtained resist pattern is used as a mask to perform etching. For example, the etching of the metal-containing film in the two-layer resist process is performed by using a chlorine-based gas to use the upper resist pattern as a mask. In this way, a metal-containing film pattern is formed. Next, the obtained metal-containing film pattern is used as a mask to perform etching of the substrate to be processed. The etching of the processed object can be performed using conventional methods. For example, if the processed object is SiO 2 For SiN and silicon dioxide-based low dielectric constant insulating films, etching is performed mainly using fluorine-based gases.

[0419] The metal-containing film obtained from the metal-containing film-forming composition of the present invention has a characteristic of being excellent in etching resistance when etching these workpieces.

[0420] The organic resist underlayer film material that can be used for the resist underlayer film is, for example, a well-known organic resist underlayer film material for the three-layer resist method or the two-layer resist method using a silicon resist composition. For example, Japanese Patent Publication No. 2012-1687, Japanese Patent Publication No. 2012-77295, Japanese Patent Publication No. 2004-264710, Japanese Patent Publication No. 2005-043471, Japanese Patent Publication No. 2005-250434, Japanese Patent Publication No. 2007-293294, Japanese Patent Publication No. 2008-65303, Japanese Patent Publication No. 2009-11 004-205685, Japanese Patent Application Laid-Open No. 2007-171895, Japanese Patent Application Laid-Open No. 2009-14816, Japanese Patent Application Laid-Open No. 2007-199653, Japanese Patent Application Laid-Open No. 2008-274250, Japanese Patent Application Laid-Open No. 2010-122656, Japanese Patent Application Laid-Open No. 2012-214720, Japanese Patent Application Laid-Open No. 2014-2 9435, International Publication No. WO2012 / 077640, International Publication No. WO2010 / 147155, International Publication No. WO2012 / 077640, International Publication No. WO2010 / 147155, International Publication No. WO2012 / 176767, Japanese Patent Application Publication No. 2005-128509, Japanese Patent Application Publication No. 2 Resins and compositions disclosed in Japanese Patent Application No. 006-259249, Japanese Patent Application No. 2006-259482, Japanese Patent Application No. 2006-293298, Japanese Patent Application No. 2007-316282, Japanese Patent Application No. 2012-145897, Japanese Patent Application No. 2017-119671, and Japanese Patent Application No. 2019-44022.

[0421] The resist lower film can be formed on the substrate by spin coating, etc., similarly to the photoresist composition, using a composition solution containing the organic resist lower film material. After the organic resist lower film is formed by spin coating, etc., it is preferably baked to evaporate the organic solvent. The baking temperature is preferably within the range of 100 to 600° C. and the baking time is preferably within the range of 10 to 300 seconds.

[0422] Instead of using the above-mentioned organic resist underlayer film material, an organic hard mask formed by a CVD method or an ALD method may be used.

[0423] In the case of three-layer resist processing, dry etching of the metal-containing film is performed, for example, using a chlorine-based gas with the upper resist pattern as a mask. This forms a metal-containing film pattern. Next, the obtained metal-containing film pattern is used as a mask, and the resist lower film is etched using an oxygen-based gas. This forms a resist lower film pattern. Next, the obtained organic resist lower film pattern is used as a mask to perform etching processing on the processed substrate.

[0424] The metal-containing film obtained from the metal-containing film-forming composition of the present invention is characterized by excellent etching resistance when etching these resist underlayer films.

[0425] The object to be processed (substrate to be processed) is not particularly limited, and Si, α-Si, p-Si, SiO 2 , SiN, SiON, W, TiN, Al and other substrates, and a processed layer formed on the substrate. The processed layer can be Si, SiO 2 , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si and other Low-k films and their barrier films, usually can form a film thickness of 50 to 10,000nm, especially 100 to 5,000nm. In addition, when forming the processed layer, the substrate and the processed layer can be made of different materials.

[0426] Here, use Figure 1 The following is an example of a method for forming a pattern formed by the three-layer resist process. Figure 1 (A), on the processed layer 2 of the processed substrate 10 composed of the substrate 1 and the processed layer 2 thereon, a resist underlayer film 3 is formed using an organic resist underlayer film material, a metal-containing film 4 is formed on the resist underlayer film 3 using the metal-containing film-forming composition of the present invention, and a resist upperlayer film 5 is formed on the metal-containing film 4 using a photoresist material. Then, as Figure 1 (B), the exposed portion 6 of the resist upper film is subjected to pattern exposure. Figure 1 (C), developing with a developer to form a resist upper film pattern 5a on the resist upper film. Then, as Figure 1 (D), the resist upper layer film having formed the pattern 5a is used as a mask, and the pattern is transferred to the aforementioned metal-containing film 4 by dry etching to obtain the metal-containing film pattern 4a. Then, as Figure 1 (E), using the metal-containing film of the transferred pattern 4a as a mask, dry etching is used to transfer the pattern on the resist lower film to obtain the resist lower film pattern 3a. Then, as Figure 1(F) is to use the resist underlayer film having the pattern 3a formed thereon as a mask to process the processed layer 2 on the substrate 1 to form a pattern 2a on the processed substrate 10.

[0427] Again, use Figure 2 , an example of a method for forming a pattern formed by the above-mentioned two-layer resist process is described. In this example, first, as Figure 2 (G), a metal-containing film 4 is formed on the processed layer 2 of the processed substrate 10 composed of the substrate 1 and the processed layer 2 thereon using the metal-containing film-forming composition of the present invention, and a resist upper layer film 5 is formed on the metal-containing film 4 using a photoresist material. Then, as Figure 2 (H), the exposed portion 6 of the resist upper film is subjected to pattern exposure. Figure 2 (I) is developed with a developer to form a resist upper film pattern 5a on the resist upper film. Figure 2 (J), the resist upper layer film having formed the pattern 5a is used as a mask, and the pattern is transferred to the aforementioned metal-containing film 4 by dry etching to obtain the metal-containing film pattern 4a. Then, as Figure 2 (K), using the metal-containing film on which the pattern 4a has been formed as a mask, the processed layer 2 on the substrate 1 is processed to form a pattern 2a on the processed substrate 10.

[0428] [Example]

[0429] The present invention will be described in more detail below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto.

[0430] [(A) Synthesis Example of Metal Compound]

[0431] In the following synthesis examples, the following organic group raw material group G: (G1) to (G10) and silicon-containing organic group raw material group H: (H1) to (H2) were used.

[0432] The raw material group G: (G1) to (G10) and the raw material group H: (H1) to (H2) are as follows.

[0433] [Chemistry 45]

[0434]

[0435] [Chemistry 46]

[0436]

[0437] As the metal source M, the following metal compounds were used.

[0438] (M1): diisopropoxybis(2,4-pentanedionato)titanium(IV) (75 mass % concentration 2-propanol (IPA) solution)

[0439] (M2): Tetraisopropoxytitanium (Sigma-Aldrich Corp, 377996)

[0440] (M3): Zr(OBu) 4 : Tetrabutoxyzirconium (IV) (80 mass % 1-butanol solution) (Tokyo Chemical Industry Co., Ltd., Z0016)

[0441] (M4): Hf(OBu) 4 :Hafnium(IV)-butoxide (Sigma-Aldrich Corp, 667943)

[0442] (M5):Ti(OBu) 4 :Tetrabutyl orthotitanate (Tokyo Chemical Industry Co., Ltd., B0742)

[0443] (M6): Butoxytitanium tetramer (Fuji Film Wako Pure Chemical Industries, Ltd.)

[0444] [Synthesis Example A1] Synthesis of Metal Compound (A-1)

[0445] Under nitrogen atmosphere, 50.9 g of diisopropoxybis(2,4-pentanedionato)titanium(IV) (M1) (mass of metal compound: 38.2 g) was dissolved in 180.0 g of propylene glycol monoethyl ether (hereinafter referred to as PGEE), and 20.2 g of deionized water was added dropwise at room temperature for 10 minutes while stirring. Then, the mixture was reacted at 60°C for 2 hours and then cooled to room temperature. After adding 250 g of propylene glycol monoethyl ether, the mixture was concentrated under reduced pressure using a rotary evaporator to obtain a PGEE solution of the metal compound (A-1).

[0446] [Synthesis Example A2] Synthesis of Metal Compound (A-2)

[0447] Under nitrogen environment, 28.4 g of tetraisopropoxytitanium (M2) was dissolved in 50.0 g of 2-propanol, and a solution of 50.0 g of IPA in 2.7 g of deionized water was added dropwise at room temperature for 2 hours while stirring. 12.4 g of the organic group raw material group (G1) was added to the obtained solution, and stirred at room temperature for 30 minutes. After the solution was concentrated at 30°C under reduced pressure, it was heated to 60°C and continued to be heated under reduced pressure until the distillate no longer appeared. When the distillate was no longer visible, 120.0 g of PGMEA / PGME (weight ratio 70 / 30) solution was added, and heated at 40°C under reduced pressure until IPA no longer distilled, to obtain a PGMEA / PGME solution of the metal compound (A-2).

[0448] [Synthesis Examples A3 to A8] Synthesis of Metal Compounds (A-3) to (A-8)

[0449] Except for using the above-mentioned metal source M and the above-mentioned compound group G in the feed amounts shown in Table 1, the metal compounds (A-3) to (A-8) shown in Table 1 were obtained under the same reaction conditions as Synthesis Example A1.

[0450] [Table 1]

[0451]

[0452]

[0453] [Synthesis Example A9] Synthesis of Metal Compound (A-9)

[0454] Under nitrogen environment, 11.8g of tetrabutyl orthotitanate (M5) was dissolved in 20.6g of PGMEA / PGME (weight ratio 70 / 30) solution, and the reaction temperature was raised to 50°C while stirring, and 6.5g of compound H1 was added dropwise to the above solution. After the addition, the reaction temperature was set to 60°C and continued for 2 hours. Then, 6.4g of compound G3 suspended in 8.6g of PGMEA / PGME (weight ratio 70 / 30) solution was added to the above reaction system to obtain a mixture, and the reaction temperature was maintained at 60°C and continued to stir for 1 hour. After cooling to room temperature, the obtained reaction solution was filtered with a 0.45μm PTFE filter to obtain a PGMEA / PGME solution of the metal compound (A-9).

[0455] [Synthesis Examples A10 to A16] Synthesis of Metal Compounds (A-10) to (A-16)]

[0456] The metal source M, compound group G and compound group H were used in the feed amounts shown in Table 2, and the metal compounds (A-10) to (A-16) shown in Table 2 were obtained under the same reaction conditions as in Synthesis Example A9.

[0457] [Table 2]

[0458]

[0459] [(B) Synthesis of surface modifier]

[0460] (B) Synthesis of polymer compounds (B-1) to (B-14) of the surface modifier and polymer compounds (B-15) to (B-16) for comparison. These polymer compounds were prepared using the following monomers (J1) to (J13).

[0461] [Chemistry 47]

[0462]

[0463] [Synthesis Example B1] Synthesis of polymer compound (B-1)

[0464] In a 500 ml flask, 100 g of monomer 1 (raw material J1) and 290.0 g of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were weighed and degassed while stirring to prepare a monomer solution. In another 500 ml flask, 2.9 g of 2,2-azobis(2-methylpropionic acid) dimethyl ester (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) and 50.0 g of PGMEA were weighed and degassed while stirring to prepare a polymerization initiator solution. In a 1 L flask under a nitrogen atmosphere, 60 g of PGMEA was weighed, and after degassed while stirring, the internal temperature was heated until it reached 80°C. The above-mentioned monomer solution and polymerization initiator solution were added simultaneously and separately over 4 hours. After heating and stirring for 16 hours after the addition, the mixture was cooled to room temperature. The obtained polymerization solution was added dropwise to 1,500 g of hexane that had been stirred, and the precipitated polymer was filtered. The obtained polymer was washed twice with 600 g of hexane and then vacuum dried at 50° C. for 20 hours to obtain a polymer compound (B-1) in the form of a white powder. The GPC analysis showed that the weight average molecular weight (Mw) of the polymer compound (B-1) was 10,000 and the degree of dispersion (Mw / Mn) was 2.0.

[0465] [Synthesis Examples B2 to B14 and Comparative Synthesis Examples B15 to B16] Synthesis of Polymer Compounds (B-2) to (B-16)

[0466] Except that monomer 1, or monomer 1 and monomer 2, or monomer 1, monomer 2 and monomer 3 were used in the feed amounts shown in Table 3, polymer compounds (B-2) to (B-16) shown in Table 3 were obtained under the same reaction conditions as in Synthesis Example B1. Table 3 below also shows the weight average molecular weight (Mw) and dispersity (Mw / Mn) of each polymer compound.

[0467] [Table 3]

[0468]

[0469] [Preparation of Metal-Containing Film-Forming Compositions (MUL1 to 16, Comparative MUL1 to 5)]

[0470] The preparation of the metal-containing film-forming composition used any of the above-mentioned metal compounds (A-1) to (A-16), any of the polymer compounds (B-1) to (B-16) as a surface modifier, the following compounds (AG1) to (AG3) as a thermal acid generator, the following compound (AG4) or (AG5) as a photoacid generator, the following compound (XL1) or (XL2) as a crosslinking agent, and a solvent (C1: ethylene glycol dibenzyl ether: boiling point 364°C) as a high boiling point solvent. After dissolving them in an organic solvent containing 0.001% by mass of PF636 (manufactured by OMNOVA) in the proportions shown in Table 4, the mixture was filtered with a 0.1 μm fluororesin filter to prepare metal-containing film-forming compositions (MUL1 to 16, comparison MUL1 to 5). The organic solvent was a mixed solvent of PGMEA and PGEE as shown in Table 4.

[0471] [Chemistry 48]

[0472]

[0473] [Table 4]

[0474]

[0475]

[0476] [Evaluation of solvent resistance and contact angle]

[0477] In Examples 1-1 to 1-16 and Comparative Examples 1-1 to 1-4, the metal-containing film-forming compositions prepared above (MUL-1 to 16, Comparative Examples MUL-1 to 4) were respectively coated on silicon substrates, and after the coatings were fired at 250°C for 60 seconds, the film thickness of the coatings from the center to the periphery of the substrate was measured, and the average film thickness (a [nm]) was calculated. Then, PGMEA solvent was dispensed on the coatings, left for 30 seconds, then spin-dried, and then baked at 100°C for 60 seconds to evaporate PGMEA, and the film thickness (b [nm]) of the coatings was measured. The difference in film thickness before and after PGMEA treatment was calculated (residual film rate: (b / a) × 100). The results are shown in Table 5 below.

[0478] In addition, the contact angle (CA1) with pure water was measured for the film fired at 250° C. for 60 seconds. The results are shown in Table 5 below.

[0479] In Comparative Example 1-5 using a metal-containing film-forming composition (Comparative Example MUL-5), precipitates occurred after the sample preparation, so the evaluation was discontinued. In the metal-containing film-forming composition (Comparative Example MUL-5), the polymer compound (B-16) used as the surface modifier (B) contained a hydroxyl-containing structural unit, so it was presumed that the precipitate was generated by reaction with the metal compound.

[0480] [Table 5]

[0481]

[0482]

[0483] As shown in Table 5, the metal-containing film materials (MUL-1 to 16) of the present invention have good film-forming properties and almost no film reduction due to solvent treatment, which shows that a film with good solvent resistance can be obtained. In addition, by using a surface modifier, a film having a contact angle of more than 60° to pure water can be formed, and good adhesion to the resist pattern can be expected. In particular, Examples 1-5 to 1-16 using a metal compound containing a cross-linking group represented by any of the above-mentioned general formulas (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3) have high contact angles. Among them, Examples 1-5 to 1-8 using hydrolysis condensates of metal compounds (metal compounds A-5 to A-8), Examples 1-10 to 1-14 using a polymer compound containing a structural unit containing F atoms as a surface modifier, and Example 1-16 using a high boiling point solvent as an additive have high contact angles.

[0484] [Evaluation of etching resistance]

[0485] In Examples 2-1 to 2-16 and Comparative Examples 2-1 to 2-4, the metal-containing film-forming composition (MUL-1 to 16, and Comparative Examples MUL-1 to 4) is respectively coated on a silicon substrate, and the coating is heated at 250°C for 60 seconds using a hot plate to form a metal-containing film (film thickness a) with a thickness of 50 nm.

[0486] In Comparative Example 2-5, the following resist interlayer film material (SOG-1) containing silicon atoms was applied, and the coated film was baked at 220° C. for 60 seconds to form a resist interlayer film with a film thickness of 50 nm.

[0487] An ArF silicon-containing intermediate film polymer (SiP1) and a thermal crosslinking catalyst (CAT1) as an anti-etching intermediate film material (SOG-1) containing silicon atoms are dissolved in a solvent (a mixed solvent of the following solvent 1 and solvent 2) containing 0.1% by mass of FC-4430 (produced by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 6, and filtered with a fluororesin filter with a pore size of 0.1 μm to prepare an anti-etching intermediate film material (SOG-1) containing silicon atoms.

[0488] [Table 6]

[0489]

[0490] The structural formulas of the ArF silicon-containing intermediate film polymer (SiP1) and the thermal crosslinking catalyst (CAT1) used are shown below.

[0491] [Chemistry 49]

[0492]

[0493] Next, using ULVAC's CE-300I etching equipment, the following conditions were used to perform the etching using CF 4 Gas and O 2 The film thickness b was measured by etching with each gas. The film thickness etched in one minute was calculated from the film thickness (film thickness b-film thickness a) etched during the specified time using each gas, and the etching rate (nm / min) was defined. The results are shown in Table 7.

[0494] CF 4 Gas Dry Etching Conditions

[0495] Pressure: 1Pa

[0496] Antenna RF power: 100W

[0497] Bias RF power: 15W

[0498] CF 4 Gas flow rate: 15sccm

[0499] Time: 30 seconds

[0500] Take O 2 Gas Dry Etching Conditions

[0501] Pressure: 1Pa

[0502] Antenna RF power: 300W

[0503] Bias RF power: 10W

[0504] O 2 Gas flow rate: 25sccm

[0505] Time: 30 seconds

[0506] [Table 7]

[0507]

[0508] As shown in Table 7, it can be seen that the metal-containing film-forming compositions (MUL-1 to 16) of the present invention are all effective for CF 4 Gas and O 2 Gas exhibits excellent etching resistance. 4 Since it has excellent gas etching resistance, it is ideal for double-layer resist processing in which a resist pattern is transferred to a substrate to be processed by combining it with a photoresist upper layer film.

[0509] Furthermore, the metal-containing film compositions (MUL-1 to 16) of the present invention are compared with SOG-1 used in Comparative Examples 2-5. 2 Since it has excellent resistance to gas etching, it can be said to be suitable for three-layer resist processing in which a resist pattern is transferred to a substrate to be processed in combination with an organic resist underlayer film.

[0510] [Pattern Formation Method]

[0511] In Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-4, as for the organic lower layer film on the substrate, ODL-306 manufactured by Shin-Etsu Chemical Co., Ltd. was used to spin-coat on a Si wafer and the coating was baked at 350°C for 60 seconds to form a carbon film with a thickness of 45 nm. The carbon ratio of the carbon film is 88%. A composition prepared by diluting the metal-containing film-forming composition (MDL-3, 8, 12 and Comparative Examples MDL-2 to 4) with an organic solvent (PGMEA / PGME=700 / 300 parts by mass) was applied thereon, and heated at 250°C for 60 seconds using a hot plate to form a resist intermediate film with a thickness of 10 nm. An ArF single-layer resist of the resist upper layer film material was applied thereon, and the coating was baked at 105°C for 60 seconds to form a photoresist film with a thickness of 100 nm. A wet protective film material (TC-1) was applied on the photoresist film, and the coated film was baked at 90° C. for 60 seconds to form a protective film with a film thickness of 50 nm.

[0512] In Comparative Example 3-4, a composition prepared by diluting the silicon atom-containing resist intermediate film material (SOG-1) used in Comparative Example 2-5 with an organic solvent (PGEE / pure water = 5000 / 600 parts by mass) was applied, and the coating was baked at 220°C for 60 seconds to form a resist intermediate film with a film thickness of 10 nm.

[0513] The resist upper film material (single-layer resist for ArF) is prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) according to the proportions shown in Table 8 in a solvent containing 0.1% by mass of a surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), and filtering with a 0.1 μm fluororesin filter.

[0514] [Table 8]

[0515]

[0516] The polymer (RP1), the acid generator (PAG1), and the basic compound (Amine1) used for the resist upper layer film material (single-layer resist for ArF) are shown below.

[0517] [Chemistry 50]

[0518]

[0519] The wet protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent according to the ratio shown in Table 9 and filtering the solution through a 0.1 μm fluororesin filter.

[0520] [Table 9]

[0521]

[0522] The protective film polymer (PP1) used in the wet protective film material (TC-1) is shown below.

[0523] [Chemistry 51]

[0524]

[0525] Then, the film was exposed with an ArF immersion exposure device (manufactured by Nikon Co., Ltd.; NSR-S610C, NA1.30, σ0.98 / 0.78, 35 degree dipole s-polarized illumination, 6% half-step phase shift mask), baked (PEB) at 100°C for 60 seconds, and developed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 50nm1:1 positive line and space pattern (resist upper film pattern).

[0526] The reflectivity was calculated using PROLITH 2020a (LITHO TECH JAPAN). The thickness of the metal-containing film was fixed at 10 nm, and the reflectivity of the metal-containing film at a wavelength of 193 nm was calculated when the refractive index n was 1.80 to 2.30 and the attenuation coefficient k was 0.19 to 0.50. The results are as follows: Figure 3It is preferred that the reflectivity from the base substrate during pattern exposure can be reduced to a smaller optical constant (n / k).

[0527] The optical constants of the metal-containing film-forming composition are obtained by coating the metal-containing film-forming composition on a silicon substrate, firing the coated film at 250° C. for 60 seconds, and then using a variable incident angle spectroscopic ellipsometer (VASE) manufactured by JAWollam.

[0528] The LWR of the pattern was observed using CG5000 (Hitachi Advanced Technologies Co., Ltd.), and the cross section of the pattern was observed using S-4700 (electron microscope manufactured by Hitachi, Ltd.).

[0529] The results are shown in Table 10.

[0530] Next, the resist upper film pattern is used as a mask to etch the resist intermediate film to form a hard mask pattern by dry etching, the organic lower film is etched to form a pattern using the obtained hard mask pattern as a mask, and the SiO 2 The film was etched and the etching conditions were as follows.

[0531] (Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-3)

[0532] Transfer conditions of the hard mask pattern to the metal-containing film (resist intermediate film).

[0533] Cl 2 Gas Dry Etching Conditions

[0534] Pressure: 1Pa

[0535] Antenna RF power: 320W

[0536] Bias RF power: 30W

[0537] Cl 2 Gas flow rate: 25sccm

[0538] Time: 10 seconds

[0539] (Comparative Example 3-4)

[0540] Transfer conditions of the hard mask pattern to the SOG-1 film (resist intermediate film).

[0541] CF 4 Gas Dry Etching Conditions

[0542] Pressure: 1Pa

[0543] Antenna RF power: 100W

[0544] Bias RF power: 15W

[0545] CF 4 Gas flow rate: 15sccm

[0546] Time: 15 seconds

[0547] Transfer conditions of the resist interlayer film pattern to the organic underlayer film.

[0548] O 2 Gas Dry Etching Conditions

[0549] Pressure: 1Pa

[0550] Antenna RF power: 300W

[0551] Bias RF power: 10W

[0552] O 2 Gas flow rate: 25sccm

[0553] Time: 20 seconds

[0554] Resist underlayer pattern for SiO 2 Membrane transfer conditions.

[0555] CF 4 Gas Dry Etching Conditions

[0556] Pressure: 1Pa

[0557] Antenna RF power: 100W

[0558] Bias RF power: 15W

[0559] CF 4 Gas flow rate: 15sccm

[0560] Time: 60 seconds

[0561] [Table 10]

[0562]

[0563] As shown in Table 10, Examples 3-1 to 3-3 using the metal-containing film-forming composition (MUL-3, 8, 12) of the present invention confirmed that the pattern shapes after development were all good. It is speculated that the addition of the surface modifier improves the adhesion with the resist upper film pattern and the refractive index n at a wavelength of 193nm is high. Even a thin film with a film thickness of 10nm can still suppress the reflected light from the substrate to less than 1%, which is the main reason for obtaining a good resist pattern. If it is a metal-containing film-forming composition of the present invention, it is possible to improve the adhesion with the resist pattern without deteriorating the characteristics as a high refractive index material, which is particularly effective when a zirconium-containing metal-containing film-forming composition showing a high refractive index at a wavelength of 193nm is used as a resist lower film.

[0564] Furthermore, after the substrate is transferred and then etched, the resist upper layer film pattern is finally well transferred to the substrate, and it has been confirmed that it is suitable for use in microfabrication using a multilayer resist method.

[0565] In Comparative Examples 3-1 and 3-2 in which no surface modifier was used and Comparative Example 3-3 in which a polymer compound different from the present invention was used as a surface modifier, collapse of the resist upper film pattern was observed after development.

[0566] Comparative Example 3-4, in which SOG-1 was used as the resist intermediate film material, showed that the LWR after development was less than that of Examples 3-1 to 3-3 using the metal-containing film-forming composition (MUL-3, 8, 12) of the present invention, probably because the reflectivity during pattern exposure was high at 4.4%. In addition, in Comparative Example 3-4, it was confirmed that the pattern shape after substrate transfer etching was an undercut shape. It is presumed that the reason is that the resist lower layer film has insufficient resistance to oxygen used in dry etching processing.

[0567] From the above, it can be seen that the metal-containing film-forming composition and pattern forming method of the present invention have high adhesion with the pattern of the upper film of the resist and have the effect of suppressing the collapse of the fine pattern, and can give the pattern shape of the upper film of the resist with high rectangularity. Therefore, it is particularly suitable for multilayer resist processing and is extremely useful in fine patterning for semiconductor device manufacturing.

[0568] This specification includes the following aspects.

[0569] [1] A metal-containing film-forming composition, characterized in that:

[0570] Containing (A) a metal compound, (B) a surface modifier, and (C) a solvent,

[0571] The metal compound contains at least one metal atom selected from the group consisting of Ti, Zr and Hf,

[0572] The surface modifier (B) is a polymer compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), wherein the polymer compound does not contain a repeating unit containing a hydroxyl group.

[0573] [Chemistry 52]

[0574]

[0575] In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R 3 It is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

[0576] [2] The metal-containing film-forming composition according to [1], wherein the heterocyclic structure is a heterocyclic structure containing an oxygen atom.

[0577] [3] The metal-containing film-forming composition according to [1] or [2], wherein R in the general formula (1) and (2) is 2 It is a compound selected from the following formula (R 2 -1)~(R 2 -3) is a monovalent organic group,

[0578] [Chemistry 53]

[0579]

[0580] In the formula, R 4 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the chain represents an atomic bond.

[0581] [4] The metal-containing film-forming composition according to any one of [1] to [3], wherein the surface modifier (B) is a polymer compound further comprising any of the repeating units represented by the following formula (3a) or (3b),

[0582] [Chemistry 54]

[0583]

[0584] In the above formula, R F1 is a monovalent organic group having 1 to 20 carbon atoms and containing at least one F atom, R F2 is a F atom or a monovalent organic group having 1 to 10 carbon atoms and containing one or more F atoms, R 1 is a hydrogen atom or a methyl group, and n represents 1 to 5.

[0585] [5] The metal-containing film-forming composition according to any one of [1] to [4], wherein the weight average molecular weight of the polymer compound used as the surface modifier (B) is 6,000 to 50,000.

[0586] [6] The metal-containing film-forming composition according to any one of [1] to [5], wherein the dispersion degree represented by weight average molecular weight / number average molecular weight of the polymer compound used as the surface modifier (B) is 3.0 or less.

[0587] [7] A metal-containing film-forming composition as described in any one of [1] to [6], wherein the content of the surface modifier (B) contained in the metal-containing film-forming composition is not less than 1 part by mass and not more than 50 parts by mass relative to 100 parts by mass of the metal compound.

[0588] [8] The metal-containing film-forming composition according to any one of [1] to [7], further comprising

[0589] (D) Thermal acid generator,

[0590] (E) Photoacid generator,

[0591] (F) a cross-linking agent, and

[0592] (G) Surfactant

[0593] At least one of the following.

[0594] [9] The metal-containing film-forming composition according to any one of [1] to [8], wherein the solvent (C) contains (C-1) a high boiling point solvent,

[0595] The high boiling point solvent (C-1) is one or more organic solvents having a boiling point of 180 degrees or higher.

[0596]

[10] The metal-containing film-forming composition according to any one of [1] to [9], wherein the metal compound (A) is a metal compound represented by the following general formula (4):

[0597] [Chemistry 55]

[0598] L a MX b (4)

[0599] In the formula, M is any one of Ti, Zr or Hf. L is a monodentate ligand or a polydentate ligand having 1 to 30 carbon atoms, and X is selected from a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR a R b The hydrolyzable group in R a and R bEach independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a+b=4, and a and b are integers of 0-4.

[0600]

[11] The metal-containing film-forming composition according to

[10] , wherein

[0601] The metal compound (A) is a reaction product of a compound derived from the metal compound represented by the general formula (4) and an organic compound having 1 to 30 carbon atoms and containing at least one crosslinking group represented by any of the following general formulas (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3),

[0602] [Chemistry 56]

[0603]

[0604] In the above general formulas (a-1) to (a-4), R a It is hydrogen or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding part.

[0605] [Chemistry 57]

[0606]

[0607] In the above general formula, R b is a hydrogen atom or a methyl group, which may be the same as or different from each other in the same formula, and R c It is hydrogen or a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; * represents a bonding portion.

[0608] [Chemistry 58]

[0609]

[0610] In the above general formulas (c-1) to (c-3), Y 1 is a divalent organic group having 1 to 20 carbon atoms, R is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, R d It is an organic group represented by the following general formula (c-4), in which the protective group is released by the action of either or both of acid and heat to generate one or more hydroxyl groups or carboxyl groups, and * represents a bonding part.

[0611] [Chemistry 59]

[0612]

[0613] In the above general formula (c-4), R e is an organic group from which the protective group is released by the action of either acid or heat or both, and * indicates 1 The bonding portion.

[0614]

[12] A pattern forming method is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0615] (I-1) After applying the metal-containing film-forming composition as described in any one of [1] to

[11] on a substrate to be processed, forming a metal-containing film by heat treatment,

[0616] (I-2) forming a resist upper layer film on the aforementioned metal-containing film using a photoresist material,

[0617] (I-3) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0618] (I-4) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching, and

[0619] (I-5) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

[0620]

[13] A pattern forming method is a method for forming a pattern on a processed substrate, characterized by comprising the following steps:

[0621] (II-1) forming a resist underlayer film on a substrate to be processed,

[0622] (II-2) coating the metal-containing film-forming composition as described in any one of [1] to

[11] on the resist underlayer film, and then performing a heat treatment to form a metal-containing film,

[0623] (II-3) forming a resist upper layer film on the aforementioned metal-containing film using a photoresist material,

[0624] (II-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film,

[0625] (II-5) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching,

[0626] (II-6) using the metal-containing film to which the pattern has been transferred as a mask, transferring the pattern to the resist underlayer film by dry etching,

[0627] (II-7) The substrate to be processed is processed using the patterned resist underlayer film as a mask to form a pattern on the substrate to be processed.

[0628] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any device having substantially the same configuration and exhibiting the same functions and effects as the technical concept of the claims of the present invention is included in the technical scope of the present invention.

[0629] Description of Reference Numerals

[0630] 1:Substrate

[0631] 2: Processing layer

[0632] 2a: Pattern (pattern formed on the processed layer)

[0633] 3: Resist lower layer film

[0634] 3a: Resist lower film pattern

[0635] 4: Metal-containing films

[0636] 4a: Metal-containing film pattern

[0637] 5: Resist upper film

[0638] 5a: Resist upper film pattern

[0639] 6: Exposure part

[0640] 10: Processed substrate

Claims

1. A metal-containing film-forming composition, Its characteristics are: Containing (A) a metal compound, (B) a surface modifier, and (C) a solvent, The metal compound contains at least one metal atom selected from the group consisting of Ti, Zr and Hf, The surface modifier (B) is a polymer compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and the polymer compound does not contain a repeating unit containing a hydroxyl group. In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R 3 It is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

2. The metal-containing film-forming composition according to claim 1, in, The heterocyclic structure is a heterocyclic structure containing an oxygen atom.

3. The metal-containing film-forming composition according to claim 1, in, In the general formulas (1) and (2), R 2 It is a compound selected from the following formula (R 2 -1)~(R 2 -3) is a monovalent organic group, In the formula, R 4 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the chain represents an atomic bond.

4. The metal-containing film-forming composition according to claim 1, in, The surface modifier (B) is a polymer compound further comprising any of the repeating units represented by the following formula (3a) or formula (3b), In the above formula, R F1 is a monovalent organic group having 1 to 20 carbon atoms and containing at least one F atom, R F2 is a F atom or a monovalent organic group having 1 to 10 carbon atoms and containing one or more F atoms, R 1 is a hydrogen atom or a methyl group, and n represents 1 to 5.

5. The metal-containing film-forming composition according to claim 1, in, The weight average molecular weight of the polymer compound used as the (B) surface modifier is 6,000 to 50,000.

6. The metal-containing film-forming composition according to claim 1, in, The polymer compound used as the surface modifier (B) has a dispersity expressed by weight average molecular weight / number average molecular weight of 3.0 or less.

7. The metal-containing film-forming composition according to claim 1, in, The content of the (B) surface modifier contained in the metal-containing film-forming composition is 1 part by mass or more and 50 parts by mass or less relative to 100 parts by mass of the metal compound.

8. The metal-containing film-forming composition according to claim 1, further comprising (D) Thermal acid generator, (E) Photoacid generator, (F) a cross-linking agent, and (G) Surfactant At least one of the following.

9. The metal-containing film-forming composition according to claim 1, in, The (C) solvent contains (C-1) a high boiling point solvent, The high boiling point solvent (C-1) is one or more organic solvents having a boiling point of 180 degrees or higher.

10. The metal-containing film-forming composition according to claim 1, in, The (A) metal compound is derived from a metal compound represented by the following general formula (4): LaMXb(4) In the formula, M is any one of Ti, Zr or Hf, L is a monodentate ligand or a polydentate ligand having 1 to 30 carbon atoms, and X is selected from a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NRaR b The hydrolyzable groups in b Each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; a+b=4, and a and b are integers of 0-4.

11. The metal-containing film-forming composition according to claim 10, in, The metal compound (A) is a reaction product of a compound derived from the metal compound represented by the general formula (4) and an organic compound having 1 to 30 carbon atoms and containing at least one crosslinking group represented by any of the following general formulae (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3), In the above general formulae (a-1) to (a-4), Ra is hydrogen or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion. In the above general formula, R b is a hydrogen atom or a methyl group, which may be the same as or different from each other in the same formula, and R c is hydrogen or a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, * represents a bonding part, In the above general formulas (c-1) to (c-3), Y 1 is a divalent organic group having 1 to 20 carbon atoms, R is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, R d It is an organic group represented by the following general formula (c-4), in which the protective group is released by the action of either or both of acid and heat to generate one or more hydroxyl groups or carboxyl groups, * represents a bonding part, In the above general formula (c-4), R e is an organic group from which the protective group is released by the action of either acid or heat or both, and * indicates 1 The bonding portion.

12. A method for forming a pattern on a processed substrate, characterized by comprising the following steps: (I-1) After applying the metal-containing film-forming composition according to any one of claims 1 to 11 onto a substrate to be processed, forming a metal-containing film by heat treatment, (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film, (I-4) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching, and (I-5) The substrate to be processed is processed using the patterned metal-containing film as a mask to form a pattern on the substrate to be processed.

13. A method for forming a pattern on a processed substrate, characterized by comprising the following steps: (II-1) forming a resist underlayer film on a substrate to be processed, (II-2) after applying the metal-containing film-forming composition according to any one of claims 1 to 11 onto the resist underlayer film, forming a metal-containing film by heat treatment, (II-3) forming a resist upper layer film on the metal-containing film using a photoresist material, (II-4) after pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film, (II-5) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching, (II-6) using the metal-containing film to which the pattern has been transferred as a mask, transferring the pattern to the resist underlayer film by dry etching, (II-7) The substrate to be processed is processed using the patterned resist underlayer film as a mask to form a pattern on the substrate to be processed.

Images