Compound for forming metal-containing film, composition for forming metal-containing film, method for producing compound for forming metal-containing film, and pattern formation method

Abstract

To provide a compound for forming a metal-containing film having excellent dry-etching resistance to a conventional organic underlay film material and having together high filling characteristics and / or high flattening property.SOLUTION: (A) A metal-containing film forming compound derived from a metal-containing compound obtained by hydrolyzing or condensing, or hydrolysis condensing the metal compound represented by formula (A-1), further having a ligand derived from an organic compound represented by the following formula (1). M(OR1A)4(A-1) [M is Ti, Zr, Hf] R2ACOXCOOH (1) [R2A is a divalent organic group containing at least one of a crosslinking group represented by any one of (a-1)-(a-4), and X is a divalent organic group].SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a compound for forming a metal-containing film, a composition for forming a metal-containing film, a method for producing the compound for forming a metal-containing film, and a method for forming a pattern. [Background technology]

[0002] As LSIs become more highly integrated and faster, pattern dimensions are becoming finer. Lithography technology has achieved the formation of finer patterns by shortening the wavelength of light sources and selecting appropriate resist compositions to match them, in line with this trend. The core of this technology is a positive photoresist composition used in a single layer. This single-layer positive photoresist composition has a skeleton in the resist resin that is resistant to dry etching using chlorine- or fluorine-based gas plasma, and also has a switching mechanism that dissolves the exposed areas, forming a pattern by dissolving the exposed areas, and then dry etching the substrate using the remaining resist pattern as an etching mask.

[0003] However, when the thickness of the photoresist film used is kept the same and the pattern is made finer, that is, when the pattern width is made smaller, the resolution performance of the photoresist film is reduced, and when the photoresist film is pattern-developed using a developer, the so-called aspect ratio becomes too large, resulting in problems such as pattern collapse. For this reason, the photoresist film has been made thinner as the pattern becomes finer.

[0004] On the other hand, in the processing of a substrate to be processed, a method is usually used in which a photoresist film on which a pattern is formed is used as an etching mask to process the substrate by dry etching, but in reality, there is no dry etching method that can obtain perfect etching selectivity between the photoresist film and the substrate to be processed. Therefore, there is a problem that the photoresist film is also damaged and collapsed during processing of the substrate, and the resist pattern cannot be accurately transferred to the substrate to be processed. Therefore, with the miniaturization of patterns, a higher dry etching resistance has been required for the resist composition. However, on the other hand, in order to increase the resolution, a resin with low light absorption at the exposure wavelength has been required for the resin used in the photoresist composition. Therefore, as the exposure light has become shorter in wavelength from i-line to KrF and ArF, the resin has also changed to novolac resin, polyhydroxystyrene, and resin with an aliphatic polycyclic skeleton, but in reality, the etching speed under dry etching conditions during substrate processing has become faster, and recent photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] For this reason, it has become necessary to dry etch the substrate to be processed using a thinner photoresist film with a weaker etching resistance, and securing the materials and processes for this processing step has become an urgent need.

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

[0007] One of the multilayer resist methods is a three-layer resist method that can be performed using a general resist composition used in a single-layer resist method. In this three-layer resist method, for example, an organic film made of novolac resin or the like is formed on a substrate to be processed as a resist underlayer film, a silicon-containing resist intermediate film is formed on the organic film as a resist intermediate film, and a normal organic photoresist film is formed on the organic film as a resist upper layer film. When dry etching is performed using fluorine-based gas plasma, the organic resist upper layer film has a good etching selectivity to the silicon-containing resist intermediate film, so that the resist upper layer film pattern can be transferred to the silicon-containing resist intermediate film by dry etching using fluorine-based gas plasma. According to this method, even if a resist composition that is difficult to form a pattern with a sufficient film thickness 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, a pattern can be transferred to the silicon-containing resist intermediate film (resist intermediate film), and then, by performing pattern transfer by dry etching using oxygen-based or hydrogen-based gas plasma, a pattern of an organic film (resist underlayer film) made of novolac resin or the like that has sufficient dry etching resistance for processing a substrate can be obtained. As the above-mentioned resist underlayer film, many films are already known, for example, the one described in Patent Document 1.

[0008] On the other hand, in recent years, the miniaturization of DRAM memories has accelerated, and the need for a resist underlayer film having further improved dry etching resistance and excellent filling and planarization properties has increased. As a coating-type organic underlayer film material having excellent filling and planarization properties, for example, the one described in Patent Document 2 has been reported, but in terms of application to the latest generation, there are concerns about dry etching resistance, and the application limit of conventional coating-type organic underlayer film materials is approaching.

[0009] In order to solve the above problems, development of a resist underlayer film using a material containing a metal element is being considered. Patent Document 3 reports that a material using a Ti compound exhibits excellent dry etching resistance against CHF3 / CF4-based gas and CO2 / N2-based gas.

[0010] On the other hand, one of the problems when using metal compounds for resist underlayer films is embeddability. Although Patent Document 3 does not mention embeddability, metal oxide compounds generally have a large thermal shrinkage during baking, and after high-temperature baking, they induce a significant deterioration in filling properties, so there is a concern that they are insufficient as resist underlayer film materials that require high-level planarization properties, embedding properties, and heat resistance properties. Patent Documents 4 and 5 report that metal compounds modified with specific ligands have excellent embeddability, but the baking temperature for the embeddability evaluation that has been carried out is as low as 150°C, and there is a concern that they are insufficient as resist underlayer films that require heat resistance (for example, properties against heat treatment that may be performed after the formation of the resist underlayer film). In addition, since a metal compound in which a hydrolyzable group is protected by a silicon-containing organic group is used, the condensation reaction is difficult to promote, and the density of the metal film obtained during baking is insufficient, and there is a concern that the dry etching resistance is insufficient.

[0011] As a method for improving embedding properties, it is conceivable to use a ligand with excellent thermosetting properties. Patent Document 6 reports that a metal compound having a substituted or unsubstituted ethenyl group or a substituted or unsubstituted ethynyl group has excellent thermosetting properties, and therefore has excellent resolution and sensitivity as a radiation-sensitive composition. In the examples, metal compounds having ligands derived from 4-vinylbenzoic acid and 4-allyloxybenzoic acid are mentioned. However, there is a concern that they are insufficient as a resist underlayer film material, which requires high heat resistance for the resist material. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] JP 2004-205685 A [Patent Document 2] Patent No. 6714493 [Patent Document 3] Patent No. 6189758 [Patent Document 4] Patent No. 6786391 [Patent Document 5] Patent No. 7050137 [Patent Document 6] JP 2020-201480 A Summary of the Invention [Problem to be solved by the invention]

[0013] The present invention has been made in view of the above circumstances, and aims to provide a compound for forming a metal-containing film that has excellent dry etching resistance compared to conventional organic underlayer film materials and also has high embedding properties and / or high planarization properties, a method for producing the compound, a composition for forming a metal-containing film containing the compound, and a pattern formation method using the composition. [Means for solving the problem]

[0014] In order to solve the above problems, the present invention provides a compound for forming a metal-containing film, comprising: The compound for forming a metal-containing film (A) is a compound derived from a metal-containing compound obtained by hydrolysis or condensation, or hydrolysis and condensation, of a metal compound represented by the following formula (A-1), and further has a ligand derived from an organic compound represented by the following formula (1): M(OR 1A )4(A-1) R 2A COXCOOH (1) (Wherein, M is Ti, Zr, or Hf; R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by any one of the following general formulas (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms. [ka] (In the above general formulas (a-1) to (a-4), R arepresents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.

[0015] Such a compound for forming a metal-containing film contains a ligand derived from an organic compound of formula (1) containing at least one of the crosslinking groups represented by any one of (a-1) to (a-4), and therefore when used in a composition for forming a metal-containing film, it is possible to provide a composition for forming a metal-containing film that exhibits small volumetric shrinkage during baking and has excellent flattening and / or filling properties even after high-temperature baking. In addition, since the compound is derived from a metal-containing compound obtained by hydrolysis or condensation, or hydrolysis and condensation, when used in a composition for forming a metal-containing film, it is possible to form a dense metal-containing film, and it is possible to provide a metal-containing film that has extremely excellent dry etching resistance for a substrate to be processed.

[0016] The (A) metal-containing film-forming compound is one or more selected from a hydrolysate of only the metal compound represented by the formula (A-1), a condensate of only the metal compound represented by the formula (A-1), and a hydrolysis condensate of only the metal compound represented by the formula (A-1); An organic compound represented by the formula (1); Preferably, the metal-containing compound is a reactant of

[0017] Such a compound for forming a metal-containing film can efficiently introduce a ligand derived from the organic compound of formula (1) into a metal compound, and therefore, when used in a composition for forming a metal-containing film, a metal-containing film having both high embedding properties and high dry etching resistance can be provided.

[0018] In the formula (1), R 2A is preferably a structure represented by the following general formula (B-1). [ka] (In the above general formula (B-1), R A1is the structure represented by the above general formula (a-1), and R A2 is either of the structures represented by the above general formula (a-2) or (a-3), Z is either an oxygen atom or a secondary amine, L is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R A3 is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 or more and 6 or less, 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.

[0019] In the general formula (1), R 2A has the structure represented by the above formula (B-1), it becomes possible to achieve a high compatibility between the thermal fluidity and thermosetting property of the above-mentioned metal-containing film-forming compound, and when this is used in a metal-containing film-forming composition, it is possible to provide a metal-containing film-forming composition that exhibits superior planarization properties and / or filling properties.

[0020] In the formula (1), the organic group X is preferably a saturated hydrocarbon group having 2 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms.

[0021] When the organic group X in the formula (1) has such a structure, it is possible to further improve the thermal fluidity of the above-mentioned metal-containing film-forming compound, and when this is used in a metal-containing film-forming composition, it is possible to provide a metal-containing film-forming composition that exhibits superior planarization properties and / or filling properties.

[0022] In the formula (1), the organic group X is preferably a group represented by any one of the following formulas (2). [ka] (In the above general formula (2), R a and R b is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and R c is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, and R a and R bmay be bonded to form a cyclic substituent. *1 and *2 each represent the bond to the carbonyl group, and *1 and *2 may be reversed.)

[0023] When the organic group X in the formula (1) has such a structure, it is possible to further improve the thermal fluidity of the above-mentioned metal-containing film-forming compound, and when this is used in a metal-containing film-forming composition, it is possible to provide a metal-containing film-forming composition that exhibits superior planarization properties and / or filling properties.

[0024] For example, the (A) metal-containing film-forming compound may include a compound having a structure represented by the following general formula (m-1). [ka] (In the above formula (m-1), R ae ~R de each independently represents R in the above formula (A-1). 1A or COXCOR in the above formula (1) 2A Either ae ~R de At least one of the COXCOR in the above formula (A-1) 2A where n is 1 to 20, and M is the same as M in the above formula (A-1).

[0025] (A) The metal-containing film-forming compound can include, but is not limited to, compounds having the structures shown above.

[0026] It is preferable that the (A) compound for forming a metal-containing film further contains, in addition to the ligand derived from the organic compound represented by formula (1), at least one additional ligand selected from the group consisting of a ligand derived from an organic compound represented by formula (3) below and a ligand derived from any one of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and it is preferable that the additional ligand does not contain a group represented by the above general formulas (a-1) to (a-4). R 3A COOH (3) (In the formula, R 3A is a monovalent organic group having 1 to 20 carbon atoms.

[0027] When such a compound is used in a composition for forming a metal-containing film, it is possible to promote a crosslinking reaction during baking, and the baking temperature can be set to a low temperature range. In addition, the promotion of the crosslinking reaction makes it possible to form a dense metal-containing film, and the etching resistance can be improved.

[0028] In this case, for example, the (A) metal-containing film-forming compound may include a compound having any one of the structures shown below. [ka] (Above R 3a is either a monovalent organic group having 1 to 20 carbon atoms and not containing a crosslinking group, as represented by the above general formulas (a-1) to (a-4), or a structure represented by the following formula: 1A is R in the above formula (A-1) 1A is the same as R 2A is R in the above formula (1). 2A where n is 1 to 20, and M is the same as M in the above formula (A-1). [ka] (In the above formula, R 3b is an alkyl group having 1 to 10 carbon atoms, and * represents the bond to the carbonyl carbon.

[0029] When including additional ligands, the (A) metal-containing film-forming compound can include, but is not limited to, compounds having the structures shown above, for example.

[0030] The present invention also provides a metal-containing film-forming composition, The compound (A) for forming a metal-containing film of the present invention and (B) Organic solvent The present invention provides a composition for forming a metal-containing film, which comprises:

[0031] Such a composition for forming a metal-containing film contains a metal-containing compound that has excellent heat resistance and thermal fluidity, and therefore it is possible to provide a composition for forming a metal-containing film that has excellent dry etching resistance compared to conventional organic underlayer film materials, and also has high embedding properties and / or high planarization properties compared to conventional metal-containing underlayer film materials.

[0032] The composition further comprises: (C) a crosslinking agent, (D) a surfactant, and (E) Acid generator It may contain one or more of the following:

[0033] A composition for forming a metal-containing film that contains the above additives is a composition for forming a metal-containing film that has better coatability, dry etching resistance, and filling and / or planarization properties.

[0034] It is preferable that the (B) organic solvent contains a (B-1) high boiling point solvent, and the (B-1) high boiling point solvent is one or more organic solvents having a boiling point of 180° C. or higher.

[0035] By imparting thermal fluidity to the above-mentioned metal-containing film-forming compound by adding a high-boiling point solvent, the metal-containing film-forming composition also has higher filling and / or planarizing properties.

[0036] It is preferable that the metal-containing film-forming composition further contains a flowability promoter (BP) having an organic group and an aromatic ring, which is represented by the following general formula (bp1a). [ka] (wherein * represents the bond site to the oxygen atom, R B is a divalent organic group having 1 to 10 carbon atoms, R A is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

[0037] By imparting heat resistance and thermal fluidity to the above-mentioned metal-containing film-forming compound by adding a flowability promoter (BP), the metal-containing film-forming compound also has high-level filling properties and / or planarization properties.

[0038] The flow promoter (BP) preferably has at least one structural unit represented by any one of the following general formulae (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5). [ka] In the general formulae (BP-1) and (BP-2), W1 and W2 each independently represent a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. a1 is a group represented by the following general formula (4). Y is a group represented by the following general formula (5). n1 is 0 or 1, n2 is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. [ka] (In the above general formula (BP-3), Z1 is a group represented by the following general formula (6), R a1 is the following general formula (4), n4 is 0 or 1, n5 is 1 or 2, and each V independently represents a hydrogen atom or a linking portion. [ka] (* indicates the bond to the oxygen atom.) [ka] (* represents a bond.) [ka] (In the above general formula (6), W1, W2, Y, and n1 are the same as defined above.) [ka] (In the formula, m3 and m4 represent 1 or 2, and Z2 is either a single bond or a structure represented by the following general formula (7). R x is any of the structures represented by the following general formula (8). [ka] (In the formula, * represents a bond, l represents an integer of 0 to 3, and R az ~R fz each independently represents a hydrogen atom or an optionally fluorine-substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a phenylethyl group; R az and R bz may be bonded to form a cyclic compound.) [ka] (In the formula, * represents a bonding site to the aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9).) [ka] (wherein * represents the bond site to the carbonyl group, R i R is the above general formula (4). j represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. 3z and n 4z represents the number of substituents on the aromatic ring, and each represents an integer of 0 to 7. 3z +n 4z n is between 0 and 7. 5z represents 0 to 2.) [ka] (In the above general formula (BP-5), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X1 is a divalent organic group having 1 to 30 carbon atoms, R a1is the above general formula (4). p is an integer of 0 to 5, q1 is an integer of 1 to 6, p+q1 is an integer of 1 or more and 6 or less, and q2 is 0 or 1.

[0039] A composition for forming a metal-containing film to which a flowability promoter (BP) having at least one of the structural units represented by (BP-1) to (BP-5) above has been added has better filling and / or planarizing properties.

[0040] The present invention also relates to a method for producing a condensation product of only a metal compound represented by the following formula (A-1), a hydrolysis product of only a metal compound represented by the following formula (A-1), and a hydrolysis condensation product of only a metal compound represented by the following formula (A-1), which is obtained by reacting one or more compounds selected from the group consisting of a hydrolysis product of only a metal compound represented by the following formula (A-1), with an organic compound represented by the following formula (1), or The present invention provides a method for producing (A) a compound for forming a metal-containing film, which comprises hydrolyzing or condensing, or hydrolyzing and condensing, a metal compound represented by the following general formula (A-2): M(OR 1A )4(A-1) R 2A COXCOOH (1) (Wherein, M is Ti, Zr, or Hf; R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by any one of the following general formulas (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms. [ka] (In the above general formulas (a-1) to (a-4), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q is 0 or 1, and * is a bond. (R 2A COXCOO) x M(OR 1A ) y (A-2) (Wherein, M is Ti, Zr, or Hf; R 1A is a monovalent organic group having 1 to 20 carbon atoms, R2A is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by the above general formulas (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, x+y=4, and x and y are integers of 1 or more.

[0041] Such a production method can provide a compound for forming a metal-containing film, which contains a ligand derived from an organic compound of formula (1) containing at least one of the crosslinking groups represented by any one of (a-1) to (a-4), and when this compound is used in a composition for forming a metal-containing film, it is possible to provide a composition for forming a metal-containing film that exhibits small volumetric shrinkage during baking and has excellent flattening and / or filling properties even after high-temperature baking. In addition, it is possible to provide a compound derived from a metal-containing compound obtained by hydrolyzing or condensing, or by hydrolysis and condensation, of a metal compound represented by formula (A-1). When this compound is used in a composition for forming a metal-containing film, it is possible to form a dense metal-containing film, and it is possible to provide a metal-containing film that has extremely excellent dry etching resistance for a substrate to be processed.

[0042] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (I-1) a step of applying the composition for forming a metal-containing film of the present invention onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (I-2) forming a resist top layer film on the metal-containing film using a photoresist material; (I-3) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern is formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0043] By the pattern formation method using the two-layer resist process, a fine pattern can be formed on a workpiece (substrate).

[0044] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (II-1) A step of applying the composition for forming a metal-containing film of the present invention onto a substrate to be processed and then heat-treating the composition to form a metal-containing film; (II-2) forming a resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (II-5) a step of transferring the pattern to the resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) a step of transferring a pattern to the metal-containing film by dry etching using the resist intermediate film to which the pattern has been transferred as a mask; and (II-7) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0045] The pattern formation method using the three-layer resist process described above makes it possible to form fine patterns on a workpiece with high precision.

[0046] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (III-1) A step of applying the composition for forming a metal-containing film of the present invention onto a substrate to be processed and then heat-treating the composition to form a metal-containing film; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist top layer film on the organic thin film using a photoresist material; (III-5) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (III-6) a step of transferring a pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (III-7) A step of transferring a pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0047] The pattern formation method using the four-layer resist process described above makes it possible to form fine patterns on a workpiece with high precision.

[0048] In this case, the inorganic hard mask intermediate film is preferably formed by a CVD method or an ALD method.

[0049] When the inorganic hard mask is formed by a CVD method or an ALD method, a fine pattern can be formed on a workpiece with higher accuracy.

[0050] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (IV-1) A step of applying the composition for forming a metal-containing film of the present invention onto a substrate to be processed and then heat-treating the composition to form a metal-containing film; (IV-2) forming an organic intermediate film on the metal-containing film; (IV-3) forming a silicon-containing resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the organic intermediate film; (IV-4) forming a resist top layer film on the silicon-containing resist intermediate film or the organic thin film using a photoresist material; (IV-5) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (IV-6) a step of transferring a pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern is formed as a mask; (IV-7) A step of transferring a pattern to an organic intermediate film by dry etching using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; (IV-8) A step of transferring a pattern to the metal-containing film by dry etching using the organic intermediate film as a mask; and (IV-9) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0051] By using the pattern forming method using the multi-layer resist process, a fine pattern can be formed on a workpiece with high precision.

[0052] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (V-1) a step of forming a resist underlayer film on a substrate to be processed; (V-2) a step of forming a resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (V-3) forming a resist upper layer film on the resist intermediate film or on a combination of the inorganic hard mask intermediate film and an organic thin film using a photoresist material; (V-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (V-5) a step of transferring a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (V-6) a step of transferring a pattern to the resist underlayer film by dry etching using the resist intermediate film or the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; (V-7) a step of applying the composition for forming a metal-containing film of the present invention onto the resist underlayer film on which the pattern has been formed, and then heat-treating the composition to form a metal-containing film, thereby filling spaces between the resist underlayer film patterns with the metal-containing film; (V-8) a step of etching back the metal-containing film covering the resist underlayer film on which the pattern is formed by a chemical stripper or dry etching to expose an upper surface of the resist underlayer film on which the pattern is formed; (V-9) a step of removing the resist intermediate film or the hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) a step of removing the resist underlayer film on which the pattern is formed and the surface is exposed by dry etching to form a reverse pattern of the original pattern on the metal-containing film; (V-11) A step of processing the substrate to be processed using the metal-containing film on which the reverse pattern is formed as a mask to form a reverse pattern on the substrate to be processed. The present invention provides a method for forming a tone-reversal pattern, comprising the steps of:

[0053] The above-described method for forming a pattern using a reversal process makes it possible to form a fine pattern on a workpiece with even greater precision. Effect of the Invention

[0054] As described above, the compound for forming a metal-containing film of the present invention is a compound derived from a metal-containing compound obtained by hydrolysis or condensation, or hydrolysis and condensation, of the metal compound represented by the above formula (A-1), and further is a compound for forming a metal-containing film having a ligand derived from the organic compound represented by the above formula (1). Therefore, when this compound is used in a composition for forming a metal-containing film, it is possible to provide a composition for forming a metal-containing film that has small volume shrinkage during baking and has excellent planarization properties and / or filling properties even after high-temperature baking.

[0055] In particular, in a fine patterning process using a multilayer resist method in the manufacturing process of semiconductor device, even on a substrate to be processed having areas that are difficult to fill and / or planarize, such as dense areas of high aspect ratio fine pattern structures typified by DRAM memories that are becoming increasingly miniaturized, the metal-containing film-forming composition containing the metal-containing film-forming compound of the present invention can fill without causing defects such as voids or peeling, and further has superior dry etching resistance compared to conventional coating-type resist underlayer film materials, making it possible to form fine patterns on the substrate to be processed with even greater precision than with conventional resist underlayer films.

[0056] Furthermore, according to the method for producing a compound for forming a metal-containing film of the present invention, it is possible to produce a compound for forming a metal-containing film, which is derived from a metal-containing compound obtained by hydrolysis or condensation, or hydrolysis and condensation, of a metal compound represented by the above formula (A-1), and which further has a ligand derived from the organic compound represented by the above formula (1). Therefore, when this compound is used in a composition for forming a metal-containing film, it is possible to provide a composition for forming a metal-containing film that exhibits small volume shrinkage during baking and has excellent planarization properties and / or filling properties even after high-temperature baking.

[0057] Furthermore, the pattern formation method of the present invention uses the metal-containing film-forming composition of the present invention, and therefore can form a fine pattern on a workpiece with even greater precision. [Brief description of the drawings]

[0058] [Figure 1] FIG. 1 is an explanatory diagram of an example of the pattern forming method of the present invention (three-layer resist process). [Diagram 2] FIG. 2 is an explanatory diagram of an example of the tone reversal patterning method of the present invention (reversal of the SOC pattern in a three-layer resist process). [Diagram 3] FIG. 3 is an explanatory diagram of a method for evaluating embedding characteristics. [Figure 4] FIG. 4 is an explanatory diagram of a method for evaluating flattening characteristics. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0059] As described above, there has been a demand for the development of a metal-containing film-forming composition that has excellent embedding properties and flatness and is used to form a metal-containing film that can transfer a resist pattern to a substrate to be processed with higher precision in a fine patterning process using a multilayer resist method, a metal-containing film-forming compound useful for the composition, and a pattern formation method using the composition.

[0060] The present inventors have focused on metal materials that exhibit superior etching resistance compared to conventional resist underlayer film materials and have conducted intensive research. On the other hand, conventional metal compounds for forming resist underlayer films have poor heat resistance and undergo rapid volumetric shrinkage during baking, making it difficult to fill and flatten the steps of the substrate to be processed after high-temperature baking. The present inventors considered that if the compound has an organic group with excellent heat resistance, it can reduce rapid volumetric shrinkage during baking and improve thermal fluidity, so that it is possible to fill the steps of the substrate to be processed without generating voids even after high-temperature baking. Furthermore, it was assumed that if the structure contains a crosslinking group at the end, it will be a compound for forming a metal-containing film with superior heat resistance because it has excellent thermosetting properties during baking. Furthermore, since there is a concern that the dry etching resistance of the metal-containing film will deteriorate due to the introduction of an organic ligand with excellent heat resistance, the present inventors assumed that it will be possible to improve the dry etching resistance without deteriorating the filling properties by using a compound derived from a metal-containing compound obtained by hydrolysis or condensation, or hydrolysis and condensation of a metal compound.

[0061] As a result of further intensive research, the present inventors have found that a compound for forming a metal-containing film, which is derived from a metal-containing compound obtained by hydrolysis or condensation, or hydrolysis and condensation, of a metal compound represented by the following formula (A-1), and which contains a ligand derived from an organic compound represented by formula (1) containing one or more of the crosslinking groups represented by (a-1) to (a-4), has excellent thermosetting properties and therefore can reduce rapid volumetric shrinkage during baking, and also has good thermal fluidity and therefore can achieve advanced filling properties and / or advanced planarization properties, and can provide a resist underlayer film with excellent dry etching resistance, thereby completing the present invention.

[0062] That is, the present invention provides (A) a compound for forming a metal-containing film, The (A) compound for forming a metal-containing film is a compound derived from a metal-containing compound obtained by hydrolysis or condensation, or hydrolysis and condensation, of a metal compound represented by the following formula (A-1), and further has a ligand derived from an organic compound represented by the following formula (1). M(OR 1A )4(A-1) R 2A COXCOOH (1) (Wherein, M is Ti, Zr, or Hf; R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by any one of the following general formulas (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms. [ka] (In the above general formulas (a-1) to (a-4), R a represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.

[0063] The present invention will be described in detail below, but the present invention is not limited thereto.

[0064] <(A) Metal-containing film-forming compound> The compound (A) for forming a metal-containing film of the present invention is a compound derived from a metal-containing compound obtained by hydrolysis or condensation, or hydrolysis and condensation, of a metal compound represented by the following formula (A-1), and is characterized in that it further has a ligand derived from an organic compound represented by the following formula (1). M(OR 1A )4(A-1) R 2A COXCOOH (1) (Wherein, M is Ti, Zr, or Hf; R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by any one of the following general formulas (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms. [ka] (In the above general formulas (a-1) to (a-4), R a represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.

[0065] Compounds derived from metal-containing compounds obtained by hydrolysis or condensation, or hydrolysis and condensation of metal compounds have at least one [metal]-[oxygen]-[metal] bond, and therefore when a metal-containing film is formed using such a compound, a metal-containing film with high hardness and excellent density can be provided. In addition, by carrying out hydrolysis or condensation, or hydrolysis and condensation during compound synthesis, volumetric shrinkage accompanying the condensation reaction during film baking can be reduced, making it possible to further improve the embedding properties.

[0066] In the above formula (A-1), R 1A represents a monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an isopropyl group or an n-butyl group from the viewpoint of productivity of the metal compound.

[0067] Examples of the metal compound represented by the above formula (A-1) include titanium tetraisopropoxide, titanium butoxide tetramer, zirconium (IV) tetrabutoxide, hafnium (IV) n-butoxide, zirconium (IV) tetraisopropoxide, and zirconium (IV) tetrapropoxide.

[0068] In the above formula (1), R 2A is a divalent organic group having 2 to 20 carbon atoms and containing at least one crosslinking group represented by any one of the above general formulas (a-1) to (a-4).

[0069] By having a ligand derived from such an organic compound, the thermosetting property of the (A) metal-containing film-forming compound is improved, and when this is used in a metal-containing film-forming composition, the volume shrinkage during high-temperature baking can be reduced, and a metal-containing film-forming composition having excellent filling and / or planarization properties can be provided.

[0070] Among (a-1) to (a-4) above, R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, preferably a hydrogen atom, a methyl group, or a phenyl group from the viewpoint of raw material availability, and more preferably a hydrogen atom from the viewpoint of thermosetting properties.

[0071] The (A) metal-containing film-forming compound is one or more selected from a hydrolysate of only the metal compound represented by the formula (A-1), a condensate of only the metal compound represented by the formula (A-1), and a hydrolysis condensate of only the metal compound represented by the formula (A-1); An organic compound represented by the formula (1); Preferably, the metal-containing compound is a reactant of

[0072] Such a compound for forming a metal-containing film can efficiently introduce a ligand derived from the organic compound of formula (1) into a metal compound, and therefore, when used in a composition for forming a metal-containing film, a metal-containing film having both high embedding properties and high dry etching resistance can be provided.

[0073] In the formula (1), R 2A is preferably a structure represented by the following general formula (B-1). [ka] (In the above general formula (B-1), R A1 is the structure represented by the above general formula (a-1), and R A2 is either of the structures represented by the above general formula (a-2) or (a-3), Z is either an oxygen atom or a secondary amine, L is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R A3 is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 or more and 6 or less, 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.

[0074] In the above general formula (B-1), it is preferable that r is 1 to 10, t is 1 to 6, s is 0 to 5, t+s is 1 or more and 6 or less, u is 0 or 1, and m is 0 or 1. When m is 1, it is preferable that L is methylene. In a more preferable structure, r is 1 to 4, t is 1 to 2, s is 0 to 1, and m is 0.

[0075] In the formula (1), R 2A is a structure represented by the above general formula (B-1), the thermal fluidity and thermosetting properties of the above (A) metal-containing film-forming compound can be further improved. When this is used in a metal-containing film-forming composition, a metal-containing film-forming composition exhibiting superior planarization properties and / or filling properties can be provided.

[0076] In the formula (1), the organic group X is preferably a saturated hydrocarbon group having 2 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms.

[0077] Such a structure can further improve the thermal fluidity of the (A) metal-containing film-forming compound, and when used in the (A) metal-containing film-forming composition, it can provide a metal-containing film-forming composition that exhibits superior planarization and / or filling properties.

[0078] In the formula (1), the organic group X is preferably a group represented by any one of the following formulas (2). [ka] (In the above general formula (2), R a and R b is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and R c is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, and R a and R b may be bonded to form a cyclic substituent. *1 and *2 each represent the bond to the carbonyl group, and *1 and *2 may be reversed.)

[0079] In the formula (1), when the organic group X has such a structure, the thermal fluidity of the (A) metal-containing film-forming compound can be further improved, and when this is used in a metal-containing film-forming composition, a metal-containing film-forming composition exhibiting superior planarization properties and / or filling properties can be provided.

[0080] As preferred structures of the above formula (1), the following compounds can be shown, for example, but the present invention is not limited thereto.

[0081] [ka]

[0082] [ka]

[0083] From the viewpoint of embedding properties, in the above formula (B-1), Z is more preferably a secondary amine.

[0084] The (A) compound for forming a metal-containing film may contain one ligand derived from the organic compound represented by the formula (1) above, or a plurality of ligands having different structures, and may be appropriately adjusted according to the required properties required when used in a composition for forming a metal-containing film. In addition, the compound may have a ligand other than the ligand derived from the organic compound represented by the formula (1) above. For example, the compound may contain a ligand derived from an alkyl group having 1 to 10 carbon atoms.

[0085] The (A) metal-containing film-forming compound preferably contains a compound having a structure represented by the following general formula (m-1). [ka] (In the above formula (m-1), R ae ~R de each independently represents R in the above formula (A-1). 1A or COXCOR in the above formula (1) 2A Either ae ~R de At least one of the COXCOR in the above formula (A-1) 2A where n is 1 to 20, and M is the same as M in the above formula (A-1).

[0086] The (A) compound for forming a metal-containing film is a compound derived from a metal-containing compound obtained by hydrolysis or condensation, or hydrolysis and condensation, of the metal compound represented by the formula (A-1) above, and preferably further contains, in addition to the ligand derived from the organic compound represented by the formula (1) above, at least one additional ligand selected from the ligand derived from the organic compound represented by the following formula (3) and the ligand derived from any of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and more preferably the additional ligand does not contain a crosslinking group represented by the general formulas (a-1) to (a-4) above. R 3ACOOH (3) (In the formula, R 3A is a monovalent organic group having 1 to 20 carbon atoms.

[0087] When such a compound further containing an additional ligand is used in the metal-containing film-forming composition, it is possible to promote the crosslinking reaction during baking, and the baking temperature can be set to a low temperature range. In addition, the promotion of the crosslinking reaction makes it possible to form a dense metal-containing film, which is preferable because it can improve the etching resistance.

[0088] The ligand derived from the organic compound represented by formula (3) preferably contains at least one aromatic ring, heteroaromatic ring, and alicyclic structure, and examples thereof include the following.

[0089] [ka] (In the above formula, R 3Ae is a monovalent organic group having 1 to 10 carbon atoms, n is 1 to 10, and * indicates the bond to the carbonyl carbon.

[0090] The ligand derived from any one of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride is preferably unsubstituted or substituted with a monovalent organic group having 1 to 10 carbon atoms, and more preferably unsubstituted.

[0091] When a compound further containing an additional ligand derived from such an organic compound is used in a composition for forming a metal-containing film, the deterioration of the filling characteristics can be minimized and the dry etching resistance can be improved, which is preferable.

[0092] When the (A) compound for forming a metal-containing film contains at least one additional ligand selected from the group consisting of a ligand derived from an organic compound represented by the above formula (3) and a ligand derived from any one of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, it is preferable that the compound contains a compound having any one of the structures shown below or a mixture of these compounds. [ka] (Above R 3a is either a monovalent organic group having 1 to 20 carbon atoms and not containing a crosslinking group, as represented by the above general formulas (a-1) to (a-4), or a structure represented by the following formula: 1A is R in the above formula (A-1) 1A is the same as R 2A is R in the above formula (1). 2A where n is 1 to 20, and M is the same as M in the above formula (A-1). [ka] (In the above formula, R 3b is an alkyl group having 1 to 10 carbon atoms, and * represents the bond to the carbonyl carbon.

[0093] In addition to the ligand derived from the organic compound represented by the above formula (1) and the above additional ligand, the ligand may further contain a ligand derived from a dihydric or trihydric alcohol and / or a ligand derived from a β-diketone.

[0094] When such a compound is used in a composition for forming a metal-containing film, it is possible to promote a crosslinking reaction during baking, and it is also possible to set the baking temperature at that time in a low temperature range. By promoting the crosslinking reaction, it is possible to form a dense metal-containing film, and it is preferable because etching resistance can be improved.

[0095] Examples of the dihydric or trihydric alcohol include the compounds described in paragraphs

[0055] to

[0060] of Japanese Patent No. 6,189,758, and among them, any of the following compounds described in paragraph

[0061] is preferable.

[0096] [ka]

[0097] The β-diketone preferably has a structure represented by the following formula (3-a).

[0098] [ka] (In the above formula, R 3A and R 3B are each independently a monovalent organic group having 1 to 20 carbon atoms, and R 3c is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0099] Above R 3A and R 3B are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkoxy group or a carbonyloxy hydrocarbon-substituted hydrocarbon group, more preferably an alkyl group, an aryl group, an alkoxy group, or an alkoxycarbonylalkyl group, and even more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a methoxycarbonylmethyl group.

[0100] Above R 3c is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0101] Specific examples of β-diketones include 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, acetoacetate, α-alkyl-substituted acetoacetate, β-ketopentanoate, benzoylacetate, 1,3-acetonedicarboxylate, malonic acid diester, di-tert-butyl malonate, α-alkyl-substituted malonic acid diester, α-cycloalkyl-substituted malonic acid diester, and α-aryl-substituted malonic acid diester. More preferred are 2,4-pentanedione, 3-methyl-2,4-pentanedione, ethyl acetoacetate, diethyl malonate, or di-tert-butyl malonate, and even more preferred are 2,4-pentanedione, 3-methyl-2,4-pentanedione, or di-tert-butyl malonate.

[0102] When such a compound is used in a composition for forming a metal-containing film, it is possible to promote a crosslinking reaction during baking, and it is also possible to set the baking temperature at that time in a low temperature range. By promoting the crosslinking reaction, it is possible to form a dense metal-containing film, and it is preferable because etching resistance can be improved.

[0103] The (A) metal-containing film-forming compound may contain, in addition to the ligand derived from the organic compound represented by formula (1), one or more additional ligands selected from the ligand derived from the organic compound represented by formula (3) and the ligand derived from any of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, and may be appropriately adjusted according to the required properties required when used in a metal-containing film-forming composition. In addition, the compound may contain the ligand derived from the dihydric or trihydric alcohol and / or the ligand derived from the β-diketone, and may be appropriately adjusted according to the required properties required when used in a metal-containing film-forming composition.

[0104] When the (A) compound for forming a metal-containing film contains a ligand different from the ligand derived from the organic compound represented by formula (1), it is preferable that the compound contains one or more ligands with different structures derived from succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, and more preferably contains one of the ligands derived from succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride. By using a carbonyl ligand like the organic compound represented by formula (1), the storage stability of the (A) compound for forming a metal-containing film can be improved.

[0105] In the (A) metal-containing film-forming compound, the content of the ligand derived from the organic compound represented by the formula (1) is preferably 10 mol% or more of the total of the ligands coordinated to the metal atom M, more preferably 30 mol% or more, and even more preferably 50 mol% or more, with the upper limit being preferably 100 mol%. The ligand other than the ligand derived from the organic compound represented by the formula (1) is preferably 90 mol% or less of the total of the ligands coordinated to the metal atom M, more preferably 70 mol% or less, and even more preferably 50% mol% or less, with the lower limit being preferably 0 mol%. The compound may further contain ligands other than the ligands described above, such as ligands derived from an alkyl group having 1 to 10 carbon atoms, with the content of these being preferably 0 mol% to 50 mol%, and more preferably 0 mol% to 30 mol% of the total of the ligands coordinated to the metal atom M.

[0106] If the content of the ligand derived from the organic compound represented by the above formula (1) is 10 mol % or more, the metal-containing film-forming composition can have excellent embedding properties, which is preferable. When the metal-containing film-forming composition is used in a process for embedding finer patterns, it is preferable to increase the content of the ligand derived from the organic compound represented by the above formula (1), and it is particularly preferable to make the content 50 mol % or more.

[0107] <Synthesis of compounds for forming metal-containing films> The (A) metal-containing film-forming compound of the present invention is, for example, a compound derived from one or more selected from the hydrolysis product of only the metal compound represented by the formula (A-1), the condensation product of only the metal compound represented by the formula (A-1), and the hydrolysis condensation product of only the metal compound represented by the formula (A-1), and contains a ligand derived from the organic compound represented by the formula (1). As long as such a compound can be obtained, the synthesis method is not particularly limited. For example, it can be obtained by reacting one or more selected from the hydrolysis product of only the metal compound represented by the formula (A-1), the condensation product of only the metal compound represented by the formula (A-1), and the hydrolysis condensation product of only the metal compound represented by the formula (A-1) with the organic compound represented by the formula (1).

[0108] Alternatively, (A) the compound for forming a metal-containing film may be a compound for forming a metal-containing film obtained by hydrolysis or condensation, or hydrolysis and condensation, of a metal compound represented by the following general formula (A-2) having a ligand derived from an organic compound represented by formula (1). (R 2A COXCOO) x M(OR 1A ) y (A-2) (Wherein, M is Ti, Zr, or Hf; R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by the above general formulas (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, x+y=4, and x and y are integers of 1 or more.

[0109] That is, the method for producing a compound for forming a metal-containing film of the present invention includes the steps of: reacting at least one selected from a hydrolysate of only a metal compound represented by the following formula (A-1), a condensate of only a metal compound represented by the following formula (A-1), and a hydrolysis condensate of only a metal compound represented by the following formula (A-1) with an organic compound represented by the following formula (1); A metal compound represented by the following general formula (A-2) is hydrolyzed or condensed, or hydrolyzed and condensed: Includes. M(OR 1A )4(A-1) R 2A COXCOOH (1) (Wherein, M is Ti, Zr, or Hf; R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by any one of the following general formulas (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms. [ka] (In the above general formulas (a-1) to (a-4), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q is 0 or 1, and * is a bond. (R 2A COXCOO) x M(OR 1A ) y (A-2) (Wherein, M is Ti, Zr, or Hf; R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by the above general formulas (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, x+y=4, and x and y are integers of 1 or more.

[0110] Compounds derived from at least one selected from the group consisting of a hydrolyzate of only the metal compound represented by formula (A-1), a condensate of only the metal compound represented by formula (A-1), and a hydrolysis condensate of only the metal compound represented by formula (A-1) have at least one [metal]-[oxygen]-[metal] bond, and therefore when a metal-containing film is formed using the compounds, a metal-containing film having high hardness and excellent density can be provided. In addition, by carrying out hydrolysis or condensation, or hydrolysis condensation during compound synthesis, volume shrinkage accompanying the condensation reaction during film baking can be reduced, making it possible to further improve the embedding properties.

[0111] The hydrolysis or hydrolysis condensation of the metal compound represented by formula (A-1) or the metal compound represented by formula (A-2) (hereinafter referred to as metal monomer) can be produced without a catalyst or in the presence of an acid or an alkali catalyst. In this case, the target product can be produced using one or more compounds selected from inorganic acids, aliphatic sulfonic acids, aromatic sulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids as the acid catalyst. Specific examples of the acid catalyst include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, and benzoic acid. The amount of the catalyst used is preferably 1×10 per mole of the metal M-containing monomer. -6 ~10 moles, more preferably 1 x 10 -5 ~5 moles, more preferably 1 × 10 -4 ~1 mol.

[0112] Alternatively, the compound may be produced by hydrolysis and condensation of a monomer containing metal M in the presence of an alkali catalyst. The alkali catalyst used in this case is, for example, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclocyclononene, diazabicycloundecene, hexamethylenetetraamine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylethanolamine, N,N-diethylethanolamine, or the like. Examples of the catalyst include amine, N-(β-aminoethyl)ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, N-tert-butylethanolamine, N-tert-butyldiethanolamine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. The amount of the catalyst used is preferably 1×10 per mole of the metal M-containing monomer. -6 mol to 10 mol, more preferably 1×10 -5 mol to 5 mol, more preferably 1×10 -4 mol to 1 mol.

[0113] The amount of water added when obtaining a metal-containing compound from these metal M-containing monomers by hydrolysis or hydrolysis condensation is preferably 0.01 to 10 mol, more preferably 0.05 to 5 mol, further preferably 0.1 to 3 mol, and particularly preferably 0.1 to 1 mol per mol of the hydrolyzable substituent bonded to the metal M-containing monomer. Addition of 10 mol or less is economical since the apparatus used for the reaction does not become excessively large, and is also preferable since the stability of the metal-containing compound is not impaired.

[0114] As an operation method, the metal M-containing monomer is added to the aqueous catalyst solution to initiate the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, the metal M-containing monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is preferably 0 to 200°C, more preferably 5 to 150°C. A method in which the temperature is kept at 5 to 150°C during the dropwise addition of the metal M-containing monomer, and then the mixture is aged at 20 to 150°C is preferred.

[0115] As another reaction procedure, water or a water-containing organic solvent is added to the metal M-containing monomer or an organic solvent containing the metal M-containing monomer to initiate the hydrolysis reaction. At this time, the catalyst may be added to the metal M-containing monomer or an organic solvent containing the metal M-containing monomer, or may be added to the water or water-containing organic solvent. The reaction temperature is preferably 0 to 200°C, more preferably 5 to 150°C. A method in which the temperature is kept at 5 to 150°C during the dropwise addition of the metal M-containing monomer and then aging is performed at 20 to 150°C is preferred.

[0116] Examples of organic solvents that can be added to the aqueous catalyst solution or that can dilute the metal-containing compound include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, acetylacetone, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl pivaloyl acetate, methyl isobutyroyl acetate, methyl caproyl acetate, methyl lauroyl acetate, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 2,3-butanediol, 2,3-pentanediol, glycerin, diethylene glycol, hexylene glycol, and mixtures thereof are preferred.

[0117] The amount of the organic solvent used is preferably 0 to 1,000 ml, particularly preferably 0 to 500 ml, per mole of the metal-containing compound. If the amount of the organic solvent used is 1,000 ml or less, the reaction vessel will not become excessively large, which is economical.

[0118] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out, and the alcohol generated in the hydrolysis and condensation reaction is removed under reduced pressure to obtain an aqueous solution of the reaction mixture. At this time, the amount of acid or alkali that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid or alkali used in the catalyst, and any substance that can be neutralized may be used.

[0119] Subsequently, it is preferable to remove by-products such as alcohol generated in the hydrolysis condensation reaction from the reaction mixture. The temperature at which the reaction mixture is heated depends on the types of the organic solvent added and the alcohol generated in the reaction, but is preferably 0 to 200°C, more preferably 10 to 150°C, and even more preferably 15 to 150°C. The degree of reduced pressure at this time varies depending on the types of organic solvent and alcohol to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less in absolute pressure, and even more preferably 50 kPa or less in absolute pressure. Although it is difficult to know the exact amount of alcohol removed at this time, it is desirable to remove about 80 mass% or more of the generated alcohol.

[0120] Preferred final solvents to be added to the metal-containing compound solution include butanediol monomethyl ether, propylene glycol 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-butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, 1-butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, Examples of such an alcohol include ethanol, 2-butanol, 2-methyl-1-propanol, 4-methyl-2-pentanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diamyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, and cyclopentyl methyl ether.

[0121] By using such a metal-containing compound, it is possible to provide a metal-containing film-forming composition that exhibits excellent storage stability and does not change in characteristics over a long period of time.

[0122] The (A) compound for forming a metal-containing film of the present invention can be produced by adding an organic compound represented by formula (1) to the metal-containing compound obtained by the above-mentioned hydrolysis or hydrolytic condensation or to a reaction mixture containing the same.

[0123] Similarly, when producing a compound for forming a metal-containing film (A) containing a ligand other than that of formula (1), the compound can be produced by adding an organic compound derived from the ligand to the metal-containing compound obtained by the above-mentioned hydrolysis or hydrolysis condensation or to a reaction mixture containing the same.

[0124] <Metal-containing film forming composition> The present invention can also provide a composition for forming a metal-containing film, which comprises the above-mentioned (A) compound for forming a metal-containing film and (B) an organic solvent.

[0125] Such a composition for forming a metal-containing film contains a compound for forming a metal-containing film that has a high degree of both thermal fluidity and thermosetting properties, and therefore can provide a metal-containing film material that has excellent dry etching resistance compared to conventional organic underlayer film materials, as well as excellent filling properties and / or excellent planarization properties.

[0126] Hereinafter, components contained in the composition for forming a metal-containing film of the present invention other than the above (A) compound for forming a metal-containing film will be described.

[0127] <(B) Organic solvent> The (B) organic solvent that can be used in the metal-containing film-forming composition of the present invention is not particularly limited, but is preferably one that dissolves and / or disperses the above-mentioned (A) metal-containing film-forming compound, as well as the (C) crosslinking agent, (D) surfactant, (E) acid generator, (F) metal oxide nanoparticles having an average primary particle size of 100 nm or less, and other additives, which may be included.

[0128] Specifically, the organic solvents described in paragraphs

[0091] to

[0092] of JP 2007-199653 A can 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, γ-butyrolactone, or a mixture containing one or more of these is preferably used.

[0129] The amount of the organic solvent to be added is preferably within a range of 200 to 10,000 parts, and more preferably 250 to 5,000 parts, per 100 parts by mass of the (A) compound for forming a metal-containing film.

[0130] <(B-1) High boiling point solvent> In the metal-containing film-forming composition of the present invention, the (B) organic solvent may be used as a mixture of one or more organic solvents having a boiling point of less than 180° C. and one or more organic solvents ((B-1) high boiling point solvents) having a boiling point of 180° C. or higher. That is, the (B) organic solvent may contain the (B-1) high boiling point solvent, and the (B-1) high boiling point solvent may be one or more organic solvents having a boiling point of 180 degrees (180° C.) or higher.

[0131] The (B-1) high boiling point solvent is not particularly limited and may be, for example, a hydrocarbon, an alcohol, a ketone, an ester, an ether, or a chlorine-based solvent, but is preferably one capable of dissolving and / or dispersing each component of the metal-containing film-forming composition of the present invention. Specific examples of the (B-1) high boiling point solvent include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, 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 monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples of the diethyl ester include 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, and dibutyl adipate. These may be used alone or in combination.

[0132] (B-1) The high boiling point solvent may be appropriately selected from the above-mentioned solvents according to the temperature at which the metal-containing film-forming composition of the present invention is heat-treated. The boiling point of the high boiling point solvent is preferably 180°C to 300°C, more preferably 200°C to 300°C. If the solvent has such a boiling point, there is no risk of the solvent volatilizing too quickly during baking (heat treatment), so that sufficient thermal fluidity can be obtained during film formation, and it is believed that a resist underlayer film having excellent filling / flattening properties can be formed. In addition, if the solvent has such a boiling point, the solvent does not volatilize and remains in the film after baking, so there is no risk of adversely affecting the film properties such as etching resistance.

[0133] When (D) a high boiling point solvent is used, the blending amount is preferably 1 to 30 parts by mass per 100 parts by mass of the organic solvent having a boiling point of less than 180° C. Such a blending amount is preferable because it can impart sufficient thermal fluidity during baking and does not remain in the film, leading to deterioration of the film properties such as etching resistance.

[0134] When the metal-containing film-forming composition is a metal-containing film-forming composition that can be used as a resist underlayer film in a multilayer resist method, it is sufficient that the composition contains one or more of the above-mentioned (A) metal-containing film-forming compounds and (B) organic solvent, and may contain additives such as (C) crosslinking agent, (D) surfactant, (E) acid generator, and (F) metal oxide nanoparticles having an average primary particle size of 100 nm or less, as necessary. In another aspect, the metal-containing film-forming composition of the present invention may further contain one or more of (C) crosslinking agent, (D) surfactant, and (E) acid generator.

[0135] The metal-containing film-forming composition of the present invention may further contain components other than those described above, such as additives for imparting filling properties and / or planarizing properties.

[0136] Hereinafter, examples of components contained in the composition for forming a metal-containing film of the present invention other than the above (A) the compound for forming a metal-containing film and (B) the organic solvent will be described.

[0137] [(C) Crosslinking agent] In addition, the metal-containing film-forming composition of the present invention may further contain a crosslinking agent (C) in order to enhance the curability of the metal-containing film-forming compound and further suppress intermixing with a layer formed on the metal-containing film, such as a resist top layer film. The crosslinking agent is not particularly limited, and various known crosslinking agents can be widely used. Examples include melamine-based crosslinking agents, acrylate-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, epoxy-based crosslinking agents, and phenol-based crosslinking agents (e.g., methylol or alkoxymethyl-type crosslinking agents of polynuclear phenols). The content of the crosslinking agent (C) is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the metal-containing film-forming compound (A).

[0138] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof.

[0139] A specific example of the acrylate crosslinking agent is dipentaerythritol hexaacrylate.

[0140] Specific examples of glycoluril crosslinking agents include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and / or hydroxy substituted products thereof, and partial self-condensates thereof.

[0141] Specific examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof.

[0142] Specific examples of the urea-based crosslinking agent include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxyl substituted derivatives, and partial self-condensates thereof.

[0143] A specific example of the β-hydroxyalkylamide crosslinking agent is N,N,N',N'-tetra(2-hydroxyethyl)adipamide.

[0144] Specific examples of the isocyanurate crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate.

[0145] Specific examples of the aziridine crosslinking agent include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0146] 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-tertbutyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymer.

[0147] Specific examples of epoxy crosslinking agents include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0148] Specific examples of polynuclear phenol-based crosslinking agents include compounds represented by the following general formula (XL-1). [ka] (In the formula, Q is a single bond or a q1-valent hydrocarbon group having 1 to 20 carbon atoms. R3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. q1 is an integer of 1 to 5.)

[0149] Q is a single bond or a q1-valent hydrocarbon group having 1 to 20 carbon atoms. q1 is an integer of 1 to 5, and is 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 from which q hydrogen atoms have been removed. R3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an octyl group, an ethylhexyl group, a decyl group, and an eicosanyl group. R3 is preferably a hydrogen atom or a methyl group.

[0150] Specific examples of the compound represented by the above general formula (XL-1) include the following compounds. Among these, from the viewpoint of improving the curability and thickness uniformity of the organic film, hexamethoxymethylated triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred. R3 is the same as above.

[0151] [ka]

[0152] [ka]

[0153] <(D) Surfactant> To improve the coating property in spin coating, the metal-containing film-forming composition of the present invention may contain (D) a surfactant. For example, the surfactants described in

[0142] to

[0147] of JP-A-2009-269953 may be used. The amount of the surfactant added is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, based on 100 parts by mass of the metal-containing film-forming compound (A).

[0154] <(E) Acid Generator> In the metal-containing film-forming composition of the present invention, an acid generator can be added to further promote the curing reaction of the (A) metal-containing film-forming compound. The acid generator may be one that generates an acid by thermal decomposition or one that generates an acid by light irradiation, and any of these may be added. Specifically, the materials described in paragraphs

[0061] to

[0085] of JP-A-2007-199653 may be added, but are not limited thereto.

[0155] The acid generators can be used alone or in combination of two or more. When an acid generator is added, the amount of the acid generator is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, based on 100 parts by mass of the (A) compound for forming a metal-containing film.

[0156] <(F) Metal oxide nanoparticles> In addition, in order to further improve the dry etching resistance, the metal-containing film-forming composition of the present invention may contain (F) metal oxide nanoparticles. Specifically, metal oxide nanoparticles selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles are preferred.

[0157] By selecting the above metal oxides, it is possible to form a metal-containing film having better dry etching resistance.

[0158] The (F) metal oxide nanoparticles preferably have an average primary particle diameter of 100 nm or less, more preferably an average primary particle diameter of 50 nm or less, even more preferably an average primary particle diameter of 30 nm or less, and particularly preferably an average primary particle diameter of 15 nm or less. The average primary particle diameter of the metal oxide nanoparticles before being dispersed in an organic solvent can be determined by a method of directly measuring the size of the primary particles from an electron microscope photograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the particle. Next, the volume (mass) of each of 100 or more particles is determined by approximating it to a rectangular parallelepiped of the determined particle diameter, and the volume average particle diameter is determined and taken as the average particle diameter. The same results can be obtained using any of the transmission type (TEM), scanning type (SEM), and scanning transmission type (STEM) electron microscopes.

[0159] Within this particle size range, the particles can exhibit good dispersibility in the composition for forming a metal-containing film, and can improve the dry etching resistance of the metal-containing film without deteriorating the filling / planarization properties of dense areas of a fine pattern structure.

[0160] When (F) metal oxide nanoparticles are added, the amount added is preferably 5 to 50 parts, more preferably 10 to 30 parts, per 100 parts by mass of (A) the compound for forming a metal-containing film.

[0161] <Liquid additives and thermally decomposable polymers> In addition, in the metal-containing film-forming composition of the present invention, as an additive for imparting filling / flattening properties, for example, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a thermally decomposable polymer having a weight loss rate of 40% by mass or more between 30° C. and 250° C. and a weight average molecular weight of 300 to 200,000 is preferably used. This thermally decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formula (DP1) or (DP1a).

[0162] [ka] (In the formula, R6 is a hydrogen atom or an optionally substituted saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. Y 1 is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.

[0163] [ka] (In the formula, R 6a is an alkyl group having 1 to 4 carbon atoms. a is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms, which may have an ether bond; and n represents the average number of repeating units and is 3 to 500.

[0164] When the liquid additive or the thermally decomposable polymer is added, the amount added is preferably 5 to 100 parts, more preferably 10 to 50 parts, per 100 parts by mass of the (A) compound for forming a metal-containing film.

[0165] <Flow promoter (BP)> In addition, a flow promoter (BP) can be added to the metal-containing film-forming composition of the present invention as an additive for imparting filling and / or planarization properties. The flow promoter (BP) preferably has an organic group represented by the following general formula (bp1a) and an aromatic ring.

[0166] [ka] (wherein * represents the bond site to the oxygen atom, R B is a divalent organic group having 1 to 10 carbon atoms, R A is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

[0167] The flow promoter (BP) has an organic group represented by the general formula (bp-1a) and can impart thermal flowability and thermosetting properties to the (A) metal-containing film-forming compound. Also, the flow promoter (BP) has an aromatic ring and can mitigate the deterioration of the dry etching resistance of the (A) metal-containing film-forming compound.

[0168] The flow promoter (BP) preferably has at least one structural unit represented by any one of the following general formulae (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5).

[0169] (Constituent units: BP-1, BP-2 and BP-3) [ka] In the general formulae (BP-1) and (BP-2), W1 and W2 each independently represent a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. a1 is represented by the following general formula (4). Y is a group represented by the following general formula (5). n1 is 0 or 1, n2 is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. [ka] (In the above general formula (BP-3), Z1 is a group represented by the following general formula (6), R a1 is the following general formula (4), n4 is 0 or 1, n5 is 1 or 2, and each V independently represents a hydrogen atom or a linking portion. [ka] (* indicates the bond to the oxygen atom.) [ka] (* represents a bond.) [ka] (In the above general formula (6), W1, W2, Y, and n1 are the same as defined above.)

[0170] Resins having a structural unit represented by any one of the general formulas (BP-1), (BP-2) and (BP-3) have excellent heat resistance because they have a high carbon density fused carbon ring including a cardo structure. Because of the above characteristics, a metal-containing film capable of filling a stepped substrate without generating voids can be formed even when subjected to high-temperature baking. In addition, because they have excellent dry etching resistance, even when added to the metal-containing film-forming composition of the present invention, they can impart heat resistance and thermal fluidity without significantly deteriorating the excellent dry etching resistance of the metal-containing film-forming composition.

[0171] The resin having a structural unit represented by any one of the above general formulae (BP-1), (BP-2) and (BP-3) may be a compound represented by the following general formulae (bp-1) and / or (bp-2) and / or (bp-3). [ka] (In the above general formulas (bp-1) and (bp-2), W1, W2, R a1 , Y, n1, and n2 are the same as those explained above for general formulae (BP-1) and (BP-2).

[0172] [ka] (In the above general formula (bp-3), Z1, R a1 , n4, and n5 are the same as those explained for general formula (BP-3) above.)

[0173] Specific examples of the resin having a structural unit represented by any one of the above general formulas (bp-1), (bp-2) and (bp-3) include, but are not limited to, the following compounds.

[0174] [ka]

[0175] With regard to the above resins (bp-1), (bp-2) and (bp-3), the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn in terms of polystyrene as measured by gel permeation chromatography (i.e., dispersity) is preferably within the range of 1.00≦Mw / Mn≦1.25, and more preferably 1.00≦Mw / Mn≦1.10.

[0176] A compound having a degree of dispersion in such a range can provide a metal-containing film-forming composition with better thermal fluidity, and thus can provide a metal-containing film-forming composition with better embedding and / or planarization properties when incorporated into a material.

[0177] Alternatively, the resin having a structural unit represented by any one of the above general formulae (BP-1), (BP-2) and (BP-3) may be a polymer having repeating units represented by the following general formulae (bp-4) and / or (bp-5) and / or (bp6). [ka] (In the above general formulas (bp-4) and (bp-5), W1, W2, R a1 Y, n1, and n2 are the same as those explained in the above general formulae (BP-1) and (BP-2), and L1 is a divalent organic group having 1 to 40 carbon atoms.

[0178] [ka] (In the above general formula (bp-6), Z1, R a1 , n4, and n5 are the same as those explained in the general formula (BP-3), and L1 is a divalent organic group having 1 to 40 carbon atoms.

[0179] These are polymers obtained by using a compound represented by any one of the general formulas (bp-1), (bp-2) and (bp-3), and since the compound is used, the polymers have excellent dry etching resistance and heat resistance. In addition, since the polymers are not monomers but have repeating units, the outgassing components are small, and since the polymers have molecular weight distribution, the crystallinity is relaxed and improvement in film formability can be expected.

[0180] L1, which is a linking group constituting the repeating unit of any of the above general formulae (bp-4), (bp-5), and (bp-6), is a divalent organic group having 1 to 40 carbon atoms, and specific examples thereof include the following.

[0181] [ka]

[0182] Furthermore, the linking group L1 of the above-described polymer is preferably represented by the following general formula (10). [ka] (In the above general formula (10), R1 is a hydrogen atom or an organic group containing an aromatic ring having 1 to 20 carbon atoms, and the dashed line represents a bond.)

[0183] Specific examples of the above general formula (10) include the following, and among the following, a methylene group, that is, R3 is a hydrogen atom, is preferred in terms of ease of availability of raw materials.

[0184] [ka]

[0185] Furthermore, the weight average molecular weight of the polymer having a repeating structural unit represented by any one of the above general formulae (bp-4), (bp-5) and (bp-6) in terms of polystyrene as determined by gel permeation chromatography is preferably 1,000 to 12,000, and more preferably Mw is 2,000 to 10,000.

[0186] Within this molecular weight range, the solubility in organic solvents can be ensured, and the generation of sublimates during baking can be suppressed. In addition, the thermal fluidity of the metal-containing film-forming composition is good, so that when the metal-containing film-forming composition is blended with a material, a metal-containing film-forming composition having better embedding and / or planarization properties can be provided.

[0187] (Body unit: BP-4) [ka] (In the formula, m3 and m4 represent 1 or 2, and Z2 is either a single bond or a structure represented by the following general formula (7). R x is any of the structures represented by the following general formula (8). [ka] (In the formula, * represents a bond, l represents an integer of 0 to 3, and R az ~R fz each independently represents a hydrogen atom or an optionally fluorine-substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a phenylethyl group; R az and R bz may be bonded to form a cyclic compound.) [ka] (In the formula, * represents a bonding site to the aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9).) [ka] (wherein * represents the bond site to the carbonyl group, R i is the above general formula (4). j represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. 3z and n4z represents the number of substituents on the aromatic ring, and each represents an integer of 0 to 7. 3z +n 4z n is between 0 and 7. 5z represents 0 to 2.)

[0188] From the viewpoint of dry etching resistance and heat resistance, in the above general formula (BP-4), Z2 is preferably either a single bond or a structure represented by the above formula (4A). [ka] (In the formula, * represents a bond, and l is the same as in formula (7) above.)

[0189] In the above general formula (8), when Q1 represents a linear hydrocarbon group having 1 to 30 carbon atoms, a methylene group constituting Q1 may be substituted with an oxygen atom or a carbonyl group. From the viewpoints of dry etching resistance and heat resistance, Q1 is preferably a structure represented by the above general formula (9).

[0190] Compounds containing a structural unit represented by the above general formula (BP-4) have a structure in which aromatic rings are linked by a single bond or general formula (7), and therefore have a high carbon density, and compositions for forming metal-containing films containing these compounds have excellent heat resistance. In addition, as shown in the above formula (7), the linking group Z2 can be appropriately selected from various linking groups in accordance with the desired performance. In particular, by introducing the structure represented by the above formula (4A) as the linking group Z2, heat resistance and / or etching resistance can be imparted without impairing film formability. In addition, the highly flexible terminal portion R x Since the composition for forming a metal-containing film has a rigid aromatic ring structure, it is possible to form a thick film without generating defects such as cracks. xcontains a terminal group Q1 that imparts thermal fluidity, and as the terminal group Q1, a flexible hydrocarbon structure that contributes to improving thermal fluidity and a rigid aromatic ring structure that contributes to etching resistance and heat resistance can be introduced in any ratio according to the required performance. As described above, the metal-containing film-forming composition to which these compounds are added can achieve a high level of both embedding ability and / or flattening property and heat resistance, and can form a thick film according to the required properties.

[0191] (Body unit: BP-5) [ka] (In the above general formula (BP-5), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X1 is a divalent organic group having 1 to 30 carbon atoms, R a is the above general formula (4). p is an integer of 0 to 5, q1 is an integer of 1 to 6, p+q1 is an integer of 1 or more and 6 or less, and q2 is 0 or 1.

[0192] In the above general formula (BP-5), examples of the divalent organic group having 1 to 30 carbon atoms represented by X1 include alkanediyl groups such as a methylene group, an ethanediyl group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, an octanediyl group, and a decanediyl group; monocyclic cycloalkanediyl groups such as a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclooctanediyl group, a cyclodecanediyl group, a methylcyclohexanediyl group, and an ethylcyclohexanediyl group; a bicyclo[2.2.1]heptanediyl group, a bicyclo[2.2.2]octanediyl group, a tricyclo[5.2.1.0]diyl group, and the like. 2,6 ]Decanediyl group (dicyclopentylene group), tricyclo[3.3.1.1 3,7 ]decanediyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 ] Polycyclic cycloalkanediyl groups such as dodecanediyl group and adamantanediyl group; arenediyl groups such as phenylene group and naphthylene group.

[0193] Examples of the alkanediyloxy group represented by X1 include groups in which the alkanediyl group and an oxygen atom are combined, etc. Examples of the cycloalkanediyloxy group represented by X include groups in which the cycloalkanediyl group and an oxygen atom are combined, etc.

[0194] A part or all of the hydrogen atoms of the above alkanediyl group, cycloalkanediyl group, alkanediyloxy group, cycloalkanediyloxy group, arenediyl group, etc. may be substituted. Examples of the substituent include the above R a The examples of the substituent that may be possessed by the organic group represented by the following formula include the same groups as those mentioned above.

[0195] Examples of the organic group represented by X1 include groups represented by the following formulas. [ka] (In the above formula, * represents a bond.)

[0196] From the viewpoint of availability of raw materials, a preferred example of X1 is a methylene group.

[0197] Specific examples of resins having a structural unit represented by the above general formula (BP-5) include the following.

[0198] [ka]

[0199] [ka]

[0200] Since the polymer containing the structural unit represented by the above general formula (BP-5) has a structure in which aromatic rings are linked by an organic group (X1), the carbon density is high, and therefore the metal-containing film-forming composition containing these compounds exhibits high dry etching resistance and is excellent in heat resistance. Furthermore, since the organic group of the structure represented by the above general formula (4), which contributes to improving thermal fluidity, is directly bonded to the aromatic ring, which is the core structure of the resin, via an oxygen atom, the metal-containing film-forming composition to which these polymers are added can achieve a high level of both embedding and / or planarization properties and heat resistance and / or etching resistance. In addition, since the aromatic ring structure of the core is not too rigid and forms a repeating structure via the organic group (X1), which is the linking group, it is possible to form the metal-containing film-forming composition without generating defects such as cracks.

[0201] In the composition for forming a metal-containing film of the present invention, the content of the flow promoter (BP) is preferably 50 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less, relative to 100 mass parts of the compound for forming a metal-containing film.

[0202] The amount of the fluidity promoter added can be adjusted to any ratio according to the required characteristics of the process using the metal-containing film-forming composition of the present invention. If it is desired to minimize the deterioration of dry etching resistance, the ratio of the fluidity promoter can be reduced, and if it is desired to tolerate the deterioration of dry etching resistance to a certain extent and further improve the embedding property / flattening property, the ratio of the fluidity promoter can be increased.

[0203] <Metal-containing film formation method> The present invention provides a method for forming a metal-containing film (filling film) that functions, for example, as a resist underlayer film of a multilayer resist film used in lithography or a planarizing film for semiconductor manufacturing, using the above-mentioned composition for forming a metal-containing film.

[0204] In the method for forming a resist underlayer film using the composition for forming a metal-containing film of the present invention, the composition for forming a metal-containing film is coated on a substrate to be processed by spin coating or the like. By using the spin coating or the like, good embedding properties can be obtained. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote a crosslinking reaction in order to prevent mixing with the resist upper layer film or the resist intermediate film. The baking is preferably performed at 100°C or higher and 600°C or lower for 10 to 600 seconds, more preferably at 200°C or higher and 500°C or lower for 10 to 300 seconds. Considering the influence on device damage and wafer deformation, the upper limit of the heating temperature in the wafer process of lithography is preferably 600°C or lower, more preferably 500°C or lower.

[0205] In addition, in a method for forming a resist underlayer film using the composition for forming a metal-containing film of the present invention, the composition for forming a metal-containing film of the present invention can be coated on a substrate to be processed by a spin coating method or the like as described above, and the composition for forming a metal-containing film can be baked and cured in an atmosphere having an oxygen concentration of 0.1 vol.% or more and 21 vol.% or less to form a metal-containing film.

[0206] By baking the metal-containing film-forming composition of the present invention in such an oxygen atmosphere, a sufficiently cured film can be obtained. Although the atmosphere during baking may be air, it is preferable to seal in an inert gas such as N2, Ar, or He to reduce oxygen in order to prevent oxidation of the metal-containing film. In order to prevent oxidation, it is necessary to control the oxygen concentration, which is preferably 1000 ppm or less, more preferably 100 ppm or less (volume basis). Preventing oxidation of the metal-containing film during baking is preferable because it does not increase absorption or reduce etching resistance.

[0207] <Pattern Forming Method Using Composition for Forming Resist Underlayer Film> In addition, the present invention provides a method for forming a pattern by a two-layer resist process using the above-mentioned composition for forming a metal-containing film, which is a method for forming a pattern on a substrate to be processed, comprising the steps of: (I-1) a step of applying the composition for forming a metal-containing film onto a substrate to be processed and then heat-treating the composition to form a metal-containing film; (I-2) forming a resist top layer film on the metal-containing film using a photoresist material; (I-3) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern is formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0208] Since the resist top layer film in the two-layer resist process exhibits etching resistance to chlorine-based gases, it is preferable that the dry etching of the metal-containing film in the two-layer resist process is performed using the resist top layer film as a mask with an etching gas mainly containing a chlorine-based gas.

[0209] In addition, the present invention provides a method for forming a pattern by a three-layer resist process using the above-mentioned composition for forming a metal-containing film, which is a method for forming a pattern on a substrate to be processed, comprising the steps of: (II-1) a step of applying the composition for forming a metal-containing film onto a substrate to be processed and then heat-treating the composition to form a metal-containing film; (II-2) forming a resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (II-5) a step of transferring the pattern to the resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) a step of transferring a pattern to the metal-containing film by dry etching using the resist intermediate film to which the pattern has been transferred as a mask; and (II-7) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0210] An example of a pattern forming method by a three-layer resist process will be described with reference to FIG. 1. In the present invention, as a pattern forming method by a three-layer resist process using the above-mentioned metal-containing film forming composition, as shown in FIG. 1(A), a metal-containing film 3 is formed on a processable layer 2 of a processable substrate 1A having a processable layer 2 formed on a substrate 1, using the above-mentioned metal-containing film forming composition, a resist intermediate film 4 is formed on the metal-containing film 3 using a resist intermediate film material, and a resist upper layer film 5 is formed on the intermediate film 4 using a photoresist material. Subsequently, as shown in FIG. 1(B), an exposed portion 6 of the resist upper layer film is exposed to a pattern. Next, as shown in FIG. 1(C), development is performed with a developer to form a resist upper layer film pattern 5a on the resist upper layer film. Next, as shown in FIG. 1(D), a pattern is transferred to the resist intermediate film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and a resist intermediate film pattern 4a is formed. Next, as shown in Fig. 1(E), the silicon-containing resist intermediate film with the transferred pattern is used as a mask to transfer the pattern to the metal-containing film by dry etching to form a metal-containing film pattern 3a. Next, as shown in Fig. 1(F), the processable layer 2 of the processable substrate 1A is processed using the metal-containing film with the pattern formed thereon as a mask to form a pattern 2a on the processable substrate 1A.

[0211] The silicon-containing resist intermediate film that can be used as the intermediate film in the above-mentioned three-layer resist process shows the etching resistance by chlorine-based gas.Therefore, when using the silicon-containing resist intermediate film as the intermediate film in the above-mentioned three-layer resist process, the dry etching of the metal-containing film that uses the silicon-containing resist intermediate film as a mask is preferably carried out by using the etching gas that mainly comprises chlorine-based gas.

[0212] As the silicon-containing resist intermediate film that can be used in the above three-layer resist process, a polysiloxane-based intermediate film is also preferably used. By imparting an anti-reflection effect to the silicon-containing resist intermediate film, reflection can be suppressed. In particular, for 193 nm exposure, if a material containing many aromatic groups and having high etching selectivity with the substrate is used as the organic film, the k value becomes high and the substrate reflection becomes high, but by imparting absorption to the silicon-containing resist intermediate film so that the k value becomes appropriate, it is possible to suppress reflection and make the substrate reflection 0.5% or less. As the silicon-containing resist intermediate film having an anti-reflection effect, anthracene is preferably used for 248 nm and 157 nm exposure, and polysiloxane that has a pendant light-absorbing group having a phenyl group or a silicon-silicon bond and is crosslinked by acid or heat is preferably used for 193 nm exposure.

[0213] In addition, in the present invention, as another embodiment of the pattern forming method by the four-layer resist process using the above-mentioned metal-containing film forming composition, a metal-containing film is formed on a substrate to be processed using the above-mentioned metal-containing film forming composition, a silicon-containing resist intermediate film is formed on the metal-containing film using a silicon-containing resist intermediate film material, an organic antireflective coating (BARC) or an adhesion film is formed on the silicon-containing resist intermediate film, a resist upper layer film is formed on the BARC using a photoresist material, the resist upper layer film is pattern-exposed, and then developed with a developer to form a pattern on the resist upper layer film, the resist upper layer film on which the pattern is formed is used as a mask to transfer the pattern to the BARC or adhesion film and the silicon-containing resist intermediate film by dry etching, the silicon-containing resist intermediate film on which the pattern is transferred is used as a mask to transfer the pattern to the metal-containing film by dry etching, and the substrate to be processed is processed using the metal-containing film on which the pattern is formed as a mask to form a pattern on the substrate to be processed.

[0214] Alternatively, an inorganic hard mask may be formed instead of the silicon-containing intermediate film. In this case, the method for forming a pattern on a substrate to be processed includes the steps of: (III-1) A step of applying the composition for forming a metal-containing film onto a substrate to be processed and then heat-treating the composition to form a metal-containing film; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist top layer film on the organic thin film using a photoresist material; (III-5) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (III-6) a step of transferring a pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (III-7) A step of transferring a pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. According to the pattern forming method having the above-mentioned features, a pattern, for example a semiconductor device circuit pattern, can be formed on a substrate to be processed.

[0215] As described above, when an inorganic hard mask is formed on a metal-containing film, a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, examples of methods for forming a silicon nitride film are described in JP-A-2002-334869 and WO-A-2004 / 066377. The thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. In addition, as the inorganic hard mask, a SiON film, which has a high effect as an anti-reflection film, is most preferably used. Since the substrate temperature when forming the SiON film is 300 to 500°C, the metal-containing film needs to withstand a temperature of 300 to 500°C. The metal-containing film-forming composition used in the present invention has high heat resistance and can withstand high temperatures of 300 to 500°C, so that it is possible to combine an inorganic hard mask formed by a CVD method or an ALD method with a metal-containing film formed by a spin coating method.

[0216] As described above, a photoresist film may be formed on the inorganic hard mask as a resist top layer, but an organic anti-reflective coating (BARC) or adhesion film may be formed on the inorganic hard mask by spin coating, and a photoresist film may be formed on top of that. In particular, when a SiON film is used as the inorganic hard mask, the two-layer anti-reflective coating of the SiON film and the BARC makes it possible to suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another advantage of forming the BARC is that it has the effect of reducing the tailing of the photoresist pattern directly above the SiON film.

[0217] For example, one aspect of the pattern formation method of the present invention is a method for forming a pattern on a substrate to be processed, comprising the steps of: (IV-1) A step of applying the composition for forming a metal-containing film onto a substrate to be processed and then heat-treating the composition to form a metal-containing film; (IV-2) forming an organic intermediate film on the metal-containing film; (IV-3) forming a silicon-containing resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the organic intermediate film; (IV-4) forming a resist top layer film on the silicon-containing resist intermediate film or the organic thin film using a photoresist material; (IV-5) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (IV-6) a step of transferring a pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern is formed as a mask; (IV-7) A step of transferring a pattern to an organic intermediate film by dry etching using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; (IV-8) A step of transferring a pattern to the metal-containing film by dry etching using the organic intermediate film as a mask; and (IV-9) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The pattern forming method is characterized by comprising the steps of:

[0218] In the above pattern forming method, the resist upper layer film may be either positive or negative, and may be the same as a commonly used photoresist composition. The photoresist composition may contain metal atoms such as Sn, In, Ga, Ge, Al, Ce, La, Cs, Zr, Hf, Ti, Bi, Sb, and Zn. When forming the resist upper layer film using the above photoresist composition, it may be formed by spin coating or deposition processing using CVD or ALD.

[0219] When forming a photoresist composition by spin coating, the resist is prebaked after coating, preferably at 60 to 180° C. for 10 to 300 seconds. Thereafter, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain a resist pattern. The thickness of the resist top layer is not particularly limited, but is preferably 10 to 500 nm, particularly preferably 20 to 400 nm.

[0220] When the photoresist composition is formed by deposition processing by CVD or ALD, the resist composition is an EUV photosensitive metal oxide film, and the metal is selected from Sn, Zr, Hf, Ti, Bi, Sb, etc., among which Sn, which has excellent EUV photosensitivity, is preferred. The metal oxide-containing film may be a photosensitive organometallic oxide film such as an organotin oxide (e.g., haloalkyl Sn, alkoxyalkyl Sn, or amidoalkyl Sn). Some specific examples of suitable precursors include trimethyltin chloride, dimethyltin dichloride, methyltin trichloride, tris(dimethylamino)methyltin(IV), and (dimethylamino)trimethyltin(IV).

[0221] Metal oxide-containing films may be deposited by PECVD or PEALD, for example using a Lam Vector® tool, with the Sn oxide precursor separated from the O precursor / plasma in the ALD embodiment. The deposition temperature is preferably in the range of 50° C. to 600° C. The deposition pressure is preferably between 100 and 6000 mTorr. The flow rate of the metal oxide-containing film precursor liquid (e.g., organotin oxide precursor) may be 0.01 to 10 cmm and the gas flow rate (CO2, CO, Ar, N2) may be 100 to 10000 sccm. The plasma power may be 200 to 1000 W per 300 mm wafer station using a high frequency plasma (e.g., 13.56 MHz, 27.1 MHz, or higher). The deposition thickness is preferably 100 to 2000 Å.

[0222] Examples of the exposure light include high energy rays with a wavelength of 300 nm or less, specifically, excimer lasers with wavelengths of 248 nm, 193 nm, and 157 nm, soft X-rays with wavelengths of 3 to 20 nm, electron beams, and X-rays.

[0223] The method for forming the pattern on the resist upper layer film is preferably photolithography with a wavelength of 5 nm or more and 300 nm or less, direct drawing with an electron beam, nanoimprinting, or a combination of these.

[0224] In the pattern forming method, the development method is preferably alkaline development or development using an organic solvent.

[0225] Next, etching is performed using the obtained resist pattern as a mask. In the three-layer resist process, etching of the silicon-containing resist intermediate film and the inorganic hard mask is performed using a fluorocarbon-based gas as a mask for the upper resist pattern. This forms a silicon-containing resist intermediate film pattern and an inorganic hard mask pattern.

[0226] Next, the metal-containing film is etched using the silicon-containing resist intermediate film pattern or the inorganic hard mask pattern as a mask. The etching of the metal-containing film is preferably performed using an etching gas mainly containing a chlorine-based gas.

[0227] The next etching of the workpiece can also be done by a normal method, for example, if the workpiece is SiO2, SiN, or a silica-based low dielectric constant insulating film, etching is done mainly with fluorocarbon gases. When etching the substrate with fluorocarbon gases, the silicon-containing resist intermediate film pattern in the three-layer resist process is peeled off at the same time as the substrate is processed.

[0228] The metal-containing film obtained by using the metal-containing film-forming composition of the present invention is characterized by excellent etching resistance when etching the workpiece.

[0229] The workpiece (substrate) is not particularly limited, and may be a substrate such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, or Al, or a substrate on which a workpiece layer is formed. As the workpiece layer, various low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, or Al-Si and their stopper films are used, and may be formed to a thickness of usually 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming a workpiece layer, the substrate and the workpiece layer are made of different materials.

[0230] In the pattern forming method using the resist underlayer film forming composition of the present invention, it is preferable to use a substrate to be processed having a structure or step having a height of 30 nm or more. As described above, the metal-containing film forming composition of the present invention has excellent filling / flattening properties, so that even if the substrate to be processed has a structure or step (unevenness) having a height of 30 nm or more, a flat cured film can be formed. The height of the structure or step of the substrate to be processed is preferably 30 nm or more, more preferably 50 nm or more, and more preferably 100 nm or more. In the method for processing a stepped substrate having a pattern of the above height, the metal-containing film forming composition of the present invention is formed into a film and filled / flattened, so that the film thickness of the resist intermediate film and resist top layer film formed thereafter can be made uniform, which is very preferable.

[0231] Furthermore, in the present invention, a pattern formation method by a four-layer resist process using the above-mentioned metal-containing film-forming composition includes forming a metal-containing film on a substrate to be processed using the above-mentioned metal-containing film-forming composition, forming an organic intermediate film on the metal-containing film using an organic intermediate film material, forming a silicon-containing resist intermediate film on the organic intermediate film using a silicon-containing resist intermediate film material, forming an organic antireflective coating (BARC) or adhesion film on the silicon-containing resist intermediate film as necessary, forming a resist upper layer film on the silicon-containing film or on the BARC using a photoresist material, and exposing the resist upper layer film to a pattern. and then developing the resist top layer film with a developer to form a pattern in the resist top layer film, transferring the pattern to the BARC or adhesion film and the silicon-containing resist intermediate film by dry etching using the resist top layer film on which the pattern has been formed as a mask, transferring the pattern to the organic intermediate film by dry etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask, transferring the pattern to the metal-containing film using the organic intermediate film as a mask, and processing the processed substrate using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the processed substrate.

[0232] As the organic intermediate film material that can be used for the organic intermediate film, those already known as underlayer films for the three-layer resist method or the two-layer resist method using a silicon resist composition, 4,4'-(9-fluorenylidene)bisphenol novolac resin (molecular weight 11,000) described in JP-A-2005-128509, and many other resins including novolac resins, known as resist underlayer film materials for the two-layer resist method or the three-layer resist method, can be used. In addition, when it is desired to increase the heat resistance more than that of normal novolac, a polycyclic skeleton such as 6,6'-(9-fluorenylidene)-di(2-naphthol) novolac resin can be introduced, and further a polyimide resin can be selected (for example, JP-A-2004-153125).

[0233] The organic intermediate film can be formed on a substrate to be processed by spin coating or the like using a composition solution in the same manner as the photoresist composition. After forming the organic underlayer film by spin coating or the like, it is desirable to bake the film to evaporate the organic solvent. The baking temperature is preferably in the range of 80 to 400°C, and the baking time is preferably in the range of 10 to 300 seconds.

[0234] Instead of the organic resist underlayer film material, an organic hard mask formed by a CVD method or an ALD method can also be used.

[0235] Since the organic intermediate film in the above multilayer resist process exhibits etching resistance to chlorine-based gases, it is preferable that in the above multilayer resist process, the dry etching of the metal-containing film is performed using the organic intermediate film as a mask by using an etching gas mainly containing a chlorine-based gas.

[0236] <Method of forming a tone-reversal pattern using a composition for forming a metal-containing film> In addition, the present invention provides a tone-reversal pattern forming method using the above-mentioned metal-containing film-forming composition, which is a method for forming a pattern on a substrate to be processed, comprising the steps of: (V-1) a step of forming a resist underlayer film on a substrate to be processed; (V-2) a step of forming a resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (V-3) forming a resist upper layer film on the resist intermediate film or on a combination of the inorganic hard mask intermediate film and an organic thin film using a photoresist material; (V-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (V-5) a step of transferring a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (V-6) a step of transferring a pattern to the resist underlayer film by dry etching using the resist intermediate film or the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; (V-7) a step of applying the composition for forming a metal-containing film onto the resist underlayer film on which the pattern has been formed, and then heat-treating the composition to cover the resist underlayer film with a metal-containing film, thereby filling spaces between the resist underlayer film patterns with the metal-containing film; (V-8) a step of etching back the metal-containing film covering the resist underlayer film on which the pattern is formed by a chemical stripper or dry etching to expose an upper surface of the resist underlayer film on which the pattern is formed; (V-9) a step of removing the resist intermediate film or the hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) a step of removing the resist underlayer film on which the pattern is formed and the surface is exposed by dry etching to form a reverse pattern of the original pattern on the metal-containing film; (V-11) A step of processing the substrate to be processed using the metal-containing film on which the reverse pattern is formed as a mask to form a reverse pattern on the substrate to be processed. The present invention provides a method for forming a tone-reversal pattern, comprising the steps of:

[0237] A tone-reversal pattern forming method using a metal-containing film-forming composition will be described with reference to FIG. 2. In the present invention, as a tone-reversal pattern forming method using such a metal-containing film-forming composition, as shown in FIG. 2(G), a resist underlayer film 7 is formed on a processable layer 2 of a processable substrate 1A having a processable layer 2 formed on a substrate 1, a resist intermediate film 4 or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film and an organic thin film is formed on the resist underlayer film 7, and a resist upper layer film 5 is formed on the resist intermediate film 4 or the combination of an inorganic hard mask intermediate film and an organic thin film using a photoresist material. Subsequently, as shown in FIG. 2(H), the exposed portion 6 of the resist upper layer film is exposed to a pattern. Next, as shown in FIG. 2(I), the resist upper layer film is developed with a developer to form a resist upper layer film pattern 5a on the resist upper layer film. Next, as shown in FIG. 2(J), the resist upper layer film on which the pattern is formed is used as a mask to transfer the pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching to form a resist intermediate film pattern 4a or an inorganic hard mask intermediate film pattern. Next, as shown in FIG. 2(K), the resist intermediate film on which the pattern is transferred, or the inorganic hard mask intermediate film is used as a mask to transfer the pattern to the resist underlayer film by dry etching to form a resist underlayer film pattern 7a. Next, as shown in FIG. 2(L), the resist underlayer film on which the pattern is formed is coated with a metal-containing film 8 using the above-mentioned metal-containing film forming composition, and the space between the resist underlayer film patterns 7a is filled with the metal-containing film 8. Next, the metal-containing film covering the resist underlayer film on which the pattern is formed is etched back by a chemical stripper or dry etching to form an inverted metal-containing film pattern 8a as shown in FIG. 2(M). Next, the resist intermediate film 4a or the hard mask intermediate film remaining on the upper surface of the resist underlayer film pattern 7a is removed by dry etching to expose the upper surface of the resist underlayer film pattern 7a as shown in Fig. 2(N). Next, the resist underlayer film pattern 7a with the exposed surface is removed by dry etching to obtain a metal-containing film having a reverse pattern 8a of the original pattern formed thereon as shown in Fig. 2(O).Next, as shown in FIG. 2(P), the processable layer 2 is processed using the metal-containing film on which the reversal pattern is formed as a mask, to form a reversal pattern 2b in the processable layer of the processable substrate.

[0238] As described above, when forming a resist underlayer film on a substrate to be processed, the resist underlayer film can be formed by a method using a coating type organic underlayer film material, a CVD method, an ALD method, etc. Coating type organic underlayer film materials are disclosed in JP2012-1687A, JP2012-77295A, JP2004-264710A, JP2005-043471A, JP2005-250434A, JP2007-293294A, JP2008-65303A, JP2009-100111A, and JP2006-2009-2010. JP 2004-205685 A, JP 2007-171895 A, JP 2009-14816 A, JP 2007-199653 A, JP 2008-274250 A, JP 2010-122656 A, JP 2012-214720 A, JP 2014-29435 A, Examples of the resins and compositions disclosed in International Publication WO2012 / 077640, International Publication WO2010 / 147155, International Publication WO2012 / 077640, International Publication WO2010 / 147155, International Publication WO2012 / 176767, JP 2005-128509 A, JP 2006-259249 A, JP 2006-259482 A, JP 2006-293298 A, JP 2007-316282 A, JP 2012-145897 A, JP 2017-119671 A, JP 2019-44022 A, and the like can be mentioned.

[0239] In the above-mentioned tone reversal pattern forming method, it is preferable to coat the obtained resist underlayer film pattern with a metal-containing film forming composition, and then remove the metal-containing film using a dry etching gas mainly composed of a chlorine-based gas to expose the upper surface of the resist underlayer film pattern. Then, the resist intermediate film or hard mask intermediate film remaining on the resist underlayer film is removed by dry etching with a fluorocarbon-based gas, and the resist underlayer film pattern with the exposed surface is removed by dry etching with an oxygen-based gas to form a metal-containing film pattern.

[0240] In the tone reversal patterning method, the resist underlayer film pattern preferably has a structure or step having a height of 30 nm or more. As described above, the metal-containing film-forming composition of the present invention has excellent filling and / or planarization properties, so that even if the processed film has a structure or step (unevenness) having a height of 30 nm or more, a flat cured film can be formed. The height of the structure or step of the resist underlayer film pattern is preferably 30 nm or more, more preferably 50 nm or more, and more preferably 100 nm or more. In the method for reversing a resist underlayer film pattern having a pattern of the above height, the metal-containing film-forming composition of the present invention is formed into a film and filled and planarized, so that the reversal and transfer of the pattern can be performed with high accuracy, which is very preferable. Compared to the resist underlayer film using a conventional coating-type organic underlayer film material, the metal-containing film-forming composition of the present invention has excellent resistance to dry etching using a fluorocarbon-based gas, so that the resist underlayer film pattern can be reversed with the metal-containing film-forming composition to form a desired resist pattern on the processed film with high accuracy. EXAMPLES

[0241] The present invention will be specifically described below using Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these.

[0242] [Synthesis example] In the following synthesis examples and comparative synthesis examples, the following organic group raw material group G: (G1) to (G14) and the silicon-containing organic group raw material group H: (H1) were used.

[0243] Raw material group G: (G1) to (G14) are shown below. [ka]

[0244] Raw material group H: (H1) is shown below. [ka]

[0245] As the metal source M, the following metal compounds were used. (M1): Titanium tetraisopropoxide (Sigma-Aldrich Corp, 377996) (M2): Titanium butoxide tetramer (FUJIFILM Wako Pure Chemical Industries, Ltd.) (M3): Zr(OBu)4: Zirconium(IV) tetrabutoxide (80% by mass solution in 1-butanol) (Tokyo Chemical Industry Co., Ltd., Z0016) (M4): Hf(OBu)4: Hafnium(IV) n-butoxide (Sigma-Aldrich Corp, 667943)

[0246] [Synthesis Example 1] Synthesis of metal-containing film-forming compound (A-1) Under a nitrogen atmosphere, a solution of 54.5 g of n-butanol in 1.6 g of deionized water was dropped into 40.5 g of n-butanol solution of 28.4 g of titanium tetraisopropoxide (M1) over 2 hours at room temperature while stirring. This caused hydrolysis and condensation of the metal compound M1. 26.4 g of organic group raw material (G1) was added to the obtained solution and stirred at room temperature for 30 minutes. After concentrating this solution 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, 69.0 g of PGMEA / PGME (weight ratio 70 / 30) solution was added and heated at 40°C under reduced pressure until IPA was no longer distilled, to obtain a PGMEA / PGME solution of the metal-containing film-forming compound (A-1). The concentration of components other than the solvent in the solution was 20% by mass.

[0247] [Synthesis Examples 2 to 12 and Comparative Synthesis Examples 13 to 16] Synthesis of metal-containing film-forming compounds (A-2) to (A-12) and comparative metal-containing film-forming compounds (R-1) to (R-4) The compounds (A-2) to (A-12) for forming a metal-containing film and the comparative compounds (R-1) to (R-4) for forming a metal-containing film shown in Table 1 were obtained under the same reaction conditions as in Synthesis Example 1, except that one of the above metal sources M and one or two of the above compound group G were used in the amounts shown in Table 1.

[0248] [Table 1]

[0249] [Comparative Synthesis Example 17] Synthesis of Comparative Metal-containing Film-forming Compound (R-5) Under a nitrogen atmosphere, 48.0 g of zirconium (IV) tetrabutoxide (80% by mass 1-butanol solution) (M3) was dissolved in 59.4 g of PGMEA / PGME (weight ratio 70 / 30) solution, and the reaction temperature was increased to 50° C. while stirring, and 20.4 g of compound H1 was dropped into the solution. After dropping, the reaction temperature was set to 60° C. and stirring was continued for 2 hours. Next, a mixture obtained by suspending 29.6 g of compound G9 in 24.8 g of PGMEA / PGME (weight ratio 70 / 30) solution was added to the reaction system, and stirring was continued for 1 hour while keeping the reaction temperature at 60° C. After cooling to room temperature, the resulting reaction solution was filtered with a 0.45 μm PTFE filter to obtain a PGMEA / PGME solution of the comparative metal-containing film-forming compound (R-5). The concentration of components other than the solvent in the solution was 21% by mass.

[0250] [Table 2]

[0251] [Synthesis of Comparative Organic Film-Forming Resin (R-6)] In a nitrogen atmosphere, 160.2g of 1,5-dihydroxynaphthalene, 56.8g of formaldehyde, and 300g of PGME (propylene glycol monomethyl ether) were added and homogenized at an internal temperature of 100℃. Then, a mixture of 8.0g of paratoluenesulfonic acid monohydrate and 8.0g of PGME, which had been mixed and homogenized in advance, was slowly dropped and reacted at an internal temperature of 80℃ for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, 2,000ml of MIBK was added, and the mixture was washed six times with 500ml of pure water, and the organic layer was dried under reduced pressure. 300g of THF was added to the residue to make a homogenous solution, and then crystallized in 2,000g of hexane. The precipitated crystals were separated by filtration, washed twice with 500g of hexane, and collected. The collected crystals were dried in a vacuum at 70℃ to obtain resin (R-6).

[0252] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, and the results were as follows: (R-6): Mw = 3,300, Mw / Mn = 2.54

[0253] [ka]

[0254] (Synthesis of Flow Enhancer) The flow promoter was synthesized using the organic group raw material group G: (G19) to (G21) and modifying agent K: (K1) to (K2) shown below.

[0255] The organic group raw material group G: (G19) to (G21) are shown below. [ka]

[0256] The modifying agents K: (K1) to (K2) are shown below. [ka]

[0257] [Synthesis of flow promoter (BPA-1)] Under a nitrogen atmosphere, 45.5 g of the compound (G19) of the organic group raw material group G, 9.8 g of potassium carbonate, and 150 g of DMF were added to obtain a uniform dispersion at an internal temperature of 50°C. 17.6 g of the modifying agent (K1) was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and then the separated water layer was removed. The organic layer was further washed six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, and the organic layer was dried under reduced pressure to obtain a flow promoter (BPA-1).

[0258] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows: (BPA-1): Mw=965, Mw / Mn=1.08

[0259] [ka]

[0260] [Synthesis of flow promoter (BPA-2)] 80.0 g of the epoxy compound (G20) of the organic group raw material group G, 51.0 g of the modifying agent (K2), and 600 g of 2-methoxy-1-propanol were made into a homogeneous solution at an internal temperature of 100° C. under a nitrogen atmosphere, and then 5.7 g of benzyltriethylammonium chloride was added and stirred at an internal temperature of 120° C. for 12 hours. After cooling to room temperature, 1,500 g of methyl isobutyl ketone was added, and the organic layer was washed five times with 300 g of pure water. The organic layer was dried under reduced pressure to obtain a flow promoter (BPA-2).

[0261] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows: (BPA-2): Mw=900, Mw / Mn=1.04

[0262] [ka]

[0263] [Synthesis of flow promoter (BPA-3)] Under a nitrogen atmosphere, 20.0 g of the resin (G21) of the organic group raw material group G, 34.5 g of potassium carbonate, and 100 g of DMF were added to obtain a uniform dispersion at an internal temperature of 50°C. 23.8 g of the modifying agent (K1) was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and then the separated water layer was removed. The organic layer was further washed six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, and the organic layer was dried under reduced pressure to obtain a flow promoter (BPA-3).

[0264] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows: (BPA-3): Mw=9,400, Mw / Mn=3.59

[0265] [ka]

[0266] [Preparation of metal-containing film-forming composition (MUL-1)] The metal-containing film-forming compound (A-1) was dissolved in a mixed solvent ((B) organic solvent) of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) containing 0.5 mass % of (D) surfactant FC-4430 (manufactured by Sumitomo 3M Limited) in the ratio shown in Table 3, and the resulting solution was filtered through a 0.02 μm membrane filter to prepare a metal-containing film-forming composition (MUL-1).

[0267] [Preparation of metal-containing film-forming compositions (MUL-2 to 18) and comparative metal-containing film-forming compositions (Comparative Examples MUL-1 to 6)] Each composition was prepared in the same manner as in the preparation of the metal-containing film-forming composition (MUL-1), except that the type and content of each component were as shown in Table 3. In Table 3, "-" indicates that the corresponding component was not used. The crosslinking agent used was one represented by the following formula (C-1). The acid generator (TAG) used was one represented by the following formula (E-1). The high boiling point solvent (B-1) used was ethylene glycol dibenzyl ether: boiling point 364°C.

[0268] [Crosslinking agent, acid generator] The crosslinking agent (C-1) and the acid generator (E-1) used in the metal-containing film-forming composition are shown below.

[0269] [ka] [ka]

[0270] [Table 3]

[0271] [Example 1 and Comparative Example 1: Evaluation of Filling Characteristics] Each of the compositions prepared above (MUL-1 to 18, and comparative examples MUL-1 to 6) was applied onto a SiO2 wafer substrate (substrate A) having a dense line and space pattern (line width 60 nm, line depth 100 nm, distance between the centers of two adjacent lines 120 nm), and heated at 350°C for 60 seconds using a hot plate to form a metal-containing film with a thickness of 80 nm.

[0272] Furthermore, each of the compositions prepared above (MUL-1 to 18, and comparative examples MUL-1 to 6) was applied onto a SiO2 wafer substrate (substrate B) having a dense line and space pattern (line width 40 nm, line depth 120 nm, distance between the centers of two adjacent lines 80 nm) and heated at 350°C for 60 seconds using a hot plate to form a metal-containing film with a thickness of 80 nm.

[0273] The substrates A and B used are base substrates 9 (SiO2 wafer substrates) having dense line and space patterns as shown in FIG. 3(Q) (overhead view) and (R) (cross-sectional view). The cross-sectional shape of each wafer substrate obtained in the filling evaluation was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd., to confirm whether or not there were voids (air gaps) inside the metal-containing film filling the gaps between the lines. The results are shown in Table 4. When a metal-containing film-forming composition with poor filling properties was used, voids were generated inside the metal-containing film filling the gaps between the lines in this evaluation. When a metal-containing film-forming composition with good filling properties was used, a void-free metal-containing film 10 was filled inside the metal-containing film filling the gaps between the lines of the base substrate 9 having a dense line and space pattern as shown in FIG. 3(S).

[0274] [Table 4]

[0275] As shown in Table 4, in Examples 1-1 to 1-18 in which the metal-containing film-forming compositions (MUL-1 to 18) of the present invention were used, it was possible to fill dense line and space patterns in each substrate without generating voids even after baking at 350°C, and it was confirmed that the compositions had good filling properties even under high-temperature baking conditions.

[0276] On the other hand, in Comparative Examples 1-1 and 1-2 using comparative metal-containing film-forming compositions (Comparative Examples MUL-1 to 2 and 5) containing compounds for forming a metal-containing film having organic ligands not containing a bridging group of formulas (a-1) to (a-4) unlike the compounds for forming a metal-containing film of the present invention, voids were observed at the bottom of the pattern after baking at 350° C. in both Substrate A and Substrate B. It is presumed that these comparative metal-containing film-forming compositions produce metal-containing films with low heat resistance, which results in large volume shrinkage due to high-temperature baking, causing the generation of voids.

[0277] On the other hand, in Comparative Examples 1-3 to 1-5 using comparative metal-containing film-forming compositions (Comparative Examples UDL-3 to 5) containing a metal-containing film-forming compound containing a crosslinking group of the formulas (a-1) to (a-4) but not a ligand derived from the organic compound represented by formula (1), it was possible to fill the dense line and space pattern without generating voids on substrate A, but the generation of voids was confirmed on substrate B containing a finer pattern. These comparative metal-containing film-forming compositions contain a crosslinking group of the formulas (a-1) to (a-4) but do not contain a ligand derived from the organic compound represented by formula (1) of the present invention, and as a result, it is presumed that the heat resistance is insufficient, and therefore voids are generated on substrate B containing a finer pattern, which is more susceptible to heat from the substrate.

[0278] [Example 2 and Comparative Example 2: Evaluation of Planarization Characteristics] A flatness evaluation was performed using the substrate B used in the above filling evaluation. Specifically, for an underlying substrate 11 (SiO2 wafer substrate) having a dense line & space pattern as shown in FIG. 4(T), the cross-sectional shape of each wafer substrate in which no voids were observed in the above filling evaluation after baking at 350°C as shown in FIG. 4(U) was observed using a scanning electron microscope (SEM), and the step (Delta 12 in FIG. 4(U)) of the filling film 12 between the dense line pattern part and the non-line pattern forming part was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 5. In this evaluation, it can be said that the smaller the step, the better the flattening characteristics.

[0279] [Table 5]

[0280] As shown in Table 5, in Examples 2-1 to 2-18 using the metal-containing film-forming composition of the present invention (MUL-1 to 18), the step between the patterned portion and the non-patterned portion of the film was small, and it was found that the planarization performance was comparable to that of Comparative Example 2-1 using an organic resist underlayer film material. In addition, MDL-14 to which a high boiling point solvent (B-1) was added, and MDL-16 to 18 to which a flow promoter (BPA-1 to 3) was added showed better planarization properties than the composition without the additive. It is presumed that the thermal flowability of the metal-containing film-forming composition could be further improved by using the additive. On the other hand, the metal-containing film-forming compound (A-1) containing only the ligand derived from the organic compound represented by formula (1) was observed to have excellent planarization compared to the metal-containing film-forming compound (A-9) further containing a ligand other than the ligand derived from the organic compound represented by formula (1).

[0281] [Example 3 and Comparative Example 3: Etching Resistance Evaluation] Each of the compositions for forming a metal-containing film (MUL-1 to 18, and comparative examples MUL-1 to 6) was applied onto a silicon substrate and heated at 350°C for 60 seconds using a hot plate to form a metal-containing film with a thickness of 80 nm, and the thickness a was measured. Next, etching was performed using CF4 gas under the following conditions using a Tokyo Electron etching device TE8500 (conditions 1 and 2), and the thickness b was measured. The thickness etched per minute was calculated as the etching rate (nm / min) from the thickness etched during the specified time (thickness a - thickness b).

[0282] For condition 1, etching rates of 50 nm / min or less were judged as "very good (A)", those between 50 nm / min and 60 nm / min were judged as "good (B)", and those greater than 60 nm / min were judged as "poor (C)". For condition 2, etching rates of 35 nm / min or less were judged as "very good (A)", those between 35 nm / min and 40 nm / min were judged as "good (B)", and those greater than 40 nm / min were judged as "poor (C)". The results are shown in Table 6.

[0283] Dry etching condition 1 Pressure: 200mT RF power: 300W CF4 gas flow rate: 100sccm Time: 20sec

[0284] Dry etching condition 2 Pressure: 160mT RF power: 1000W CF4 gas flow rate: 20sccm Ar gas flow rate: 1000sccm Time: 60sec

[0285] [Table 6]

[0286] As shown in Table 6, it was found that Examples 3-1 to 3-18, which used the metal-containing film-forming composition of the present invention (MUL-1 to 18), exhibited excellent etching resistance against CF4 gas compared to the organic underlayer film material (Comparative Example 3-6, which used the comparative metal-containing film-forming compound (R-6)). In addition, results showing excellent dry etching resistance were obtained even for Comparative Example 3-5, which used the metal-containing film-forming compound (R-5) that was not hydrolyzed and condensed. In particular, results showing high resistance were obtained for the metal-containing film-forming composition of the present invention (MUL-1 to 18) even under Condition 2, which had a high Ar flow rate. For this reason, it is considered that the composition exhibits excellent resistance to physical etching with a high Ar flow rate used in oxide film etching of advanced devices.

[0287] The metal-containing film-forming compound (A-9) further containing a ligand other than the ligand derived from the organic compound represented by formula (1) was observed to have improved dry etching resistance compared to the metal-containing film-forming compound (A-1) containing only the ligand derived from the organic compound represented by formula (1). In other words, in the present invention, the dry etching resistance and planarization characteristics can be appropriately adjusted according to the required characteristics of the process used by adjusting the ratio of the ligand derived from the organic compound represented by formula (1) contained in the metal-containing film-forming compound.

[0288] [Example 4 and Comparative Example 4: Pattern Forming Method] The above-mentioned metal-containing film-forming compositions (MUL-1 to 18, Comparative Example MUL-6) were each applied onto a SiO2 wafer substrate having a trench pattern (trench width 10 μm, trench depth 0.10 μm), and baked in air at 350 ° C for 60 seconds to form a metal-containing film with a thickness of 80 nm. A silicon atom-containing resist intermediate film material (SOG-1) was applied thereon and baked at 220 ° C for 60 seconds to form a resist intermediate film with a thickness of 50 nm, and a single layer resist for ArF of the resist upper layer film material was applied thereon and baked at 105 ° C for 60 seconds to form a photoresist film with a thickness of 100 nm. An immersion protective film material (TC-1) was applied on the photoresist film and baked at 90 ° C for 60 seconds to form a protective film with a thickness of 50 nm.

[0289] The silicon-containing resist intermediate film material (SOG-1) was prepared as follows. First, the polymer represented by ArF silicon-containing intermediate film polymer (SiP1) and the thermal crosslinking catalyst (CAT1) were dissolved in an organic solvent containing 0.1 mass% of FC-4430 (manufactured by Sumitomo 3M Limited) in the ratio shown in Table 7. The mixture thus obtained was filtered through a fluorine resin filter with a pore size of 0.1 μm to prepare the silicon-containing resist intermediate film material (SOG-1).

[0290] [Table 7]

[0291] The structural formulae of the ArF silicon-containing intermediate film polymer (SiP1) and thermal crosslinking catalyst (CAT1) used are shown below.

[0292] [ka]

[0293] The resist top layer film material (ArF single layer resist) was prepared as follows: First, the polymer (RP1), acid generator (PAG1), and basic compound (Amine1) were dissolved in a solvent containing 0.1 mass % of surfactant FC-4430 (Sumitomo 3M Limited) in the ratios shown in Table 8, and the solution was filtered through a 0.1 μm fluorine resin filter to prepare the resist top layer film material.

[0294] [Table 8]

[0295] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) used in the resist top layer material (ArF single layer resist) are shown below.

[0296] [ka]

[0297] The immersion protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent in the ratio shown in Table 9, and filtering the solution through a 0.1 μm fluorine resin filter.

[0298] [Table 9]

[0299] The protective film polymer (PP1) used in the immersion protective film material (TC-1) is shown below. [ka]

[0300] Next, the film was exposed using an ArF immersion exposure apparatus (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35 degree dipole s-polarized illumination, 6% halftone phase shift mask), baked at 100°C for 60 seconds (PEB), and developed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 55 nm 1:1 positive line and space pattern (resist upper layer film pattern).

[0301] Next, the resist intermediate film was etched by dry etching using the resist upper layer film pattern as a mask to form a hard mask pattern, the metal-containing film was etched using the obtained hard mask pattern as a mask to form a metal-containing film pattern, and the SiO2 film was etched using the obtained metal-containing film pattern as a mask. Etching was performed under the following conditions using a ULVAC etching device CE-300I.

[0302] Transfer conditions of the resist top layer pattern to the resist intermediate layer. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 60sec

[0303] Conditions for transferring hard mask patterns to metal-containing films. Dry etching conditions with Cl2 gas Pressure: 1Pa Antenna RF power: 320W Bias RF power: 30W Cl2 gas flow rate: 25sccm Time: 45 seconds

[0304] Transfer conditions of metal-containing film pattern onto SiO2 film. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 60sec

[0305] The cross section of the pattern was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 10.

[0306] [Table 10]

[0307] As shown in Table 10, in Examples 4-1 to 4-18 in which the metal-containing film-forming composition of the present invention (MUL-1 to 18) was used, the resist upper layer film pattern was successfully transferred to the substrate in all cases, and it was confirmed that the metal-containing film-forming composition of the present invention is suitable for use in fine processing by the multilayer resist method. On the other hand, in Comparative Example 4-1 in which insufficient performance was confirmed in the dry etching resistance evaluation, the pattern shape was distorted during pattern processing, and ultimately a good pattern could not be obtained.

[0308] [Example 5 and Comparative Example 5: SOC Pattern Inversion Method] A coating type resist underlayer film material (SOC-1) was applied as a resist underlayer film on a silicon wafer substrate on which a SiO2 film was formed, and baked at 350°C for 60 seconds to form a resist underlayer film with a thickness of 150 nm. A silicon atom-containing resist intermediate film material (SOG-1) was applied on top of that and baked at 220°C for 60 seconds to form a resist intermediate film with a thickness of 40 nm. A single layer resist for ArF, which is a resist upper layer film material, was applied on top of that and baked at 105°C for 60 seconds to form a photoresist film with a thickness of 100 nm. An immersion protective film material (TC-1) was applied on the photoresist film and baked at 90°C for 60 seconds to form a protective film with a thickness of 50 nm.

[0309] The silicon-containing resist intermediate film material (SOG-1), resist top film material (ArF single layer resist), and immersion protective film material (TC-1) on the photoresist film were the same as those used in the pattern formation method (Example 4).

[0310] A coating type resist underlayer film material (SOC-1) was prepared by dissolving a polymer shown as a resist underlayer film polymer (SOP1) in an organic solvent containing 0.1 mass% of FC-4430 (manufactured by Sumitomo 3M) in the ratio shown in Table 11 and filtering the resultant solution through a fluorine resin filter having a pore size of 0.2 μm.

[0311] [Table 11]

[0312] The structural formula of the resist underlayer film polymer (SOP1) used is shown in Table 12.

[0313] [Table 12]

[0314] Next, the film was exposed using an ArF immersion exposure apparatus (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35 degree dipole s-polarized illumination, 6% halftone phase shift mask), baked at 100°C for 60 seconds (PEB), and developed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 55 nm 1:1 positive line and space pattern (resist upper layer film pattern).

[0315] Next, the resist intermediate film was etched by dry etching using the resist upper layer film pattern as a mask using a Tokyo Electron etching device Telius to form a hard mask pattern, and the resist lower layer film (SOC-1) was etched using the obtained hard mask pattern as a mask to form a SOC-1 film pattern. The etching conditions are as shown below.

[0316] Transfer conditions of the resist top layer pattern to the resist intermediate layer. Chamber pressure: 50mT RF power (top): 500W RF power (bottom): 300W CF4 gas flow rate: 150sccm CHF3 gas flow rate: 50sccm Time: 20sec

[0317] Conditions for transferring the hard mask pattern to the resist underlayer film. Chamber pressure: 10mT RF power (top): 1,000W RF power (bottom): 300W CO2 gas flow rate: 150sccm CO gas flow rate: 50sccm N2 gas flow rate: 50sccm H2 gas flow rate: 150sccm Time: 90sec

[0318] Next, the above-mentioned metal-containing film-forming compositions (MUL-1 to 18, Comparative Examples MUL-1 to 2) were applied onto the obtained SOC-1 film pattern, and baked in air at 350° C. for 60 seconds to form a metal-containing film with a thickness of 80 nm. Thereafter, the metal-containing film covering the SOC-1 film pattern was etched to expose the upper surface of the SOC-1 film pattern. The resist intermediate film remaining on the surface of the SOC-1 film pattern with the upper surface exposed was removed by etching, and then the exposed SOC-1 film pattern was removed by etching, and the above pattern was inverted on the metal-containing film, and the SiO2 film was etched using the obtained metal-containing film pattern as a mask. As a comparative example, the SiO2 film was also etched using the SOC-1 film pattern as a mask without using the metal-containing film-forming composition (Comparative Example 5-3). The etching conditions are as shown below.

[0319] Conditions for etching back metal-containing film (exposing SOC-1 film pattern). Pressure: 1Pa Antenna RF power: 320W Bias RF power: 30W Cl2 gas flow rate: 25sccm Time: 20sec

[0320] Removal of the resist intermediate film remaining on the SOC-1 film pattern. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 45 seconds

[0321] Removal of SOC-1 membrane pattern. Dry etching conditions with O2 gas Pressure: 1Pa Antenna RF power: 300W Bias RF power: 0W O2 gas flow rate: 25sccm Time: 35sec

[0322] Transfer conditions of metal-containing film pattern onto SiO2 film. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 60sec

[0323] Comparative Example 5-3: Conditions for transferring a SOC-1 film pattern to a SiO2 film. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 60sec

[0324] The cross section of the pattern was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 13.

[0325] [Table 13]

[0326] As shown in Table 13, in Examples 5-1 to 5-18 in which the metal-containing film-forming composition (MUL-1 to 18) of the present invention was used, the SOC-1 film pattern was accurately inverted in all cases, and the inverted pattern was finally transferred to the substrate without pattern collapse. From this, it was confirmed that the metal-containing film-forming composition of the present invention is suitable for use in microfabrication using a tone inversion etching method in a multilayer resist process. On the other hand, in Comparative Example 5-3 in which the SOC-1 film pattern was directly transferred to a SiO2 film, the etching resistance of the SOC-1 film was insufficient, and thus distortion of the pattern shape was confirmed. In addition, in Comparative Examples 5-1 to 5-2 in which insufficient performance was confirmed in the embedding characteristic evaluation (substrate B), the metal-containing film was not filled up to the bottom between the SOC-1 film patterns, so the pattern could not be inverted, and ultimately a good inverted pattern could not be obtained.

[0327] From the above, it has become clear that a metal-containing film-forming composition containing the metal-containing film-forming compound of the present invention has both high filling and planarization properties and dry etching resistance, and is therefore extremely useful as a metal-containing layer (resist underlayer film) material used in a multilayer resist method and as a reversal agent used in a tone reversal etching method, and that the pattern formation method of the present invention using this composition can form fine patterns with high precision even if the workpiece is a substrate having steps.

[0328] The present specification includes the following aspects. [1] (A) a metal-containing film-forming compound, The compound for forming a metal-containing film (A) is a compound derived from a metal-containing compound obtained by hydrolysis or condensation, or hydrolysis and condensation, of a metal compound represented by the following formula (A-1), and further has a ligand derived from an organic compound represented by the following formula (1). M(OR 1A )4(A-1) R 2ACOXCOOH (1) (Wherein, M is Ti, Zr, or Hf; R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by any one of the following general formulas (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms. [ka] (In the above general formulas (a-1) to (a-4), R a represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond. [2] The (A) metal-containing film-forming compound, one or more selected from a hydrolysate of only the metal compound represented by the formula (A-1), a condensate of only the metal compound represented by the formula (A-1), and a hydrolysis condensate of only the metal compound represented by the formula (A-1); An organic compound represented by the formula (1); The compound for forming a metal-containing film according to [1], which is a metal-containing compound that is a reaction product of the following: [3] In the formula (1), R 2A The compound for forming a metal-containing film according to [1] or [2], wherein the compound has a structure represented by the following general formula (B-1): [ka] (In the above general formula (B-1), R A1 is the structure represented by the above general formula (a-1), and R A2 is either of the structures represented by the above general formula (a-2) or (a-3), Z is either an oxygen atom or a secondary amine, L is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R A3 is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 or more and 6 or less, 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. [4] The compound for forming a metal-containing film according to any one of [1] to [3], wherein in the formula (1), the organic group X is a saturated hydrocarbon group having 2 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms. [5] The compound for forming a metal-containing film according to any one of [1] to [4], wherein in the formula (1), the organic group X is a group represented by any one of the following formulas (2): [ka] (In the above general formula (2), R a and R b is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and R c is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, and R a and R b may be bonded to form a cyclic substituent. *1 and *2 each represent the bond to the carbonyl group, and *1 and *2 may be reversed.) [6] The compound for forming a metal-containing film according to any one of [1] to [5], characterized in that the compound (A) for forming a metal-containing film contains a compound having a structure represented by the following general formula (m-1): [ka] (In the above formula (m-1), R ae ~R de each independently represents R in the above formula (A-1). 1A or COXCOR in the above formula (1) 2A Either ae ~R de At least one of the COXCOR in the above formula (A-1) 2A where n is 1 to 20, and M is the same as M in the above formula (A-1). [7] The (A) metal-containing film-forming compound further contains, in addition to the ligand derived from the organic compound represented by formula (1), at least one additional ligand selected from the group consisting of a ligand derived from an organic compound represented by formula (3) below and a ligand derived from any one of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride; The compound for forming a metal-containing film according to any one of [1] to [5], wherein the additional ligand does not contain a group represented by the above general formulae (a-1) to (a-4). R 3A COOH (3) (In the formula, R 3A is a monovalent organic group having 1 to 20 carbon atoms. [8] The compound for forming a metal-containing film according to [7], characterized in that the compound for forming a metal-containing film (A) contains a compound having any one of the structures shown below: [ka] (Above R 3a is either a monovalent organic group having 1 to 20 carbon atoms and not containing a crosslinking group, as represented by the above general formulas (a-1) to (a-4), or a structure represented by the following formula: 1A is R in the above formula (A-1) 1A is the same as R 2A is R in the above formula (1). 2A where n is 1 to 20, and M is the same as M in the above formula (A-1). [ka] (In the above formula, R 3b is an alkyl group having 1 to 10 carbon atoms, and * represents the bond to the carbonyl carbon. [9] A metal-containing film-forming composition, (A) a compound for forming a metal-containing film according to any one of [1] to [8], (B) Organic solvent A composition for forming a metal-containing film, comprising:

[10] The composition further comprises: (C) a crosslinking agent, (D) a surfactant, and (E) Acid generator The composition for forming a resist underlayer film according to [9], characterized in that it contains one or more of the following:

[11] The composition for forming a resist underlayer film according to [9] or

[10] , characterized in that the (B) organic solvent contains (B-1) a high boiling point solvent, and the (B-1) high boiling point solvent is one or more organic solvents having a boiling point of 180° C. or higher.

[12] The composition for forming a metal-containing film according to any one of [9] to

[11] , further comprising a flowability promoter (BP) having an organic group represented by the following general formula (bp1a) and an aromatic ring: [ka] (wherein * represents the bond site to the oxygen atom, R B is a divalent organic group having 1 to 10 carbon atoms, R A is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

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

[12] , characterized in that the flow promoter (BP) has at least one structural unit represented by any one of the following general formulas (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5). [ka] In the general formulae (BP-1) and (BP-2), W1 and W2 each independently represent a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. a1 is a group represented by the following general formula (4). Y is a group represented by the following general formula (5). n1 is 0 or 1, n2 is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. [ka] (In the above general formula (BP-3), Z1 is a group represented by the following general formula (6), Ra1 is the following general formula (4), n4 is 0 or 1, n5 is 1 or 2, and each V independently represents a hydrogen atom or a linking portion. [ka] (* indicates the bond to the oxygen atom.) [ka] (* represents a bond.) [ka] (In the above general formula (6), W1, W2, Y, and n1 are the same as defined above.) [ka] (In the formula, m3 and m4 represent 1 or 2, and Z2 is either a single bond or a structure represented by the following general formula (7). R x is any of the structures represented by the following general formula (8). [ka] (In the formula, * represents a bond, l represents an integer of 0 to 3, and R az ~R fz each independently represents a hydrogen atom or an optionally fluorine-substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a phenylethyl group; R az and R bz may be bonded to form a cyclic compound.) [ka] (In the formula, * represents a bonding site to the aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9).) [ka] (wherein * represents the bond site to the carbonyl group, R i is the above general formula (4). jrepresents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. 3z and n 4z represents the number of substituents on the aromatic ring, and each represents an integer of 0 to 7. 3z +n 4z n is between 0 and 7. 5z represents 0 to 2.) [ka] (In the above general formula (BP-5), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X1 is a divalent organic group having 1 to 30 carbon atoms, R a1 is the above general formula (4). p is an integer of 0 to 5, q1 is an integer of 1 to 6, p+q1 is an integer of 1 or more and 6 or less, and q2 is 0 or 1.

[14] Reacting at least one selected from a hydrolysis product of only a metal compound represented by the following formula (A-1), a condensation product of only a metal compound represented by the following formula (A-1), and a hydrolysis condensation product of only a metal compound represented by the following formula (A-1) with an organic compound represented by the following formula (1), or A method for producing (A) a compound for forming a metal-containing film, comprising hydrolyzing or condensing, or hydrolyzing and condensing, a metal compound represented by the following general formula (A-2): M(OR 1A )4(A-1) R 2A COXCOOH (1) (Wherein, M is Ti, Zr, or Hf; R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by any one of the following general formulas (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms. [ka] (In the above general formulas (a-1) to (a-4), R a represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond. (R 2A COXCOO) x M(OR 1A ) y (A-2) (Wherein, M is Ti, Zr, or Hf; R 1A is a monovalent organic group having 1 to 20 carbon atoms, R 2A is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by the above general formulas (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, x+y=4, and x and y are integers of 1 or more.

[15] A method for forming a pattern on a workpiece substrate, comprising: (I-1) A step of applying a composition for forming a metal-containing film according to any one of [9] to

[13] onto a substrate to be processed, and then performing a heat treatment to form a metal-containing film; (I-2) forming a resist top layer film on the metal-containing film using a photoresist material; (I-3) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern is formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

[16] A method for forming a pattern on a workpiece substrate, comprising: (II-1) A step of applying a composition for forming a metal-containing film according to any one of [9] to

[13] onto a substrate to be processed, and then performing a heat treatment to form a metal-containing film; (II-2) forming a resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (II-5) a step of transferring the pattern to the resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) a step of transferring a pattern to the metal-containing film by dry etching using the resist intermediate film to which the pattern has been transferred as a mask; and (II-7) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

[17] A method for forming a pattern on a workpiece substrate, comprising: (III-1) A step of applying a composition for forming a metal-containing film according to any one of [9] to

[13] onto a substrate to be processed, and then performing a heat treatment to form a metal-containing film; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist top layer film on the organic thin film using a photoresist material; (III-5) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (III-6) a step of transferring a pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (III-7) A step of transferring a pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

[18] A method for forming a pattern on a workpiece substrate, comprising: (IV-1) A step of applying a composition for forming a metal-containing film according to any one of [9] to

[13] onto a substrate to be processed, and then performing a heat treatment to form a metal-containing film; (IV-2) forming an organic intermediate film on the metal-containing film; (IV-3) forming a silicon-containing resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the organic intermediate film; (IV-4) forming a resist top layer film on the silicon-containing resist intermediate film or the organic thin film using a photoresist material; (IV-5) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (IV-6) a step of transferring a pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern is formed as a mask; (IV-7) A step of transferring a pattern to an organic intermediate film by dry etching using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; (IV-8) A step of transferring a pattern to the metal-containing film by dry etching using the organic intermediate film as a mask; and (IV-9) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

[19] A method for forming a pattern on a workpiece substrate, comprising the steps of: (V-1) a step of forming a resist underlayer film on a substrate to be processed; (V-2) a step of forming a resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (V-3) forming a resist upper layer film on the resist intermediate film or on a combination of the inorganic hard mask intermediate film and an organic thin film using a photoresist material; (V-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (V-5) a step of transferring a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (V-6) a step of transferring a pattern to the resist underlayer film by dry etching using the resist intermediate film or the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; (V-7) a step of applying a composition for forming a metal-containing film according to any one of [9] to

[13] onto the resist underlayer film on which the pattern has been formed, and then performing a heat treatment to cover the metal-containing film and fill spaces between the resist underlayer film patterns with the metal-containing film; (V-8) a step of etching back the metal-containing film covering the resist underlayer film on which the pattern is formed by a chemical stripper or dry etching to expose an upper surface of the resist underlayer film on which the pattern is formed; (V-9) a step of removing the resist intermediate film or the hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) a step of removing the resist underlayer film on which the pattern is formed and the surface is exposed by dry etching to form a reverse pattern of the original pattern on the metal-containing film; (V-11) A step of processing the substrate to be processed using the metal-containing film on which the reverse pattern is formed as a mask to form a reverse pattern on the substrate to be processed. 13. A method for forming a tone-reversal pattern comprising:

[0329] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention. [Explanation of symbols]

[0330] 1...substrate, 1A...processed substrate, 2...processed layer, 2a...pattern (pattern formed on processed layer), 3...metal-containing film, 3a...metal-containing film pattern, 4...resist intermediate film, 4a...resist intermediate film pattern, 5...resist upper layer film, 5a...resist upper layer film pattern, 6...exposed portion, 7...resist underlayer film, 7a...resist underlayer film pattern, 8...metal-containing film, 8a...metal-containing film pattern which is the inverse of the resist underlayer film pattern, 9...underlying substrate having dense lines & spaces, 10...metal-containing resist underlayer film, 11...underlying substrate having dense lines & spaces, 12...metal-containing resist underlayer film, Delta12...step between patterned portion and non-patterned portion of metal-containing resist underlayer film 12.

Claims

1. (A) a metal-containing film-forming compound, The compound (A) for forming a metal-containing film is a compound derived from a metal-containing compound obtained by hydrolysis or condensation, or hydrolysis and condensation, of a metal compound represented by the following formula (A-1), and further has a ligand derived from an organic compound represented by the following formula (1). M (OR １Ａ ) ４ (A-1) R ２Ａ COXCOOH (1) (Wherein, M is Ti, Zr, or Hf; R １Ａ is a monovalent organic group having 1 to 20 carbon atoms, R ２Ａ is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by any one of the following general formulas (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms. [Formula 1] (In the above general formulas (a-1) to (a-4), R ａ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q is 0 or 1, and * is a bond.

2. The (A) metal-containing film-forming compound is one or more selected from a hydrolysate of only the metal compound represented by the formula (A-1), a condensate of only the metal compound represented by the formula (A-1), and a hydrolysis condensate of only the metal compound represented by the formula (A-1); An organic compound represented by the formula (1); 2. The compound for forming a metal-containing film according to claim 1, which is a metal-containing compound which is a reaction product of:

3. In the formula (1), R ２Ａ The compound for forming a metal-containing film according to claim 1, characterized in that: [chemical 2] (In the above general formula (B-1), R Ａ１is the structure represented by the above general formula (a-1), and R Ａ２ is any of the structures represented by the above general formula (a-2) or (a-3), Z is any of an oxygen atom or a secondary amine, L is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R Ａ３ is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 or more and 6 or less, 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.

4. 2. The compound for forming a metal-containing film according to claim 1, wherein in formula (1), the organic group X is a saturated hydrocarbon group having 2 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms.

5. 2. The compound for forming a metal-containing film according to claim 1, wherein in the formula (1), the organic group X is a group represented by any one of the following formulas (2): [C3] (In the above general formula (2), R ａ and R ｂ is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms; R ｃ is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms; R ａ and R ｂ may be bonded to form a cyclic substituent. *1 and *2 each represent a bond to a carbonyl group, and *1 and *2 may be reversed.)

6. The compound for forming a metal-containing film according to claim 1, characterized in that the compound for forming a metal-containing film (A) contains a compound having a structure represented by the following general formula (m-1): [C4] (In the above formula (m-1), R ａｅ ~R ｄｅ each independently represents R in formula (A-1) １Ａ or COXCOR in the above formula (1) ２Ａ R ａｅ ~R ｄｅ At least one of the COXCOR in the above formula (A-1) ２Ａ where n is 1 to 20, and M is the same as M in the above formula (A-1).

7. The (A) metal-containing film-forming compound further contains, in addition to the ligand derived from the organic compound represented by formula (1), at least one additional ligand selected from the group consisting of a ligand derived from an organic compound represented by formula (3) below and a ligand derived from any one of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride:

2. The compound for forming a metal-containing film according to claim 1, wherein the additional ligand does not contain any of the groups represented by the above general formulas (a-1) to (a-4). R ３Ａ COOH (3) (In the formula, R ３Ａ is a monovalent organic group having 1 to 20 carbon atoms.

8. The compound for forming a metal-containing film according to claim 7, characterized in that the compound for forming a metal-containing film (A) contains a compound having any one of the structures shown below. [C5] (The above R ３ａ is either a monovalent organic group having 1 to 20 carbon atoms and not containing a crosslinking group, as represented by the above general formulas (a-1) to (a-4), or a structure represented by the following formula: １Ａ is R in the above formula (A-1). １Ａ is the same as R ２Ａ is R in the above formula (1). ２Ａ where n is 1 to 20, and M is the same as M in the above formula (A-1). [C6] (In the above formula, R ３ｂ is an alkyl group having 1 to 10 carbon atoms, and * represents the bond to the carbonyl carbon.)

9. A metal-containing film-forming composition comprising: (A) a compound for forming a metal-containing film according to any one of claims 1 to 8, and (B) Organic solvent A composition for forming a metal-containing film, comprising:

10. The composition further comprises: (C) a crosslinking agent, (D) a surfactant, and (E) Acid generator The composition for forming a resist underlayer film according to claim 9, which contains one or more of the following:

11. The composition for forming a resist underlayer film according to claim 9, wherein the (B) organic solvent comprises (B-1) a high boiling point solvent, and the (B-1) high boiling point solvent is one or more organic solvents having a boiling point of 180° C. or higher.

12. The metal-containing film-forming composition according to claim 9, further comprising a flowability promoter (BP) having an organic group and an aromatic ring represented by the following general formula (bp1a): [C7] (wherein * represents the bond site to the oxygen atom, R Ｂ is a divalent organic group having 1 to 10 carbon atoms, R Ａ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

13. The metal-containing film-forming composition according to claim 12, characterized in that the flow promoter (BP) has at least one structural unit represented by any one of the following general formulas (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5). [C8] (In the above general formulae (BP-1) and (BP-2), W １ And W ２ are each independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. ａ１is a group represented by the following general formula (4). Y is a group represented by the following general formula (5). １ is 0 or 1, n ２ is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. [C9] (In the above general formula (BP-3), Z １ is a group represented by the following general formula (6), R ａ１ is the following general formula (4). ４ is 0 or 1, n ５ is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. [C10] (* indicates the bond with the oxygen atom.) [C11] (* represents a bond.) [C12] (In the above general formula (6), W １ , W ２ , Y, n １ is the same as above.) [C13] (In the formula, m ３ and m ４ represents 1 or 2; Z ２ R is either a single bond or a structure represented by the following general formula (7). ｘ is any of the structures represented by the following general formula (8). [C14] (In the formula, * represents a bond, l represents an integer of 0 to 3, and R ａｚ ~R ｆｚ each independently represents a hydrogen atom, an optionally fluorine-substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a phenylethyl group; R ａｚ and R ｂｚ may be bonded to form a cyclic compound.) [C15] (wherein * represents the bonding site to the aromatic ring, and Q １is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9): [C16] (wherein * represents the bonding site to the carbonyl group, R ｉ is the above general formula (4). ｊ represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. ３ｚ and n ４ｚ represents the number of substituents on the aromatic ring, and each represents an integer of 0 to 7. ３ｚ +n ４ｚ is 0 to 7. ５ｚ represents 0 to 2.) [C17] (In the general formula (BP-5), R １ is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms; X １ is a divalent organic group having 1 to 30 carbon atoms, R ａ１ is the above general formula (4). p is an integer of 0 to 5, q １ is an integer from 1 to 6, p+q １ is an integer of 1 to 6, and q ２ is 0 or 1.)

14. reacting at least one selected from a hydrolysate of only a metal compound represented by the following formula (A-1), a condensate of only a metal compound represented by the following formula (A-1), and a hydrolysis-condensate of only a metal compound represented by the following formula (A-1) with an organic compound represented by the following formula (1); A method for producing a compound for forming a metal-containing film (A), comprising hydrolyzing or condensing, or hydrolyzing and condensing, a metal compound represented by the following general formula (A-2): M (OR １Ａ ) ４ (A-1) R ２Ａ COXCOOH (1) (Wherein, M is Ti, Zr, or Hf; R １Ａ is a monovalent organic group having 1 to 20 carbon atoms, R ２Ａ is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by any one of the following general formulas (a-1) to (a-4), and X is a divalent organic group having 2 to 20 carbon atoms. [C18] (In the above general formulas (a-1) to (a-4), R ａ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q is 0 or 1, and * is a bond. (R ２Ａ COXCOO) ｘ M (OR １Ａ ) ｙ (A-2) (Wherein, M is Ti, Zr, or Hf; R １Ａ is a monovalent organic group having 1 to 20 carbon atoms, R ２Ａ is a divalent organic group having 2 to 20 carbon atoms containing at least one crosslinking group represented by the above general formulas (a-1) to (a-4), X is a divalent organic group having 2 to 20 carbon atoms, x+y=4, and x and y are integers of 1 or more.

15. A method for forming a pattern on a workpiece substrate, comprising the steps of: (I-1) A step of applying the composition for forming a metal-containing film according to claim 9 onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (I-2) forming a resist top layer film on the metal-containing film using a photoresist material; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (I-4) a step of transferring a pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern is formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

16. A method for forming a pattern on a workpiece substrate, comprising the steps of: (II-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 9 onto a substrate to be processed and then heat-treating the composition; (II-2) forming a resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (II-5) a step of transferring a pattern to the resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) A step of transferring a pattern to the metal-containing film by dry etching using the resist intermediate film to which the pattern has been transferred as a mask; and (II-7) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

17. A method for forming a pattern on a workpiece substrate, comprising the steps of: (III-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 9 onto a substrate to be processed and then heat-treating the composition; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist top layer film on the organic thin film using a photoresist material; (III-5) a step of pattern-exposing the resist upper layer film and then developing the same with a developer to form a pattern on the resist upper layer film; (III-6) a step of transferring a pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (III-7) A step of transferring a pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

18. A method for forming a pattern on a workpiece substrate, comprising the steps of: (IV-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 9 onto a substrate to be processed and then heat-treating the composition; (IV-2) forming an organic intermediate film on the metal-containing film; (IV-3) forming a silicon-containing resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the organic intermediate film; (IV-4) forming a resist top layer film on the silicon-containing resist intermediate film or the organic thin film using a photoresist material; (IV-5) a step of pattern-exposing the resist upper layer film and then developing the same with a developer to form a pattern on the resist upper layer film; (IV-6) A step of transferring a pattern to a silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern is formed as a mask; (IV-7) A step of transferring a pattern to an organic intermediate film by dry etching using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; (IV-8) A step of transferring a pattern to the metal-containing film by dry etching using the organic intermediate film as a mask; and (IV-9) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

19. A method for forming a pattern on a workpiece substrate, comprising the steps of: (V-1) A step of forming a resist underlayer film on a substrate to be processed; (V-2) a step of forming a resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (V-3) forming a resist upper layer film on the resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film using a photoresist material; (V-4) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (V-5) a step of transferring a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (V-6) A step of transferring a pattern to the resist underlayer film by dry etching using the resist intermediate film or the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; (V-7) a step of applying the composition for forming a metal-containing film according to claim 9 onto the resist underlayer film on which the pattern has been formed, and then heat-treating the composition to cover the metal-containing film and fill spaces between the resist underlayer film patterns with the metal-containing film; (V-8) a step of etching back the metal-containing film covering the resist underlayer film on which the pattern has been formed by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern has been formed; (V-9) A step of removing the resist intermediate film or the hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) a step of removing the resist underlayer film having the pattern formed thereon and having an exposed surface by dry etching to form a reverse pattern of the original pattern on the metal-containing film; (V-11) A step of processing the substrate to be processed using the metal-containing film on which the reverse pattern is formed as a mask to form a reverse pattern on the substrate to be processed.

13. A method for forming a tone-reversal pattern comprising:

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