Metal-containing film-forming compound, metal-containing film-forming composition, and pattern forming method

Abstract

The invention relates to a compound for forming a metal-containing film, a composition for forming a metal-containing film, and a pattern forming method. The present invention addresses the problem of providing a semiconductor device which can obtain a good pattern shape in a fine patterning process in a semiconductor device manufacturing step, the purpose of the present invention is to provide a metal-containing compound for forming a resist intermediate film which has high adhesion to a resist upper layer film and which suppresses the collapse of a fine pattern, a metal-containing composition using the compound, and a pattern forming method using the composition, as well as to provide a resist intermediate film which has high adhesion to the resist upper layer film and which suppresses the collapse of the fine pattern. The solution of the present invention is a compound for forming a metal-containing film, which is characterized by having at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and a polydentate ligand that contains a C2-13 cyclic ether structure and that is coordinated to the metal atom.

Description

Technical Field

[0001] The present invention relates to a metal-containing film-forming compound that can be used for fine patterning by a multilayer resist method in a semiconductor device manufacturing process, a metal-containing film-forming composition using the compound, 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. With this miniaturization, 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 of this is the positive photoresist composition used in a single layer. The single-layer positive photoresist composition has a skeleton in the resist resin that has etching resistance to dry etching by chlorine-based or fluorine-based gas plasma, and has a switching mechanism in which the exposed part dissolves, thereby dissolving the exposed part to form a pattern, and using the remaining resist pattern as an etching mask to dry etch the processed substrate.

[0003] However, if the thickness of the photoresist film used is maintained and it is miniaturized, that is, if the pattern width is made smaller, the resolution performance of the photoresist film is reduced. In addition, if the photoresist film is to be patterned by 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 made thinner.

[0004] On the other hand, in the processing of the processed substrate, a method of processing the substrate by dry etching is usually used, in which a photoresist film with a pattern is used 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 is a problem that the photoresist film is easily damaged and collapsed during the processing of the substrate, and the resist pattern cannot be correctly transferred to the processed substrate. Therefore, with the miniaturization of the pattern, a higher dry etching resistance is required for the resist composition. However, on the other hand, in order to improve the resolution, the resin used in the photoresist composition is required to have a small light absorption at the exposure wavelength. Therefore, as the exposure light is i-ray, KrF, ArF, the short wavelength, the resin also changes to a resin with a novolac resin, polyhydroxystyrene, and an aliphatic polycyclic skeleton. In reality, the etching speed of the dry etching conditions during substrate processing is fast, and the recent photoresist composition with high resolution has a tendency to weaken the etching resistance.

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

[0006] One method for solving such a problem is a multilayer resist method, in which a resist interlayer having an etching selectivity different from that of a photoresist film (i.e., a resist upper layer film) is inserted between the resist upper layer film and a substrate to be processed, and after the resist upper layer film has a pattern, the resist upper layer film pattern is used as a dry etching mask to transfer the pattern to the resist interlayer film by dry etching, and the resist interlayer film is further 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 performed using a general resist composition used in the single-layer resist method. The three-layer resist method is, for example, to form an organic film made of a novolac resin or the like as a resist lower film on a substrate to be processed, to form a silicon-containing resist intermediate film thereon as a resist intermediate film, and to form a normal organic photoresist film thereon as a resist upper film. When dry etching is performed by fluorine-based gas plasma, the organic resist upper film has a good etching selectivity ratio with respect to the silicon-containing resist intermediate film, so the resist upper film pattern can be transferred to the silicon-containing resist intermediate film by dry etching by fluorine-based gas plasma. According to this method, even if a resist composition that is difficult to form a pattern having a film thickness sufficient for directly processing a substrate to be processed or a resist composition that does not have sufficient dry etching resistance for processing a substrate is used, as long as 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 using oxygen or hydrogen gas plasma, a pattern of an organic film (resist underlayer film) made of novolac resin or the like having sufficient dry etching resistance for a substrate processing tool can be obtained. As resist underlayer films such as those described in Patent Document 1, many are known.

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

[0009] Silicon-containing films used in such multilayer resist methods have many problems. For example, in the case of forming a resist pattern by optical lithography, it is well known that the exposure light is reflected by the substrate, interfering with the incident light, and causing 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 must have anti-reflection properties. Furthermore, in the most advanced semiconductor process as mentioned above, the thin film of the photoresist is further advanced, so the intermediate film is also required to be thinner, and in the next generation of exposure processes, it is required to have an anti-reflection effect with a film thickness of less than 30nm. In addition, the dry etching speed of the oxygen gas plasma generally used when processing the resist lower film is preferably smaller in order to increase the etching selectivity between the intermediate film and the lower film. Considering the trend of thin film, the dry etching resistance of the intermediate film is required to be improved.

[0010] As a resist interlayer film having satisfactory antireflection effect and dry etching characteristics, a metal hard mask film containing Ti or Zr has attracted attention instead of the conventional silicon-containing film. 2 or ZrO 2 It is known as a high refractive index material, and by including it in the film, the antireflection effect under high NA exposure conditions can be improved. In addition, by including a metal-oxygen bond, excellent dry etching resistance to oxygen can be expected.

[0011] Furthermore, since the metal hard mask 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 the metal hard mask film is formed as a resist lower layer film on a substrate to be processed and a resist upper layer film is formed thereon.

[0012] On the other hand, when such a metal hard mask film is used directly below the resist upper film, the improvement of the adhesion with the resist pattern becomes a problem. The hardened metal hard mask film has a much higher surface energy (or a smaller water contact angle) than the photoresist used later. The mismatch in surface energy causes poor adhesion between the metal hard mask film and the photoresist used later, resulting in pattern collapse.

[0013] In order to suppress the collapse of the photoresist pattern on the metal hard mask film, the surface modification of the metal hard mask film is required. For example, Patent Document 7 reports a metal hard mask containing a surface-modified organic polymer. It is reported that the difference in free energy between the organic polymer and the metal compound is used to improve the adhesion with the resist pattern due to the uneven presence of the organic polymer on the surface. In order to suppress the collapse of the pattern, an organic polymer containing a surface-treated portion selected from a hydroxyl group, a protected hydroxyl group, a protected carboxyl group and a mixture thereof is used. However, in the current situation where more fine pattern formation is required, the pattern collapse suppression performance of these materials cannot be said to be sufficient. In addition, because it contains an organic polymer, there is a risk of deterioration in dry etching resistance to oxygen, so it is required to develop a metal-containing film-forming compound with excellent adhesion to the upper film of the resist.

[0014] Recently, the interaction at the interface between the upper layer film of the resist in a fine pattern and the lower layer film directly below the upper layer film of the resist will also affect the sensitivity of the resist, the shape of the pattern (rectangularity and residue in the gap portion), etc. Based on these viewpoints, the performance of the lower layer film directly below the upper layer film of the resist 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 Gazette 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] The present invention was created based on the above-mentioned circumstances, and its purpose is to provide a metal-containing film-forming compound, a metal-containing film-forming composition using the compound, and a pattern forming method using the composition, which can obtain a good pattern shape in the fine patterning process in the semiconductor device manufacturing step, has high adhesion with the upper film of the resist, and suppresses the collapse of the fine pattern.

[0029] [Methods to solve the problem]

[0030] In order to solve the above-mentioned problems, the present invention provides a metal-containing compound for film formation, which has at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and a multidentate ligand having a cyclic ether structure with 2 to 13 carbon atoms coordinated to the metal atom.

[0031] If such a metal-containing film-forming compound is used in a resist underlayer film-forming composition, a metal-containing film having high adhesion to the resist upper film, an effect of preventing collapse of fine patterns, and a good pattern shape can be formed. In addition, the obtained metal-containing film exhibits a high refractive index, so it can exert a high antireflection effect under ArF immersion and high NA exposure conditions.

[0032] Furthermore, the above-mentioned multidentate ligand is preferably a structure represented by the following general formulas (1-A) to (1-D).

[0033] [Chemistry 1]

[0034]

[0035] (In the above general formulas (1-A) to (1-D), R 1 ~R 4 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, R 5 ~R 6 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, R 7 ~R 10 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, R 11 is a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms. The compounds of the general formulae (1-A) to (1-D) above contain at least one cyclic ether structure having 2 to 13 carbon atoms. In the general formula (1-A), R2 With R 3 They may also be bonded to each other to form a cyclic ether structure having 2 to 13 carbon atoms. 5 With R 6 They may also be bonded to each other to form an unsaturated or saturated ring structure. 8 With R 9 They may also be bonded to each other to form a cyclic ether structure having 2 to 13 carbon atoms, or an unsaturated or saturated ring structure.

[0036] When the metal-containing film-forming compound has a multidentate ligand having such a structure, when used in a resist underlayer film-forming composition, higher adhesion with the resist upper layer film can be obtained, and collapse of fine patterns can be more effectively prevented.

[0037] In this case, the polydentate ligand is preferably a structure represented by the above formula (1-A) or (1-B).

[0038] Such a multidentate ligand can provide a metal-containing film-forming compound having excellent stability.

[0039] Furthermore, the cyclic ether structure is preferably any one of the structures represented by the following formulae (a-1) to (a-2).

[0040] [Chemistry 2]

[0041]

[0042] (Where R a It is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and * represents a bonding part. )

[0043] By containing such a cyclic ether structure, the epoxy or oxetane structure undergoes a ring-opening reaction during film formation by heating, and the film is cured. In addition, the hydroxyl groups generated by the ring-opening reaction also contribute to improving the adhesion with the resist upper layer film.

[0044] In addition, the above-mentioned metal-containing film-forming compound is preferably a reaction product of a metal compound represented by the following formula (2), a hydrolyzate or condensate of a metal compound represented by the following formula (2), or a metal-containing compound of either hydrolysis-condensate, and a multidentate ligand having a structure represented by the above-mentioned general formulas (1-A) to (1-D).

[0045] [Chemistry 3]

[0046] L a MX b (2)

[0047] (wherein, M is any one of Ti, Zr, and Hf. L is a monodentate ligand and / 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 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a+b=4, where a and b are integers of 0 to 4.

[0048] By using such a metal-containing film-forming compound, a metal-containing film having better dry etching resistance with respect to oxygen gas can be formed.

[0049] In this case, the metal compound represented by the above formula (2) is preferably a structure represented by the following formula (3).

[0050] [Chemistry 4]

[0051] M(OR 1A ) 4 (3)

[0052] (wherein, M is Ti, Zr, or Hf, R 1A It is a monovalent organic group having 1 to 20 carbon atoms.

[0053] A metal-containing film-forming compound having such a structure is preferred from the viewpoints of productivity and raw material availability.

[0054] Furthermore, the metal-containing film-forming compound preferably further contains a ligand derived from a silicon compound represented by the following general formula (4).

[0055] [Chemistry 5]

[0056]

[0057] (In the above general formula (4), R 3A , R 3B and R 3C It is any one of an 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 a crosslinking group having any of the structures represented by the following general formulae (b-1) to (b-3).

[0058] [Chemistry 6]

[0059]

[0060] (In the above general formulas (b-1) to (b-3), R 3is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion. )

[0061] By including such a ligand, the stability of the metal-containing film-forming compound can be further improved.

[0062] In addition, the present invention provides a metal-containing film-forming composition comprising:

[0063] (A) the above-mentioned metal-containing film-forming compound, and

[0064] (B) Organic solvent.

[0065] If such a metal-containing film-forming composition is used, a metal-containing film having high adhesion to the resist upper film, having the effect of preventing the collapse of fine patterns, and giving a good pattern shape can be formed. In addition, the obtained metal-containing film exhibits a high refractive index, so it can exert a high anti-reflection effect under ArF immersion and high NA exposure conditions.

[0066] Furthermore, the composition may contain one or more of (C) a thermal acid generator and (D) a photoacid generator.

[0067] If the metal-containing film-forming composition contains the above-mentioned additives, the metal-containing film-forming composition can be more excellent in coating properties and adhesion to the resist upper layer film.

[0068] In addition, the composition may further contain one or more of (E) a cross-linking agent and (F) a surfactant.

[0069] If the metal-containing film-forming composition contains the above-mentioned additive, the metal-containing film-forming composition can be more excellent in coating property, dry etching resistance, and filling and / or planarization characteristics.

[0070] Furthermore, the organic solvent (B) is preferably 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.

[0071] By adding a high-boiling-point solvent to the metal-containing film-forming compound to impart fluidity, it is possible to suppress the occurrence of coating defects due to drying of the metal-containing film-forming composition.

[0072] The present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, comprising the following steps:

[0073] (I-1) After applying the metal-containing film-forming composition on a substrate to be processed, heat treatment is performed to form a metal-containing film.

[0074] (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material,

[0075] (I-3) after exposing the resist upper layer film to a pattern, developing the resist upper layer film with a developer to form a pattern on the resist upper layer film,

[0076] (I-4) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching, and

[0077] (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.

[0078] In addition, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, comprising the following steps:

[0079] (II-1) forming a resist underlayer film on a substrate to be processed,

[0080] (II-2) coating the metal-containing film-forming composition on the resist underlayer film, and then performing a heat treatment to form a metal-containing film.

[0081] (II-3) forming a resist upper layer film on the metal-containing film using a photoresist material,

[0082] (II-4) After exposing the resist upper layer film to a pattern, developing the resist upper layer film with a developer to form a pattern on the resist upper layer film,

[0083] (II-5) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching,

[0084] (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,

[0085] (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.

[0086] As described above, the metal-containing film-forming compound of the present invention is, for example, a metal-containing film-forming compound containing a cyclic ether structure selected from the above formula (a-1) or (a-2). When it is used in a metal-containing film-forming composition, since a metal-containing film having excellent adhesion to the resist upper film can be formed, it can be suitable for use in various pattern forming methods such as a two-layer resist process or a three-layer resist process. In these pattern forming methods, the metal-containing film provided by the present invention can more 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.

[0087] [Effects of the Invention]

[0088] As described above, the present invention provides a metal-containing film-forming compound having high adhesion to a resist upper layer film and having an effect of preventing fine pattern collapse, a metal-containing film-forming composition using the compound, and a pattern forming method using the composition.

[0089] The resist underlayer film formed using the conventional metal-containing film-forming compound has a much higher surface energy (or a smaller water contact angle) than the photoresist used subsequently, so the mismatch in surface energy causes poor adhesion between the metal-containing film and the photoresist used subsequently, resulting in pattern collapse. In addition, when an organic polymer is mixed as a surface modifier, the dry etching resistance of the organic underlayer film during processing becomes insufficient, which may cause poor transfer of the pattern.

[0090] In contrast, the metal-containing film-forming compound of the present invention contains a cyclic ether structure, so when used in a metal-containing film-forming composition, a metal-containing film having excellent adhesion to the upper film of the resist can be formed. Therefore, it has the effect of suppressing the collapse of fine patterns, and gives the processed substrate a pattern shape of the upper film of the resist with high rectangularity, so it is very useful in a multi-layer resist process. In addition, the metal-containing film-forming compound using a multidentate ligand of the present invention can form a resist lower film with a large proportion of metal atoms compared to the metal-containing film-forming compound using a monodentate ligand. Therefore, it has excellent resistance to dry etching using oxygen and fluorine gas respectively, and in various pattern forming methods such as a two-layer resist process or a three-layer resist process, a fine pattern can be formed on the processed substrate with high precision. BRIEF DESCRIPTION OF THE DRAWINGS

[0091] [ Figure 1 ](A) to (F) are illustrations of an example of the pattern forming method of the present invention (three-layer resist process).

[0092] [ Figure 2](G) to (K) are illustrations of an example of the pattern forming method of the present invention (two-layer resist process).

[0093] [ Figure 3 ] Illustration of the calculation of reflectivity in the pattern forming method. DETAILED DESCRIPTION

[0094] As described above, there is a need to develop a metal-containing film-forming compound that can obtain a good pattern shape in a fine patterning process in a semiconductor device manufacturing step, and to provide a metal-containing film with high adhesion to a resist upper film and suppress collapse of the fine pattern, a metal-containing film-forming composition using the compound, and a pattern forming method using the composition.

[0095] As a result of in-depth studies on the above-mentioned issues, the inventors of the present application have discovered that a metal-containing film-forming compound containing a ligand with a specific structure, a metal-containing film-forming composition using the compound, and a pattern forming method using the composition can solve the above-mentioned issues, thereby completing the present invention.

[0096] That is, the present invention is a metal-containing film-forming compound having at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and a multidentate ligand having a cyclic ether structure having 2 to 13 carbon atoms coordinated to the metal atom.

[0097] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0098] <Metal-Containing Film-Forming Compound>

[0099] The present invention relates to a metal-containing film-forming compound that can be used in a metal-containing film-forming composition, wherein the metal-containing film-forming compound is characterized by having at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and a multidentate ligand having a cyclic ether structure with 2 to 13 carbon atoms coordinated to the metal atom.

[0100] If such a metal-containing film-forming compound is used in a resist underlayer film-forming composition, a metal-containing film having high adhesion to the resist upper film, an effect of preventing collapse of fine patterns, and a good pattern shape can be formed. In addition, the obtained metal-containing film exhibits a high refractive index, so it can exert a high antireflection effect under ArF immersion and high NA exposure conditions.

[0101] The polydentate ligand is preferably any one of the structures represented by the following general formulae (1-A) to (1-D).

[0102] [Chemistry 7]

[0103]

[0104] (In the above general formulas (1-A) to (1-D), R 1 ~R 4 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, R 5 ~R 6 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, R 7 ~R 10 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, R 11 is a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms. The compounds of the general formulae (1-A) to (1-D) above contain at least one cyclic ether structure having 2 to 13 carbon atoms. In the general formula (1-A), R 2 With R 3 They may also be bonded to each other to form a cyclic ether structure having 2 to 13 carbon atoms. 5 With R 6 They may also be bonded to each other to form an unsaturated or saturated ring structure. 8 With R 9 They may also be bonded to each other to form a cyclic ether structure having 2 to 13 carbon atoms, or an unsaturated or saturated ring structure.

[0105] The compounds of the above formulae (1-A) to (1-D) contain at least one cyclic ether structure having 2 to 13 carbon atoms, preferably 2 to 10 carbon atoms. More preferably, the molecule contains 1 or 2 such cyclic ether structures, and further preferably contains 1 such cyclic ether structure.

[0106] In the above formula (1-A), R 1 and R 4 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted allyl group having 2 to 10 carbon atoms, a substituted or unsubstituted ethynyl group having 2 to 10 carbon atoms, or a monovalent organic group having 1 to 20 carbon atoms containing a cyclic ether structure having 2 to 13 carbon atoms, more preferably a methyl group, an ethyl group, a phenyl group, an allyloxy group, a propargyloxy group, an alkoxy group having 1 to 10 carbon atoms, or a monovalent organic group having 1 to 20 carbon atoms containing a cyclic ether structure having 2 to 13 carbon atoms. In R 1 and R 4When the cyclic ether structure having 2 to 13 carbon atoms is not contained, methyl, methoxy and ethoxy groups are preferred.

[0107] R 2 and R 3 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted allyl group having 2 to 10 carbon atoms, a substituted or unsubstituted ethynyl group having 2 to 10 carbon atoms, or a monovalent organic group having 1 to 20 carbon atoms containing a cyclic ether structure having 2 to 13 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an allyloxy group, a propargyloxy group, or a monovalent organic group having 1 to 20 carbon atoms containing a cyclic ether structure having 2 to 13 carbon atoms. In addition, R 2 and R 3 They can also bond with each other to form a cyclic ether structure with 2 to 13 carbon atoms. 2 When there is a substituent other than a hydrogen atom, R 3 Preferably, it is a hydrogen atom. Preferably, R 2 and R 3 At least one of R is a hydrogen atom. 2 and R 3 In the case of not containing a cyclic ether structure having 2 to 13 carbon atoms, R 2 and R 3 Both are hydrogen atoms.

[0108] In the above formula (1-B), R 5 and R 6 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted allyl group having 2 to 10 carbon atoms, a substituted or unsubstituted ethynyl group having 2 to 10 carbon atoms, or a monovalent organic group having 1 to 20 carbon atoms containing a cyclic ether structure having 2 to 13 carbon atoms. In the case where the cyclic ether structure having 2 to 13 carbon atoms is not contained, R 5 and R 6 Preferably, it is a hydrogen atom. 5 With R 6 They can also bond with each other to form unsaturated or saturated ring structures.

[0109] In the above formula (1-C), R 7 and R 10 It is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom.

[0110] In the above formula (1-C), R 8 It is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, and more preferably a monovalent organic group having 1 to 20 carbon atoms which contains a cyclic ether structure having 2 to 13 carbon atoms. 9 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, more preferably a hydrogen atom or an alkyl or aryl group having 1 to 10 carbon atoms, and further preferably a hydrogen atom. 8 With R 9 They may be bonded to each other to form a cyclic ether structure having 2 to 13 carbon atoms, or an unsaturated or saturated ring structure.

[0111] In the above formula (1-D), R 11 It is preferably a divalent organic group having 1 to 20 carbon atoms and containing a cyclic ether structure having 2 to 13 carbon atoms. Y is a divalent organic group having 1 to 10 carbon atoms, preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 5 carbon atoms in view of the availability of raw materials, further preferably a methylene group or an ethylene group, and particularly preferably an ethylene group.

[0112] Since the metal-containing film-forming compound has such a multidentate ligand, when used in a resist underlayer film-forming composition, higher adhesion with the resist upper layer film can be obtained, and collapse of fine patterns can be more effectively prevented.

[0113] The cyclic ether structure (cyclic ether structure having 2 to 13 carbon atoms) is preferably any one of the structures represented by the following formulae (a-1) to (a-2).

[0114] [Chemistry 8]

[0115]

[0116] (Where R a It is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and * represents a bonding part. )

[0117] In the case of such a metal-containing film-forming compound, the epoxy or oxetane structure undergoes a ring-opening reaction during film formation by heating, thereby hardening the film. In addition, the hydroxyl groups generated by the ring-opening reaction also contribute to improving the adhesion with the resist upper layer film.

[0118] R in (a-2) above a , preferably a hydrogen atom, a methyl group or an ethyl group, more preferably an ethyl group.

[0119] Examples of the structures of the ligands derived from the formulae (1-A) to (1-D) include the following compounds, but the present invention is not limited to these.

[0120] [Chemistry 9]

[0121]

[0122] (The above R 1 , R 4 , R a Same as above, n represents 1 to 10. )

[0123] From the viewpoint of productivity and stability of the metal-containing film-forming compound, the cyclic ether structure is more preferably a structure represented by formula (a-2).

[0124] The above-mentioned multidentate ligand is more preferably a structure represented by the above formula (1-A) or (1-B).

[0125] Such a multidentate ligand can provide a metal-containing film-forming compound having excellent stability.

[0126] In addition, the above-mentioned metal-containing film-forming compound is preferably a reaction product of (a) a metal-containing compound comprising a metal compound represented by the following formula (2), a hydrolyzate or condensate of a metal compound represented by the following formula (2), or any one of the hydrolysis-condensates, and a multidentate ligand having a structure represented by the above-mentioned general formulas (1-A) to (1-D).

[0127] [Chemistry 10]

[0128] K a MX b (2)

[0129] (wherein, M is any one of Ti, Zr, and Hf. L is a monodentate ligand and / 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 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a+b=4, where a and b are integers of 0 to 4.

[0130] If such a metal-containing film-forming compound is used in a metal-containing film-forming composition, a metal-containing film having excellent dry etching resistance to oxygen gas can be formed.

[0131] [(a) Metal-containing compounds]

[0132] (Hydrolyzable Group)

[0133] Examples of the hydrolyzable group X in the formula (2) include a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, and -NR a R b . R a and R bEach independently is preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0134] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0135] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group.

[0136] Examples of the carboxylate group include an acetate group, a propionate group, a butyrate group, an n-hexanecarboxylate group, and an n-octanecarboxylate group.

[0137] Examples of the acyloxy group include an acetoxy group, an ethyryloxy group, a propionyloxy group, a butyryloxy group, a tert-butyryloxy group, a tert-valeryloxy group, a n-hexanecarbonyloxy group, and a n-octanecarbonyloxy group.

[0138] As the above-NR a R b , for example, unsubstituted amino, methylamino, dimethylamino, diethylamino, dipropylamino and the like can be mentioned.

[0139] The hydrolyzable group X is preferably an alkoxy group, more preferably an isopropoxy group, an n-butoxy group, or a tert-butoxy group.

[0140] (Single tooth matching)

[0141] Examples of the monodentate ligand L in the above formula (2) include a hydroxyl ligand, a carboxyl ligand, an amide ligand, an amine ligand, an ammonia ligand, and an olefin ligand.

[0142] Examples of the amide ligand include unsubstituted amide ligands (NH 2 ), methylamide ligand (NHMe), dimethylamide ligand (NMe 2 ), diethylamide ligand (NEt 2 ), dipropylamide ligand (NPr 2 )wait.

[0143] Examples of the amine ligand include pyridine, trimethylamine ligand, piperidine ligand and the like.

[0144] Examples of the olefin ligand include chain olefins such as ethylene and propylene, and cyclic olefins such as cyclopentene, cyclohexene and norbornene.

[0145] (Multi-toothed ligand)

[0146] Examples of the multidentate ligand L in the above formula (2) include 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, and diphosphines.

[0147] Examples of the hydroxy acid ester include glycolic acid ester, lactic acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, and salicylic acid ester.

[0148] Examples of the β-diketone include acetoacetate, α-alkyl-substituted acetoacetate, β-ketopentanoate, benzoyl acetate, and 1,3-acetone dicarboxylate.

[0149] Examples of the α,α-dicarboxylic acid esters include malonic acid diesters, α-alkyl-substituted malonic acid diesters, α-cycloalkyl-substituted malonic acid diesters, and α-aryl-substituted malonic acid diesters.

[0150] Examples of the hydrocarbon having a π bond include 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.

[0151] Examples of the diphosphine include 1,1-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, and 1,1′-bis(diphenylphosphino)ferrocene.

[0152] In the above general formula (2), a+b=4, and a and b are integers of 0 to 4. a is preferably 0 to 3, more preferably 0 to 2, further preferably 1 to 2, and particularly preferably 2. b is preferably 2 to 4, more preferably 2 or 3, and further preferably 2. By setting a and b to the above ranges, the stability of the metal compound (A) can be improved.

[0153] Examples of the metal-containing compound (a) include: titanium-containing compounds such as diisopropoxybis(2,4-pentanedione)titanium(IV), tetra-n-butoxytitanium(IV), tetra-n-propoxytitanium(IV), tri-n-butoxymonostearatetitanium(IV), butoxide titanium(IV) oligomer, aminopropyltrimethoxytitanium(IV), triethoxymono(2,4-pentanedione)titanium(IV), tri-n-propoxymono(2,4-pentanedione)titanium(IV), triisopropoxymono(2,4-pentanedione)titanium, and di-n-butoxybis(2,4-pentanedione)titanium(IV); and zirconium-containing compounds such as dibutoxybis(ethylacetoacetate)zirconium(IV), di-n-butoxybis(2,4-pentanedione)zirconium(IV), tetra-n-butoxyzirconium(IV), tetra-n-propoxyzirconium(IV), and tetraisopropyl Examples of the hafnium-containing compound include triethoxy zirconium (IV), aminopropyl triethoxy zirconium (IV), 2-(3,4-epoxycyclohexyl)ethyl trimethoxy zirconium (IV), γ-glycidoxypropyl trimethoxy zirconium (IV), 3-isocyanopropyl trimethoxy zirconium (IV), triethoxymono(2,4-pentanedione) zirconium (IV), tri-n-propoxymono(2,4-pentanedione) zirconium (IV), triisopropoxymono(2,4-pentanedione) zirconium (IV), tri(3-methacryloxypropyl)methoxyzirconium (IV), and tri(3-acryloxypropyl)methoxyzirconium (IV). Examples of the hafnium-containing compound include diisopropoxybis(2,4-pentanedione) hafnium (IV), tetrabutoxy hafnium (IV), tetraisopropoxy hafnium (IV), tetraethoxy hafnium (IV), and dichlorobis(cyclopentadienyl) hafnium (IV).

[0154] From the viewpoint of obtaining a good raw material, the metal compound represented by the above formula (2) is preferably a structure of the following formula (3).

[0155] [Chemistry 11]

[0156] M(OR 1A ) 4 (3)

[0157] (wherein, M is Ti, Zr, or Hf, R 1A It is a monovalent organic group having 1 to 20 carbon atoms.

[0158] In the above formula (3), R 1A It is a monovalent organic group having 1 to 20 carbon atoms, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, more preferably isopropyl, n-butyl or tert-butyl.

[0159] [(b) Ligand-forming compound]

[0160] During the synthesis reaction of the metal-containing film-forming compound, in addition to (a) the metal-containing compound and the polydentate ligand containing a cyclic ether structure having 2 to 13 carbon atoms, a compound that can serve as a monodentate ligand or a polydentate ligand (hereinafter referred to as (b) the ligand-forming compound) may be added to the metal-containing film-forming compound.

[0161] As for the above-mentioned (b) ligand-forming compound, in addition to organic compounds that can be hydroxyl ligands, carboxyl ligands, amide ligands, amine ligands, amino ligands, olefin ligands, etc. listed as L in the above formula (2), organic compounds that can be ligands derived from hydroxy acid esters, ligands derived from β-diketones, ligands derived from β-ketoesters, ligands derived from α,α-dicarboxylates, etc., compounds having multiple hydroxyl groups can also be listed.

[0162] 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 (c-1) to (c-4), (d-1) to (d-4), and (e-1) to (e-3).

[0163] [Chemistry 12]

[0164]

[0165] (In the above general formulas (c-1) to (c-4), R c is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion. )

[0166] [Chemistry 13]

[0167]

[0168] (In the above general formula, R d1 is a hydrogen atom or a methyl group, which may be the same or different from each other in the same formula, and R d2 It is a hydrogen atom 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 aralkyl group having 7 to 31 carbon atoms, and * represents a bonding part. )

[0169] [Chemistry 14]

[0170]

[0171] (In the above general formulas (e-1) to (e-3), Y e is a divalent organic group having 1 to 31 carbon atoms, preferably 1 to 20 carbon atoms, R e2is a hydrogen atom, a substituted or unsubstituted saturated monovalent organic group having 1 to 20 carbon atoms or an unsaturated monovalent 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 aralkyl group having 7 to 31 carbon atoms, R e1 The following general formula (e-4) represents an organic group that generates one or more hydroxyl groups or carboxyl groups by the removal of the protecting group under the action of either or both of acid and heat, and * represents a bonding part.

[0172] [Chemistry 15]

[0173]

[0174] (In the above general formula (e-4), R e3 It is an organic group whose protective group will be removed by the action of either acid, heat or both. * indicates that it is the same as Y e The bonding part.)

[0175] (b) The ligand-forming compound contains at least one cross-linking group represented by any one of the above-mentioned (c-1) to (c-4), (d-1) to (d-4), and (e-1) to (e-3), so that sufficient thermal fluidity can be obtained during film formation. Therefore, when used in a metal-containing film-forming composition, a metal-containing film with excellent flatness can be formed.

[0176] Considering the productivity and stability of the metal-containing film-forming compound, the above-mentioned (b) ligand-forming compound is preferably a compound that can become a carboxyl ligand, a compound that can become a ligand derived from β-diketone, or a compound having multiple hydroxyl groups. These can be used alone or in combination of two or more.

[0177] Examples of the compound that can serve as a ligand for the carboxyl group include compounds represented by the following formula (5).

[0178] [Chemistry 16]

[0179]

[0180] (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 one of the general formulas (d-1) to (d-4). When p is 0, X 1 It is a crosslinking group containing any one of the structures represented by the above general formulae (c-2) to (c-4) and a monovalent organic group having 8 to 30 carbon atoms in the aromatic ring.

[0181] [Chemistry 17]

[0182]

[0183] (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 (c-1) to (c-4), h represents 1 to 6, and * represents a bond to the carbon atom of the carbonyl group.

[0184] If the compound having such a structure and capable of serving as a ligand for a carboxyl group is used, the heat curing property of the metal-containing film-forming compound can be improved, and a metal-containing film having excellent resistance to intermixing with a resist upper layer film can be formed.

[0185] In the above general formula (5), p is preferably 1, and W is a structure represented by the following general formula (5-B).

[0186] [Chemistry 18]

[0187]

[0188] (In the above general formula (5-B), R A1 is the structure represented by the above general formula (c-1), R A2 is any of the structures represented by the above general formula (c-2) or (c-3), Z is any of an oxygen atom or a secondary amine, and L 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, R A3 It is a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms or 2 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.

[0189] If the compound having such a structure can serve as a carboxyl ligand, the heat resistance of the metal-containing film-forming compound is improved, so that the formed metal-containing film can exhibit excellent film-forming properties. In addition, the generation of sublimates during heat curing can be suppressed to prevent contamination of the device.

[0190] In the above general formula (5), preferably, p is 1, W is an alkoxy group having 1 to 10 carbon atoms, and X 1 Any one of the structures represented by the following general formula (5-C).

[0191] [Chemistry 19]

[0192]

[0193] (In the formula, * represents a bonding part.)

[0194] If the compound having such a structure can serve as a carboxyl ligand, the heat resistance of the metal-containing film-forming compound is improved, so that the formed metal-containing film can exhibit excellent film-forming properties. In addition, the generation of sublimates during heat curing can be suppressed, thereby preventing contamination of the device.

[0195] Alternatively, in the above general formula (5), p is preferably 0, X 1 Any one of the structures represented by the following general formula (5-D).

[0196] [Chemistry 20]

[0197]

[0198] (In the above general formula (5-D), R f The same as Rc in the above general formula (c-2) or (c-3), * represents the bond portion to the carbon atom of the carbonyl group.)

[0199] Examples of the compound that can serve as a ligand for the carboxyl group include compounds represented by the following formula (6).

[0200] [Chemistry 21]

[0201]

[0202] (In the above general formula (6), X 2 is a divalent organic group having 1 to 31 carbon atoms, R 6A It is any one of the above general formulas (e-1) to (e-3).

[0203] In the above general formula (6), X 2 It 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.

[0204] In the above general formulas (e-1) to (e-3), Y e 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 aralkyl group having 7 to 31 carbon atoms, preferably Y e It is a saturated hydrocarbon having 1 to 20 carbon atoms or an unsaturated hydrocarbon having 2 to 20 carbon atoms.

[0205] If in the above general formulas (e-1) to (e-3), Y e A saturated hydrocarbon having 1 to 20 carbon atoms or an unsaturated hydrocarbon having 2 to 20 carbon atoms can further improve the thermal curability of the metal-containing film-forming compound.

[0206] As Y eExamples of the invention include, but are not limited to, the following structures.

[0207] [Chemistry 22]

[0208]

[0209] (* 1 is the bond to the oxygen atom or nitrogen atom, 2 Represents R e1 The bonding part.)

[0210] In the above general formula (e-4), R e3 It is an organic group from which the protecting group (thermal acid unstable group) is separated by the action of either acid or heat or both, and is preferably a tertiary hydrocarbon group or a group that forms an acetal structure together with an adjacent oxygen atom, and is particularly preferably a tertiary hydrocarbon group. As the above-mentioned tertiary hydrocarbon group, it is preferably a group with 4 to 20 carbon atoms, and more preferably a group with fewer carbon atoms.

[0211] Examples of the compound that can serve as a ligand derived from β-diketone include compounds represented by formula (7).

[0212] [Chemistry 23]

[0213]

[0214] (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 also contain a crosslinking group represented by any of the general formulae (c-1) to (c-4) and (d-1) to (d-4).

[0215] The compound of the general formula (7) preferably contains at least one crosslinking group represented by any one of the general formulae (c-1) to (c-4) and (d-1) to (d-4). Such a compound is more desirable because it can further improve the thermal curability of the metal-containing film-forming compound.

[0216] Examples of the compound having a plurality of hydroxyl groups include divalent alcohols represented by any one of formulae (7-A) to (7-C).

[0217] [Chemistry 24]

[0218]

[0219] (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 (c-1) to (c-4), R 7c ~R 7fis 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 (c-1) to (c-4) and (d-1) to (d-4), 2 is a divalent organic group having 1 to 10 carbon atoms. 7a With R 7b They can also bond with each other to form unsaturated or saturated ring structures.)

[0220] The compounds of the general formulae (7-A) to (7-C) preferably contain at least one crosslinking group represented by any one of the general formulae (c-1) to (c-4) and (d-1) to (d-4). Such compounds are more desirable because they can further improve the thermal curability of the metal-containing film-forming compound.

[0221] In the metal-containing film-forming compound, the content of the multidentate ligand containing a cyclic ether structure having 2 to 13 carbon atoms is preferably 10 mol% to 100 mol% of the total content of the ligands coordinated to the metal atom, more preferably 20 mol% to 90 mol%, and further preferably 25 mol% to 75 mol%. The content of the ligand derived from the (b) ligand-forming compound is preferably 0 mol% to 50 mol% of the total content of the ligands coordinated to the metal atom, more preferably 0 mol% to 25 mol%. The ligand other than the (b) ligand-forming compound, such as the ligand derived from the alkoxy group having 1 to 10 carbon atoms, is preferably 0 mol% to 90 mol% of the total content of the ligands coordinated to the metal atom, more preferably 0 mol% to 75 mol%.

[0222] [(c) Silicon-containing compounds]

[0223] Furthermore, in the synthesis reaction of the metal-containing film-forming compound, in addition to the polydentate ligand having a cyclic ether structure having 2 to 13 carbon atoms, (c) a silicon-containing compound may be further added.

[0224] By substituting the hydrolyzable group of the (a) metal-containing compound with a silicon-containing compound, the stability of the metal-containing compound for forming a film in the metal-containing film-forming composition can be improved.

[0225] Examples of the silicon-containing compound include a structure represented by the following general formula (4).

[0226] [Chemistry 25]

[0227]

[0228] (In the above general formula (4), R 3A , R 3B and R 3CIt is any one of organic groups having 1 to 30 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, and aryl groups having 1 to 20 carbon atoms, which are crosslinking groups having any of the structures represented by the following general formulae (b-1) to (b-3).

[0229] [Chemistry 26]

[0230]

[0231] (In the above general formulas (b-1) to (b-3), R 3 is hydrogen or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.

[0232] As the silicon-containing compound, a group of any of the following formulae is more preferred, and trimethylsilanol is more preferred from the viewpoint of productivity.

[0233] [Chemistry 27]

[0234]

[0235] (In the above formula, * represents the bonding part with the metal atom.)

[0236] When the metal-containing film-forming compound contains a multidentate ligand having a cyclic ether structure with 2 to 13 carbon atoms and a ligand derived from the silicon-containing compound (c), the content of the multidentate ligand having a cyclic ether structure with 2 to 13 carbon atoms in the metal-containing film-forming compound is preferably 10 to 100 mol %, more preferably 20 to 80 mol %, and further preferably 25 to 75 mol %, of the total content of the ligands coordinated to the metal atom. The content of the ligand derived from the silicon-containing compound (c) is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, and further preferably 25 to 75 mol %, of the total content of the ligands coordinated to the metal atom. The content of the multidentate ligands of the cyclic ether structure having 2 to 13 carbon atoms and the ligands other than (c) the silicon-containing compound, such as the ligands from the alkoxy group having 1 to 10 carbon atoms, is preferably 0 to 90 mol % of the total content of the ligands coordinated to the metal atom, and more preferably 0 to 75 mol %.

[0237] [Synthesis method]

[0238] In the case of synthesizing the metal-containing film-forming compound of the present invention, as long as the metal-containing film-forming compound contains a multidentate ligand having a cyclic ether structure with 2 to 13 carbon atoms, the synthesis method is not particularly limited. For example, the metal-containing compound (a) can be obtained by reacting an alkoxy or acac metal with a multidentate ligand having a cyclic ether structure with 2 to 13 carbon atoms using a metal alkoxide or acetylacetonate (acac) metal salt. The metal-containing compound (a) can also be hydrolyzed and condensed before reacting with a multidentate ligand having a cyclic ether structure with 2 to 13 carbon atoms, or the metal-containing compound (a) can be hydrolyzed and condensed after reacting with a multidentate ligand having a cyclic ether structure with 2 to 13 carbon atoms. In the case where it is difficult to control the hydrolysis and condensation, the metal-containing compound can also be reacted with a multidentate ligand having a cyclic ether structure with 2 to 13 carbon atoms in a non-aqueous environment. These are preferably adjusted appropriately in accordance with the properties required for the metal-containing film and the metal-containing film. In the case where a multidentate ligand having a cyclic ether structure having 2 to 13 carbon atoms is used as a ligand with (c) a silicon-containing compound, it is more ideal to react (a) a metal-containing compound with (c) a silicon-containing compound and then react it with the multidentate ligand having a cyclic ether structure having 2 to 13 carbon atoms.

[0239] As a method for hydrolysis-condensation reaction using a metal-containing compound (a), for example, a method of hydrolysis-condensation reaction of a metal-containing compound (a) in a solvent containing water can be cited. In this case, other compounds with hydrolyzable groups can also be added in response to demand. In addition, as a catalyst for hydrolysis-condensation reaction, an acid such as acetic acid can also be added. As the lower limit of the amount of water used in the hydrolysis-condensation reaction, relative to the hydrolyzable groups possessed by the metal-containing compound (a), it is preferably 0.2 times mole, more preferably 1 times mole, and further preferably 3 times mole. As the upper limit of the amount of the above-mentioned water, it is preferably 20 times mole, more preferably 15 times mole, and further preferably 10 times mole.

[0240] There are no particular limitations on the solvent used in the synthesis reaction of the metal-containing film-forming compound. For example, the same solvent as exemplified as the (B) organic solvent described later can be used. Typical solvents and solvent mixtures contain ester, ether or alcohol functional groups, such as a mixture of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) in a volume ratio of 70 / 30. 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- propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diamyl ether, isopentyl 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.

[0241] <Metal-Containing Film-Forming Composition>

[0242] Furthermore, the present invention provides a metal-containing film-forming composition comprising (A) the metal-containing film-forming compound of the present invention and (B) an organic solvent.

[0243] <(A) Metal-Containing Film-Forming Compound>

[0244] The component (A) in the metal-containing film-forming composition of the present invention is the metal-containing film-forming compound of the present invention. The amount of the component (A) in the composition is not particularly limited, and can be, for example, 1 to 20 parts by mass, preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass relative to 100 parts by mass of the total amount of the composition.

[0245] <(B) Organic Solvent>

[0246] The (B) organic 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-containing film-forming compound, and when contained, the later-mentioned (C) thermal acid generator, (D) photoacid generator, (E) cross-linking agent, (F) surfactant, and other additives.

[0247] Specifically, for example, an organic solvent described 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 may be used.

[0248] 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-containing film-forming compound.

[0249] <High boiling point solvent>

[0250] In the metal-containing film-forming composition of the present invention, the organic solvent (B) may contain a high-boiling-point organic solvent. The high-boiling-point organic solvent may be one or more organic solvents having a boiling point of 180 degrees (° C.) or higher.

[0251] For example, as the (B) organic solvent, 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 (high boiling point solvent) may be used.

[0252] As the high boiling point solvent, there is no particular limitation on hydrocarbons, alcohols, ketones, esters, ethers, chlorine-based solvents, etc., as long as they can dissolve the components of the metal-containing film-forming composition of the present invention. Specific examples thereof 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, 1,2-propanediol ...1,2-propanediol, 1,3-butanediol, 1,2-propanediol, 1,3-butanediol, 1,2-propanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanedi diol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, n-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 Triethylene 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 diacetic acid Ester, dipropylene glycol 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.

[0253] The high boiling point solvent is combined with the temperature at which the metal-containing film-forming composition of the present invention is heat-treated, and can be appropriately selected from, for example, the above. The boiling point of the high boiling point solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. If it is such a boiling point, there is no risk of volatilization too fast during baking (heat treatment), so the defects caused by drying during film formation can be suppressed. In addition, if it is such a boiling point, there is no risk of remaining in the film without volatilization after baking, so there is no risk of adverse effects on the film properties such as etching resistance.

[0254] In addition, when a high boiling point solvent is used, the blending amount is preferably 1 to 30 parts by mass relative to 100 parts by mass of an organic solvent having a boiling point of less than 180° C. Such a blending amount is preferred because sufficient thermal fluidity can be imparted during baking and the solvent will not remain in the film and cause deterioration of film properties such as etching resistance.

[0255] <Other ingredients>

[0256] The above-mentioned metal-containing film-forming composition, when being used as a metal-containing film-forming composition for a resist underlayer film used in a multilayer resist method, may contain one or more of the above-mentioned (A) metal-containing film-forming compound and (B) organic solvent, and may also contain at least one of (C) a thermal acid generator, (D) a photoacid generator, (E) a cross-linking agent, and (F) a surfactant as required.

[0257] Hereinafter, components that may be contained in the metal-containing film-forming composition of the present invention other than the above-mentioned (A) metal-containing film-forming compound and (B) organic solvent will be described.

[0258] [(C) Thermal acid generator]

[0259] The metal-containing film-forming composition of the present invention preferably contains (C) a thermal acid generator in order to promote the crosslinking reaction by heat.

[0260] Examples of the thermal acid generator (C) that can be used in the metal-containing film-forming composition of the present invention include the following general formula (7) and the like.

[0261] [Chemistry 28]

[0262]

[0263] (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, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group, and a part or all of the hydrogen atoms of 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. In the case of forming a ring, R 70 and R 71 , or R 70 , R71 and R 72 represents an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring having a nitrogen atom in the ring.

[0264] The above R 70 , R 71 , R 72 , and R 73 They may be the same as or different from each other. Specifically, examples of the alkyl group 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.

[0265] Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl.

[0266] Examples of the oxoalkyl group include 2-oxocyclopentyl, 2-oxocyclohexyl, 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl.

[0267] Examples of the oxoalkenyl group include 2-oxo-4-cyclohexenyl and 2-oxo-4-propenyl.

[0268] Examples of the aryl group include phenyl, naphthyl, and the like; or alkoxyphenyl groups such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert-butoxyphenyl; alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, and 4-butylphenyl; alkylnaphthyl groups such as methylnaphthyl and ethylnaphthyl; alkoxynaphthyl groups such as methoxynaphthyl and ethoxynaphthyl; dialkylnaphthyl groups such as dimethylnaphthyl and diethylnaphthyl; and dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl.

[0269] Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group.

[0270] Examples of the aryloxyalkyl group include 2-aryl-2-oxoethyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl and 2-(2-naphthyl)-2-oxoethyl.

[0271] In addition, in R 70 and R 71 , or R 70 , R 71 and R 72In the case of forming a heteroaromatic ring having a nitrogen atom in the formula, examples include imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidinyl derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine

[0063] The invention also includes but is not limited to pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine 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, guanosine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, etc.

[0272] As mentioned above, as X A - Examples of the non-nucleophilic counter ions include halide ions such as chloride ion and bromide ion, fluoroalkylsulfonate ions such as trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion, arylsulfonate ions such as toluenesulfonate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion, alkylsulfonate ions such as methanesulfonate ion and butanesulfonate ion, Examples of the present invention include imidic acid ions such as bis(trifluoromethylsulfonyl)imide ion, bis(perfluoroethylsulfonyl)imide ion, and bis(perfluorobutylsulfonyl)imide ion; methylated acid ions such as tris(trifluoromethylsulfonyl)methide ion and tris(perfluoroethylsulfonyl)methide ion; and further examples thereof include sulfonate ions substituted with fluorine at the α-position as represented by the following general formula (8); and sulfonate ions substituted with fluorine at the α- and β-positions as represented by the following general formula (9).

[0273] [Chemistry 29]

[0274]

[0275] In the above general formula (8), R 81 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 23 carbon atoms, an acyl group, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group. 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.

[0276] Specific examples of the thermal acid generator include the following, but the thermal acid generator is not limited to these.

[0277] [Chemistry 30]

[0278]

[0279] The (C) 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 (A) metal-containing film-forming compound. If it is 0.05 parts or more, the acid generation amount or cross-linking reaction becomes sufficient, and if it is 30 parts or less, the risk of mixing caused by the acid moving to the upper layer resist is reduced.

[0280] [(D) Photoacid generator]

[0281] The metal-containing film-forming composition of the present invention may contain (D) a photoacid generator in order to appropriately adjust the pattern shape of the resist upper layer film, exposure sensitivity, etc. The photoacid generator may be used alone or in combination of two or more.

[0282] As the photoacid generator, for example, those described in paragraphs

[0160] to

[0179] of Japanese Patent Application Publication No. 2009-126940 can 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 (A) metal-containing film-forming compound. If the amount of the photoacid generator added is within the above range, the resolution is good, and there is no concern of the problem of foreign matter generated after the resist is developed or peeled off.

[0283] [(E) Cross-linking agent]

[0284] Furthermore, the metal-containing film-forming composition of the present invention may contain (E) a crosslinking agent in order to improve the curability and further suppress the intermixing with the resist upper layer film.

[0285] As a crosslinking agent, there is no particular limitation, and known crosslinking agents of various systems can be widely used. As an example, melamine crosslinking agents, glycoluril crosslinking agents, benzoguanamine crosslinking agents, urea crosslinking agents, β-hydroxyalkylamide crosslinking agents, isocyanurate crosslinking agents, aziridine crosslinking agents, oxazoline crosslinking agents, epoxy crosslinking agents, and phenol crosslinking agents can be exemplified. The above-mentioned (E) crosslinking agent can be used alone or in combination of two or more, and the amount added when the crosslinking agent is added is preferably 5 to 50 parts, more preferably 10 to 40 parts, relative to 100 parts of the above-mentioned (A) metal-containing film-forming compound. If the addition amount is 5 parts or more, sufficient curability can be exhibited, and intermixing with the upper film of the resist can be suppressed. On the other hand, if the addition amount is less than 50 parts, there will be no concern of deterioration of dry etching resistance caused by the lower ratio of the (A) metal-containing film-forming compound in the composition.

[0286] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy and / or hydroxyl-substituted melamines thereof, and partial self-condensates thereof.

[0287] Specific examples of the glycoluril-based crosslinking agent include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensates thereof.

[0288] Specific examples of the benzoguanamine-based crosslinking agent include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy and / or hydroxyl-substituted products thereof, and partial self-condensates thereof.

[0289] Specific examples of the urea crosslinking agent include dimethoxymethylated dimethoxyethylene urea, alkoxy and / or hydroxyl substitution products thereof, and partial self-condensates thereof.

[0290] Specific examples of the β-hydroxyalkylamide crosslinking agent include N,N,N′,N′-tetrakis(2-hydroxyethyl)adipamide.

[0291] Specific examples of the isocyanurate-based crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate.

[0292] Specific examples of the aziridine crosslinking agent include 4,4′-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0293] Specific examples of the oxazoline crosslinking agent include 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.

[0294] 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.

[0295] Specific examples of the phenolic crosslinking agent include compounds represented by the following general formula (10).

[0296] [Chemistry 31]

[0297]

[0298] (wherein, Q is a single bond, or a q 1 Hydrocarbyl with valence R 16 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 1 is an integer from 1 to 5.)

[0299] Q is a single bond, or a carbon number of 1 to 20 1 Hydrocarbyl with valence. 1 is an integer of 1 to 5, more preferably 2 or 3. Specific examples of Q include methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. 16 It is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosyl, and it is preferably a hydrogen atom or a methyl group.

[0300] As examples of the compound represented by the general formula (10), the following compounds can be specifically exemplified. Among them, from the viewpoint of improving the hardening property 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.

[0301] [Chemistry 32]

[0302]

[0303] [Chemistry 33]

[0304]

[0305] (Where R 16 As above.)

[0306] [(F) Surfactant]

[0307] The metal-containing film-forming composition of the present invention may contain (F) a surfactant in order to improve the coating properties in spin coating. The surfactant may be used alone or in combination of two or more.

[0308] As a surfactant, for example, those described in paragraphs

[0142] to

[0147] of Japanese Patent Publication No. 2009-269953 can be used. When a surfactant is added, the amount added is preferably 0.001 to 20 parts, more preferably 0.01 to 10 parts, relative to 100 parts of the metal-containing film-forming compound (A). If it is within such a range, the coating property is surely improved, and a thin and uniform close-contact film can be formed.

[0309] [Plasticizer]

[0310] In addition, a plasticizer may be added to the metal-containing film-forming composition of the present invention. As a plasticizer, there is no particular limitation, and plasticizers of various known systems can be widely used. As an 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 recorded in Japanese Patent Publication No. 2013-253227 can be exemplified. The amount of the added plasticizer is preferably 1% to 500% by mass relative to 100 parts of the metal-containing film-forming compound (A) above. If the amount added is in such a range, the pattern is excellent in filling and homogenization.

[0311] <Method for Forming Metal-Containing Film>

[0312] The present invention can form a metal-containing film as, for example, a resist underlayer film of a multilayer resist film used in photolithography using the metal-containing film-forming composition.

[0313] The method for forming a resist lower film using the metal-containing film-forming composition of the present invention is to apply the above-mentioned metal-containing film-forming composition on a processed substrate by spin coating or the like. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote a cross-linking reaction in order to prevent intermixing with the resist upper film. The baking is preferably performed at a temperature of 100°C to 450°C for 10 to 600 seconds, and more preferably at a temperature of 200°C to 300°C for 10 to 300 seconds. If the influence of equipment damage or deformation on the wafer is taken into consideration, the upper limit of the heating temperature in the wafer process of photolithography is preferably below 450°C, and more preferably below 300°C.

[0314] In addition, the method for forming an anti-etching underlayer film using the metal-containing film-forming composition of the present invention can also coat the metal-containing film-forming composition of the present invention on a processed substrate by the same spin coating method as mentioned above, and calcine the above-mentioned metal-containing film-forming composition in an 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.

[0315] By calcining the metal-containing film-forming composition of the present invention in such an oxygen atmosphere, a sufficiently hardened film can be obtained. The baking environment may be air, and N is sealed in order to reduce oxygen. 2 Inert gases such as Ar and He are preferably used to prevent oxidation of the metal-containing film. In order to prevent oxidation, the oxygen concentration needs to be controlled, preferably below 1000ppm, more preferably below 100ppm (volume basis). If oxidation of the metal-containing film during baking is prevented, there will be no increase in absorption or reduction in etching resistance, which is more ideal.

[0316] 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.

[0317] <Pattern Formation Method Using Metal-Containing Film-Forming Composition>

[0318] In addition, the present invention provides a pattern forming method as a pattern forming method of a two-layer resist process using the metal-containing film-forming composition of the present invention, which is a method for forming a pattern on a substrate to be processed, comprising the following steps:

[0319] (I-1) After applying the metal-containing film-forming composition of the present invention on a substrate to be processed, heat treatment is performed to form a metal-containing film.

[0320] (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material,

[0321] (I-3) after exposing the resist upper layer film to a pattern, developing the resist upper layer film with a developer to form a pattern on the resist upper layer film,

[0322] (I-4) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching, and

[0323] (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.

[0324] Since the resist upper film in the above two-layer resist process exhibits etching resistance due to chlorine-based gas, it is more ideal to use etching gas mainly composed of chlorine-based gas to perform dry etching of the metal-containing film using the resist upper film as a mask in the above two-layer resist process. Since the metal-containing film exhibits etching resistance due to fluorine-based gas, it is more ideal to use etching gas mainly composed of fluorine-based gas to perform dry etching of the processed substrate using the metal-containing film as a mask.

[0325] In addition, the present invention provides a pattern forming method as a pattern forming method of a three-layer resist process using the metal-containing film-forming composition of the present invention, which is a method for forming a pattern on a processed substrate, comprising the following steps:

[0326] (II-1) forming a resist underlayer film on a substrate to be processed,

[0327] (II-2) After coating the metal-containing film-forming composition of the present invention on the resist underlayer film, a metal-containing film is formed by heat treatment.

[0328] (II-3) forming a resist upper layer film on the metal-containing film using a photoresist material,

[0329] (II-4) After exposing the resist upper layer film to a pattern, developing the resist upper layer film with a developer to form a pattern on the resist upper layer film,

[0330] (II-5) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching,

[0331] (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,

[0332] (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.

[0333] Since the metal-containing film formed by the metal-containing film-forming composition of the present invention used as the intermediate film of the above three-layer resist process exhibits etching resistance by oxygen-based gases, it is more preferable to use an etching gas mainly composed of oxygen-based gases to dry-etch the organic resist lower film using the metal-containing film as a mask in the above three-layer resist process. Since the organic lower film exhibits etching resistance by fluorine-based gases, it is more preferable to use an etching gas mainly composed of fluorine-based gases to dry-etch the substrate to be processed using the organic lower film as a mask.

[0334] In the above pattern forming method, the resist upper layer film may be either positive or negative, and the same photoresist composition as commonly used may be used. When the resist upper layer film is formed by the above photoresist composition, spin coating is preferably used.

[0335] When the photoresist composition is used to form the resist upper film by spin coating, a pre-bake is performed after the resist is applied, preferably at 60 to 180° C. for 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, but is preferably 10 to 500 nm, and particularly preferably 20 to 400 nm.

[0336] Examples of the exposure light include high energy rays having a wavelength of 300 nm or less, and specific examples include extreme ultraviolet rays, 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.

[0337] As a method for forming a pattern of the resist upper layer film, optical lithography with a wavelength of 5 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof is preferably used.

[0338] In addition, the development method in the above-mentioned pattern forming method is preferably alkali development or development using an organic solvent.

[0339] Then, the obtained resist pattern is used as a mask for etching. For example, in the two-layer resist process, the etching of the metal-containing film 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. Then, 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 by a conventional method. For example, if the processed object is SiO 2 For low-dielectric-constant insulating films based on SiN and silicon dioxide, etching is performed mainly using a chlorofluorocarbon-based gas.

[0340] The metal-containing film obtained by using the metal-containing film-forming composition of the present invention has a characteristic of being excellent in etching resistance when etching such a workpiece.

[0341] As the organic resist underlayer film material that can be used in the above-mentioned resist underlayer film, those known as underlayer films for three-layer resist method or two-layer resist method using silicon resist composition can be exemplified. Examples include 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 Japanese Patent Application Publication No. 2004-205685, Japanese Patent Application Publication No. 2007-171895, Japanese Patent Application Publication No. 2009-14816, Japanese Patent Application Publication No. 2007-199653, Japanese Patent Application Publication No. 2008-274250, Japanese Patent Application Publication No. 2010-122656, Japanese Patent Application Publication No. 2012-214720, Japanese Patent Application Publication No. 2014- 29435, 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. Resins and compositions disclosed in Japanese Patent Application No. 2006-259249, 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.

[0342] The resist underlayer film can be formed on the substrate by spin coating, etc., similarly to the photoresist composition, using a composition solution containing the organic resist underlayer film material. After the organic resist underlayer film is formed by spin coating, etc., it is desirable to bake it in order 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.

[0343] An organic hard mask formed by a CVD method or an ALD method may be used instead of the organic resist underlayer film material.

[0344] In the case of the three-layer resist process, the dry etching of the metal-containing film is performed by using, for example, a chlorine-based gas using the upper resist pattern as a mask. Thus, a metal-containing film pattern is formed. Then, the obtained metal-containing film pattern is used as a mask, and the resist lower film is etched using an oxygen-based gas. Thus, a resist lower film pattern is formed. Then, the obtained organic resist lower film pattern is used as a mask to perform etching processing on the processed substrate.

[0345] The metal-containing film obtained by using the metal-containing film-forming composition of the present invention has a characteristic of being excellent in etching resistance when etching these resist underlayer films.

[0346] In addition, the workpiece (work substrate) is not particularly limited, and Si, α-Si, p-Si, SiO 2 , SiN, SiON, W, TiN, Al, etc., or a substrate on which a processed layer is formed. As the processed layer, Si, SiO 2 , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si and other Low-k films and their stopper films, usually with a thickness of 50 to 10,000 nm, especially 100 to 5,000 nm. In addition, in the case of forming a processed layer, the substrate and the processed layer can be made of different materials.

[0347] Here, use Figure 1 , an example of a pattern forming method for the above three-layer resist process is described. This example is, first, as Figure 1 Generally, on the processed layer 2 of the processed substrate 10 composed of the substrate 1 and the processed layer 2 thereon, an organic resist underlayer film 3 is formed using an organic resist underlayer film material, a metal-containing film 4 is formed on the organic resist underlayer film 3 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 1As in (B), the exposed portion 6 of the resist upper film is pattern exposed. Figure 1 As in (C), the resist upper film pattern 5a is formed on the resist upper film by developing with a developer. Figure 1 As in (D), the resist upper layer film having the pattern 5a is used as a mask, and the pattern is transferred to the metal-containing film 4 by dry etching to obtain the metal-containing film pattern 4a. Then, as Figure 1 As in (E), the metal-containing film to which the pattern 4a is transferred is used as a mask, and the pattern is transferred to the organic resist lower film by dry etching to obtain the organic resist lower film pattern 3a. Figure 1 Generally, the processed layer 2 on the substrate 1 is processed using the organic resist underlayer film on which the pattern 3 a is formed as a mask, thereby forming a pattern 2 a on the processed substrate 10 .

[0348] In addition, use Figure 2 , an example of a pattern forming method for the above-mentioned two-layer resist process is described. This example is, first, as Figure 2 In the same manner as in (G), on the processed layer 2 of the processed substrate 10 composed of the substrate 1 and the processed layer 2 thereon, a metal-containing film 4 is formed 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 As in (H), the exposed portion 6 of the resist upper film is pattern exposed. Figure 2 As in (I), the resist upper film pattern 5a is formed on the resist upper film by developing with a developer. Figure 2 As in (J), the resist upper layer film having the pattern 5a is used as a mask, and the pattern is transferred to the metal-containing film 4 by dry etching to obtain the metal-containing film pattern 4a. Figure 2 Generally, the metal-containing film on which the pattern 4 a is formed is used as a mask to process the layer 2 on the substrate 1 , thereby forming a pattern 2 a on the substrate 10 .

[0349] Example

[0350] Hereinafter, the present invention will be described in more detail with reference to synthesis examples, comparative synthesis examples, working examples, and comparative examples, but the present invention is not limited thereto.

[0351] [(A) Synthesis Example of Metal-Containing Film-Forming Compound]

[0352] The following synthesis examples used the organic group raw material group G: (G1) to (G15) and the silicon-containing organic group raw material group H: (H1) to (H2) shown below.

[0353] The raw material group G: (G1) to (G15) and the raw material group H: (H1) to (H2) are as follows.

[0354] [Chemistry 34]

[0355]

[0356] [Chemistry 35]

[0357]

[0358] As the metal source M, the following metal compounds were used.

[0359] (M1): Titanium tetraisopropoxide (Sigma-Aldrich Corp, 377996)

[0360] (M2): Hf(OBu) 4 :Hafnium(IV)-butoxide (Sigma-Aldrich Corp, 667943)

[0361] (M3): Zr(OBu) 4 : Zirconium (IV) tetrabutoxide (80 mass % 1-butanol solution) (Tokyo Chemical Industry Co., Ltd., Z0016)

[0362] [Synthesis Example 1] Synthesis of Metal-Containing Film-Forming Compound (A-1)

[0363] Under a nitrogen environment, 28.4 g of titanium tetraisopropoxide (M1) 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. 15.8 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 further heated to 60°C and continued to be heated under reduced pressure until no distillate was produced. When no distillate was observed, 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, thereby obtaining a PGMEA / PGME solution of a metal-containing film-forming compound (A-1).

[0364] [Synthesis of Compounds (A-2) to (A-3)]

[0365] Except for using the metal source M and the compound group G in the amounts shown in Table 1, the same reaction conditions as those in Synthesis Example 1 were followed to obtain compounds (A-2) to (A-3) shown in Table 1.

[0366] [Table 1]

[0367]

[0368] [Synthesis Example 2] Synthesis of Metal-Containing Film-Forming Compound (A-4)

[0369] Under nitrogen environment, 47.9 g of zirconium (IV) tetrabutoxide (M3) was dissolved in 65.9 g of PGMEA / PGME (weight ratio 70 / 30) solution, and the reaction temperature was raised to 60°C while stirring. A mixture obtained by suspending 18.6 g of compound G4 in 27.5 g of PGMEA / PGME (weight ratio 70 / 30) solution was added to the above reaction system, and the reaction temperature was maintained at 60°C and stirred for 1 hour. After cooling to room temperature, the obtained reaction solution was filtered with a 0.45 μm PTFE filter to obtain a PGMEA / PGME solution of a metal-containing film-forming compound (A-4).

[0370] [Synthesis of Compounds (A-5) to (A-11)]

[0371] Except for using the metal source M and the compound group G in the amounts shown in Table 2, the same reaction conditions as in Synthesis Example 2 were followed to obtain compounds (A-5) to (A-11) shown in Table 2.

[0372] [Table 2]

[0373]

[0374]

[0375] [Synthesis Example 3] Synthesis of Metal-Containing Film-Forming Compound (A-12)

[0376] Under a nitrogen environment, 12.0 g of zirconium (IV) tetrabutoxide (M3) was dissolved in 16.5 g of PGMEA / PGME (weight ratio 70 / 30) solution, and the reaction temperature was raised to 50°C while stirring, and 6.8 g of compound H1 was added dropwise to the above solution. After the addition, the reaction temperature was set to 60°C and stirring was continued for 2 hours. Then, a mixture in which 5.0 g of compound G3 was suspended in 6.8 g of PGMEA / PGME (weight ratio 70 / 30) solution was added to the above reaction system, and the reaction temperature was maintained at 60°C and stirring was continued for 1 hour. After cooling to room temperature, the obtained reaction solution was filtered with a 0.45 μm PTFE filter to obtain a PGMEA / PGME solution of a metal-containing film-forming compound (A-12).

[0377] [Synthesis of Compounds (A-13) to (A-14) and Comparative Example Compounds (R-1) to (R-4)]

[0378] Except for using the above-mentioned metal source M, the above-mentioned compound group G and the above-mentioned compound group H in the addition amounts shown in Table 3, the compounds (A-13) to (A-14) and comparative example compounds (R-1) to (R-4) shown in Table 3 were obtained under the same reaction conditions as in Synthesis Example 3.

[0379] [Table 3]

[0380]

[0381] Preparation of metal-containing film-forming compositions (MUL-1 to 19, comparative MUL-1 to 4)

[0382] In the preparation of the metal-containing film-forming composition, the metal-containing film-forming compounds (A-1) to (A-14), (AG1) as a thermal acid generator, (AG2) as a photoacid generator, (XL1) to (XL2) as crosslinking agents, and (F1: ethylene glycol dibenzyl ether: boiling point 364° C.) as a high boiling point solvent were used. After being dissolved in an organic solvent in the proportions shown in Table 4, the mixture was filtered through a 0.1 μm fluororesin filter to prepare metal-containing film-forming compositions (MUL-1 to 19, comparative MUL-1 to 4).

[0383] [Chemistry 36]

[0384]

[0385] [Table 4]

[0386]

[0387]

[0388] [Example 1: Contact angle evaluation]

[0389] The metal-containing film-forming compositions prepared above (MUL-1 to 19, comparative examples MUL-1 to 4) were applied on a silicon substrate and calcined at 250° C. for 60 seconds to prepare metal-containing films with a thickness of 45 nm. The contact angle (CA1) with pure water was measured for each cured film.

[0390] The results are shown in Table 5 below.

[0391] [Table 5]

[0392]

[0393]

[0394] As shown in Table 5, it can be seen that the metal-containing film-forming compositions (MUL-1 to 19) of the present invention having a cyclic ether structure all become films having a contact angle of more than 60° for pure water, and good adhesion to the resist pattern can be expected. In particular, it can be seen that the metal-containing film-forming compositions using compounds having an epoxy or oxetane structure have high contact angles. In addition, it can be seen that the contact angles of Examples 1-15 and 1-17 to 1-18 using compositions containing a thermal acid generator (AG1) are high. Although the effect is still uncertain, it is speculated that the hardening is accelerated by the ring-opening reaction of the epoxy or oxetane structure due to the action of the acid generator.

[0395] On the other hand, the metal-containing film-forming compositions of the comparative examples not having a cyclic ether structure (Comparative Examples MUL-1 to 4) had low contact angles, and thus it was expected that the adhesion to the resist pattern was insufficient.

[0396] [Example 2: Evaluation of optical constants (n / k)]

[0397] The metal-containing film-forming composition (MUL-2~19, comparison examples MUL-1~4) was coated on a silicon substrate and calcined at 250°C for 60 seconds. The optical constants (refractive index n, extinction coefficient k) at a wavelength of 193nm were obtained using a variable incident angle ellipsometer (VASE) manufactured by JA Woollam. The results are summarized in Table 6.

[0398] [Table 6]

[0399]

[0400]

[0401] As shown in Table 6, the metal-containing film-forming compositions (MUL-2 to 19) of the present invention containing hafnium and zirconium all have n values ​​of 1.8 or more and k values ​​between 0.1 and 0.5. Regarding the optical constants, although it also depends on the film thickness, the type of the upper film, etc., if the n value is generally between 1.8 and 2.3 and the k value is between 0.1 and 0.5, even in the case where a metal-containing film is formed as a thin film of less than 20 nm, the reflected light from the substrate during ArF immersion and high NA exposure can be suppressed to a considerable extent, and it can be suitable for use as a lower film for photoresist patterning. In the above examples, the optical constants are all within the appropriate range, and it can be seen that they can be used as resist lower films for photoresist patterning. On the other hand, Comparative Examples 2-3 and 2-4 may have more organic components in the metal-containing film, and the n value is less than 1.8, and it is expected that the performance of suppressing the reflected light from the substrate during ArF immersion and high NA exposure is not sufficient.

[0402] [Example 3: Etching resistance evaluation]

[0403] The metal-containing film-forming composition (MUL-1 to 19, and comparative examples MUL-1 to 4) was applied to a silicon substrate and heated at 250°C for 60 seconds using a hot plate to form a metal-containing film (thickness a) with a film thickness of 50 nm. Comparative Example 3-5 The following silicon-containing resist interlayer material (SOG-1) was applied and baked at 220°C for 60 seconds to form a resist interlayer with a film thickness of 50 nm.

[0404] As an anti-etching intermediate film material (SOG-1) containing silicon atoms, a polymer represented by ArF silicon-containing intermediate film polymer (SiP1) and a thermal cross-linking catalyst (CAT1) are dissolved in a solvent containing 0.1% by mass of FC-4430 (produced by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 7, and filtered through a fluororesin filter with a pore size of 0.1 μm to prepare an anti-etching intermediate film material (SOG-1) containing silicon atoms.

[0405] [Table 7]

[0406]

[0407] The structural formulas of the ArF silicon-containing interlayer polymer (SiP1) and the thermal crosslinking catalyst (CAT1) used are shown below.

[0408] [Chemistry 37]

[0409]

[0410] In Comparative Example 3-6, the following organic resist underlayer film material (SOC-1) was applied and baked at 350° C. for 60 seconds to form a resist underlayer film with a film thickness of 50 nm.

[0411] As an organic resist underlayer film material (SOC-1), a polymer represented by an organic underlayer film polymer (CP1) was dissolved in a solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 8, and the solution was filtered through a fluororesin filter having a pore size of 0.1 μm to prepare an organic resist underlayer film material (SOC-1).

[0412] [Table 8]

[0413]

[0414] The structural formula of the organic underlayer film polymer (CP1) used is shown below.

[0415] [Chemistry 38]

[0416]

[0417] Mw = 7,000, Mw / Mn = 3.50

[0418] Then, CF was used using the etching device CE-300I manufactured by ULVAC under the following conditions. 4 Gas and O 2 Each gas was used to perform etching and the film thickness b was measured. The film thickness etched in one minute was calculated from the film thickness (film thickness b - film thickness a) etched for a specified time using each gas as the etching rate (nm / min).

[0419] For CF 4 The gas etching rate was judged as “A (very good)” if it was 20 nm / min or less, “B (good)” if it was 20 nm / min to 30 nm / min, and “C (poor)” if it was 30 nm / min or more. The results are shown in Table 9.

[0420] For O 2 The gas etching rate was judged as “A (very good)” if it was 20 nm / min or less, “B (good)” if it was 20 nm / min to 30 nm / min, and “C (poor)” if it was 30 nm / min or more. The results are shown in Table 9.

[0421] CF 4 Gas Dry Etching Conditions

[0422] Pressure: 3Pa

[0423] Antenna RF power: 100W

[0424] Bias RF power: 15W

[0425] CF 4 Gas flow rate: 15sccm

[0426] Time: 30 seconds

[0427] Take O 2 Gas Dry Etching Conditions

[0428] Pressure: 3Pa

[0429] Antenna RF power: 300W

[0430] Bias RF power: 10W

[0431] O 2 Gas flow rate: 25sccm

[0432] Time: 30 seconds

[0433] [Table 9]

[0434]

[0435]

[0436] As shown in Table 9, it can be seen that the metal-containing film-forming compositions (MUL-1 to 19) of the present invention all show good 4 Gas and O 2 Compared with SOG-1 used in Comparative Example 3-5, due to the use of O 2 Since it has excellent resistance to gas etching, it can be said that it is suitable for use in a three-layer resist process in which a resist pattern is transferred to a processed substrate in combination with an organic resist underlayer film. 4 Since it has excellent gas etching resistance, it can be said that it is suitable for use in a two-layer resist process in which a resist pattern is transferred to a substrate to be processed in combination with a photoresist upper layer film.

[0437] [Example 4: Pattern Formation Method]

[0438] The above-mentioned SOC-1 was used as an organic lower film on a substrate, and was applied by spin coating on a Si wafer, and baked at 350°C for 60 seconds to form a carbon film with a thickness of 60 nm. The carbon ratio of the carbon film is 46 atomic%, and the optical constant (n / k) at a wavelength of 193 nm is 1.42 / 0.50. A composition obtained by diluting a metal-containing film-forming composition (MDL-3 to 19, and comparative examples MDL-1 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 15 nm. An ArF single-layer resist of the resist upper film material was applied thereon, and baked at 105°C for 60 seconds to form a photoresist film with a thickness of 100 nm. A wet protection film material (TC-1) was applied on the photoresist film and baked at 90° C. for 60 seconds to form a protection film with a film thickness of 50 nm.

[0439] As an anti-etching agent upper layer film material (single-layer anti-etching agent for ArF), a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) are dissolved in a solvent containing 0.1% by mass of a surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) at a ratio as shown in Table 10, and the mixture is filtered through a 0.1 μm fluororesin filter to prepare the material.

[0440] [Table 10]

[0441]

[0442] The polymer (RP1), the acid generator (PAG1), and the basic compound (Amine1) used in the resist upper layer film material (ArF single-layer resist) are shown below.

[0443] [Chemistry 39]

[0444]

[0445] As a wet protective film material (TC-1), the protective film polymer (PP1) was dissolved in an organic solvent at a ratio in Table 11, and filtered through a 0.1 μm fluororesin filter to prepare the wet protective film material (TC-1).

[0446] [Table 11]

[0447]

[0448] The protective film polymer (PP1) used in the wet protective film material (TC-1) is shown below.

[0449] [Chemistry 40]

[0450]

[0451] Then, the film was exposed using an ArF immersion exposure device (manufactured by Nikon Corporation; 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).

[0452] The reflectivity was calculated using PROLITH 2020a (Litho Tech Japan Corporation). The thickness of the metal-containing film was fixed at 10 nm, and the reflectivity of the metal-containing film was calculated when n was 1.60 to 2.20 and k was 0.15 to 0.50. The results are shown in Figure 3 The optical constant (n / k) that can reduce the reflected light from the base substrate during pattern exposure to 1.0% or less is more desirable. The pattern cross section was observed using an S-4700 (electron microscope manufactured by Hitachi, Ltd.).

[0453] The results are shown in Table 12.

[0454] Then, the resist upper film pattern is used as a mask to etch the resist intermediate film by dry etching to form a hard mask pattern, the obtained hard mask pattern is used as a mask to etch the organic lower film to form a pattern, and the obtained resist lower film pattern is used as a mask to perform SiO 2 The film was etched and the etching conditions were as follows.

[0455] The pattern cross section was observed by S-4700 (electron microscope manufactured by Hitachi, Ltd.). The results are shown in Table 12.

[0456] Transfer conditions of the hard mask pattern to the metal-containing film (resist intermediate film).

[0457] By Cl 2 Gas Dry Etching Conditions

[0458] Pressure: 1Pa

[0459] Antenna RF power: 320W

[0460] Bias RF power: 30W

[0461] Cl 2 Gas flow rate: 25sccm

[0462] Time: 15 seconds

[0463] Transfer conditions of the resist interlayer film pattern to the organic underlayer film.

[0464] By O 2 Gas Dry Etching Conditions

[0465] Pressure: 1Pa

[0466] Antenna RF power: 300W

[0467] Bias RF power: 10W

[0468] O 2 Gas flow rate: 25sccm

[0469] Time: 20 seconds

[0470] Resist underlayer pattern for SiO 2 Membrane transfer conditions.

[0471] By CF 4 Gas Dry Etching Conditions

[0472] Pressure: 1Pa

[0473] Antenna RF power: 100W

[0474] Bias RF power: 15W

[0475] CF 4 Gas flow rate: 15sccm

[0476] Time: 60 seconds

[0477] [Table 12]

[0478]

[0479] As shown in Table 12, it is confirmed that the metal-containing film-forming composition (MUL-3~19) of the present invention all have good pattern shapes after development. The metal-containing film material of the present invention contains a cyclic ether structure, so it has high adhesion to the resist pattern. In addition, it has an optical constant that can sufficiently reduce the substrate reflected light during pattern exposure, so it is estimated that a good resist pattern can be obtained. In addition, after the substrate is transferred and etched, the resist upper film pattern is finally well transferred to the substrate, confirming that it is suitable for use in micro-processing by the multilayer resist method. In contrast, the metal-containing film-forming composition (Comparative Examples MUL-1~4) of Example 1, which has a low contact angle in the contact angle evaluation, was observed to have a collapse of the resist upper film pattern after development.

[0480] As described above, the metal-containing film-forming compound of the present invention, the composition using the compound, and the pattern forming method have high adhesion with the resist upper film pattern and have the effect of suppressing the collapse of the fine pattern, and give the resist upper film a pattern shape with high rectangularity. Therefore, it is particularly suitable for use in a multilayer resist process and is extremely useful in fine patterning for semiconductor device manufacturing.

[0481] This specification includes the following inventions.

[0482] [1]: A metal-containing compound for forming a film, characterized in that the metal-containing compound for forming a film has at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and a multidentate ligand having a cyclic ether structure having 2 to 13 carbon atoms coordinated to the metal atom.

[0483] [2]: The metal-containing film-forming compound according to [1], wherein the multidentate ligand is a structure represented by the following general formulas (1-A) to (1-D):

[0484] [Chemistry 41]

[0485]

[0486] In the above general formulas (1-A) to (1-D), R 1 ~R 4 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, R 5 ~R6 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, R 7 ~R 10 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, R 11 is a monovalent organic group having 1 to 20 carbon atoms which may also contain a cyclic ether structure having 2 to 13 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms; the compounds of the above general formulae (1-A) to (1-D) contain at least one cyclic ether structure having 2 to 13 carbon atoms; in the above general formula (1-A), R 2 With R 3 They may also be bonded to each other to form a cyclic ether structure with 2 to 13 carbon atoms; in the above general formula (1-B), adjacent R 5 With R 6 They may also be bonded to each other to form an unsaturated or saturated ring structure; in the above general formula (1-C), adjacent R 8 With R 9 They may be bonded to each other to form a cyclic ether structure having 2 to 13 carbon atoms, or an unsaturated or saturated ring structure.

[0487] [3]: The metal-containing film-forming compound according to [2], wherein the multidentate ligand has a structure represented by the above formula (1-A) or (1-B).

[0488] [4]: The metal-containing film-forming compound according to any one of [1] to [3], wherein the cyclic ether structure is any one of the structures represented by the following formulae (a-1) to (a-2):

[0489] [Chemistry 42]

[0490]

[0491] In the formula, R a It is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and * represents a bonding part.

[0492] [5]: A metal-containing film-forming compound as described in any one of [2] to [4], wherein the metal-containing film-forming compound is a reaction product of a metal compound represented by the following formula (2), a hydrolyzate or condensate of a metal compound represented by the following formula (2), or a metal-containing compound of any one of the hydrolyzates and condensates thereof, and a multidentate ligand having a structure represented by the general formula (1-A) to (1-D):

[0493] [Chemistry 43]

[0494] L a MX b (2)

[0495] In the formula, M is any one of Ti, Zr, and Hf; L is a monodentate ligand and / or a polydentate ligand having 1 to 30 carbon atoms; X is selected from a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR a R b The hydrolyzable group R a and R b Each is independently 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.

[0496] [6]: The metal-containing film-forming compound according to [5], wherein the metal compound represented by the formula (2) has a structure of the following formula (3);

[0497] [Chemistry 44]

[0498] M(OR 1A ) 4 (3)

[0499] Wherein, M is Ti, Zr, or Hf, R 1A It is a monovalent organic group having 1 to 20 carbon atoms.

[0500] [7]: The metal-containing film-forming compound according to any one of [1] to [6], wherein the metal-containing film-forming compound further contains a ligand derived from a silicon compound represented by the following general formula (4):

[0501] [Chemistry 45]

[0502]

[0503] In the general formula (4), R 3A , R 3B and R 3C Any one of an 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 a crosslinking group having any of the structures represented by the following general formulae (b-1) to (b-3);

[0504] [Chemistry 46]

[0505]

[0506] In the general formulas (b-1) to (b-3), R 3 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.

[0507] [8]: A metal-containing film-forming composition, characterized in that it contains: (A) the metal-containing film-forming compound according to any one of [1] to [7], and (B) an organic solvent.

[0508] [9]: The metal-containing film-forming composition according to [8], wherein the composition contains one or more of (C) a thermal acid generator and (D) a photoacid generator.

[0509]

[10] : The metal-containing film-forming composition according to [8] or [9], further comprising one or more of (E) a cross-linking agent and (F) a surfactant.

[0510]

[11] : A metal-containing film-forming composition as described in any one of [8] to

[10] , wherein the (B) organic solvent is 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 more.

[0511]

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

[0512] (I-1) After coating a metal-containing film-forming composition as described in any one of [8] to

[11] on a substrate to be processed, heat treatment is performed to form a metal-containing film;

[0513] (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material,

[0514] (I-3) after exposing the resist upper layer film to a pattern, developing the resist upper layer film with a developer to form a pattern on the resist upper layer film,

[0515] (I-4) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching, and

[0516] (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.

[0517]

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

[0518] (II-1) forming a resist underlayer film on a substrate to be processed,

[0519] (II-2) coating the metal-containing film-forming composition as described in any one of [8] to

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

[0520] (II-3) forming a resist upper layer film on the metal-containing film using a photoresist material,

[0521] (II-4) After exposing the resist upper layer film to a pattern, developing the resist upper layer film with a developer to form a pattern on the resist upper layer film,

[0522] (II-5) using the patterned resist upper layer film as a mask, transferring the pattern to the metal-containing film by dry etching,

[0523] (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,

[0524] (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.

[0525] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any device having substantially the same configuration and exhibiting the same functions and effects as the technical concept described in the claims of the present invention is included in the technical scope of the present invention.

[0526] Description of Reference Numerals

[0527] 1:Substrate

[0528] 2: Processing layer

[0529] 2a: Pattern (pattern formed on the processed layer)

[0530] 3: Organic resist lower film

[0531] 3a: Organic resist lower film pattern

[0532] 4: Metal-containing films

[0533] 4a: Metal-containing film pattern

[0534] 5: Resist upper film

[0535] 5a: Resist upper film pattern

[0536] 6: Exposure part

[0537] 10: Processed substrate

Claims

1. A metal-containing film-forming compound, characterized in that: The metal-containing film-forming compound has at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and a multidentate ligand having a cyclic ether structure having 2 to 13 carbon atoms coordinated to the metal atom.

2. The metal-containing film-forming compound according to claim 1, wherein The multidentate ligand is a structure represented by the following general formulas (1-A) to (1-D): In the above general formulae (1-A) to (1-D), R1 to R4 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, R5 to R6 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, and R7 to R8 are 10 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a cyclic ether structure having 2 to 13 carbon atoms, R 11 is a monovalent organic group having 1 to 20 carbon atoms which may also contain a cyclic ether structure having 2 to 13 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms; the compounds of the above general formulas (1-A) to (1-D) contain at least one cyclic ether structure having 2 to 13 carbon atoms; in the above general formula (1-A), R2 and R3 may be bonded to each other to form a cyclic ether structure having 2 to 13 carbon atoms; in the above general formula (1-B), adjacent R5 and R6 may be bonded to each other to form an unsaturated or saturated ring structure; in the above general formula (1-C), adjacent R8 and R9 may be bonded to each other to form a cyclic ether structure having 2 to 13 carbon atoms, or an unsaturated or saturated ring structure.

3. The metal-containing film-forming compound according to claim 2, wherein The multidentate ligand is a structure represented by the above formula (1-A) or (1-B).

4. The metal-containing film-forming compound according to claim 1, wherein The cyclic ether structure is any one of the structures represented by the following formulae (a-1) to (a-2): In the formula, R a It is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and * represents a bonding part.

5. The metal-containing film-forming compound according to claim 2, wherein The metal-containing film-forming compound is a reaction product of a metal compound represented by the following formula (2), a hydrolyzate or condensate of the metal compound represented by the following formula (2), or a metal-containing compound of any of the hydrolysis-condensates thereof, and a multidentate ligand having a structure represented by the general formulas (1-A) to (1-D): a MXb(2) In the formula, M is any one of Ti, Zr, and Hf; L is a monodentate ligand and / or a polydentate ligand having 1 to 30 carbon atoms; X is selected from a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NRaR b The hydrolyzable groups Ra and R b Each is independently 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.

6. The metal-containing film-forming compound according to claim 5, wherein The metal compound represented by the formula (2) has a structure of the following formula (3): M(OR1A)4(3) wherein M is Ti, Zr, or Hf, and R 1A It is a monovalent organic group having 1 to 20 carbon atoms.

7. The metal-containing film-forming compound according to claim 1, wherein The metal-containing film-forming compound further contains a ligand derived from a silicon compound represented by the following general formula (4): In the general formula (4), R 3A , R 3B and R 3C Any one of an 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 a crosslinking group having any of the structures represented by the following general formulae (b-1) to (b-3); In the general formulae (b-1) to (b-3), R3 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.

8. A metal-containing film-forming composition, characterized in that: contain: (A) the metal-containing film-forming compound according to any one of claims 1 to 7, and (B) Organic solvent.

9. The metal-containing film-forming composition according to claim 8, wherein The composition contains one or more of (C) a thermal acid generator and (D) a photoacid generator.

10. The metal-containing film-forming composition according to claim 8, wherein The composition further contains one or more of (E) a crosslinking agent and (F) a surfactant.

11. The metal-containing film-forming composition according to claim 8, wherein The (B) organic solvent is 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.

12. A method for forming a pattern on a processed substrate, comprising the following steps: (I-1) After coating the metal-containing film-forming composition according to claim 8 on a substrate to be processed, heat treatment is performed to form a metal-containing film. (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) after exposing the resist upper layer film to a pattern, developing the resist upper layer film 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, comprising the following steps: (II-1) forming a resist underlayer film on a substrate to be processed, (II-2) coating the metal-containing film-forming composition according to claim 8 on the resist underlayer film, and then performing a heat treatment to form a metal-containing film; (II-3) forming a resist upper layer film on the metal-containing film using a photoresist material, (II-4) After exposing the resist upper layer film to a pattern, developing the resist upper layer film 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.

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