Compound for forming metal-containing films, composition for forming metal-containing films, and pattern forming 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 a compound for forming a metal-containing film, and a method for forming a pattern. [Background technology]

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

[0003] However, when the pattern was miniaturized while keeping the thickness of the photoresist film the same, that is, when the pattern width was reduced, the resolution performance of the photoresist film decreased. Furthermore, when attempting to develop the photoresist film with a developer, the aspect ratio became too large, resulting in pattern collapse. For this reason, the photoresist film has been made thinner as the pattern has been miniaturized.

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

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

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

[0007] One multilayer resist method is the three-layer resist method, which can be performed using the same resist compositions as those used in the single-layer resist method. In this three-layer resist method, for example, an organic film made of novolac resin or the like is deposited on the substrate to be processed as the resist underlayer, a silicon-containing resist interlayer is deposited on top of that as the resist interlayer, and a normal organic photoresist film is formed on top of that as the resist upper layer. When dry etching is performed using a fluorine-based gas plasma, the organic resist upper layer has a good etching selectivity ratio compared to the silicon-containing resist interlayer, so the resist upper layer pattern can be transferred to the silicon-containing resist interlayer by dry etching with a fluorine-based gas plasma. With this method, even if a resist composition that does not have sufficient thickness to form a pattern for direct processing of the substrate or a resist composition that does not have sufficient dry etching resistance for substrate processing is used, the pattern can be transferred to the silicon-containing resist interlayer (resist interlayer), and then by performing pattern transfer by dry etching with an oxygen-based or hydrogen-based gas plasma, a pattern of an organic film (resist underlayer) made of novolac resin or the like with sufficient dry etching resistance for substrate processing can be obtained. Many types of resist underlayer films, such as those described in Patent Document 1, are already known.

[0008] On the other hand, in recent years, the miniaturization of DRAM memory has accelerated, and there is a growing need for further improvements in dry etching resistance and for resist underlayer films with excellent embedding and planarization properties. While some coated organic underlayer film materials with excellent embedding and planarization properties have been reported, such as those described in Patent Document 2, there are concerns about dry etching resistance when considering application in advanced generations, and the applicability limits of conventional coated organic underlayer film materials are approaching.

[0009] To address the above challenges, development using materials containing metal elements in the resist underlayer film is being considered. Patent document 3 reports that materials using Ti compounds exhibit excellent dry etching resistance to CHF3 / CF4 gases and CO2 / N2 gases.

[0010] On the other hand, one challenge when using metal compounds as underlayer films for resists is their embedding properties. Although Patent Document 3 does not mention embedding properties, metal oxide compounds generally exhibit significant thermal shrinkage during baking, and high-temperature baking induces a significant deterioration in packing properties. Therefore, there are concerns that they may be insufficient as underlayer materials for resists that require high planarization, embedding, and heat resistance properties. Patent Documents 4 and 5 report that metal compounds modified with specific ligands exhibit excellent embedding properties, but the firing temperature used for the embedding property evaluations is a low 150°C, raising concerns that they may be insufficient for underlayer films that require heat resistance (for example, properties against heat treatments that may be applied after the formation of the underlayer film). Furthermore, because metal compounds with hydrolyzable groups protected by silicon-containing organic groups are used, condensation reactions are not easily promoted, resulting in insufficient density of the metal film obtained during firing and concerns about insufficient dry etching resistance.

[0011] One possible method to improve embedding properties is to use ligands with excellent thermosetting properties. Patent document 6 reports that metal compounds having substituted or unsubstituted ethynyl groups or substituted or unsubstituted ethynyl groups have excellent thermosetting properties and therefore exhibit excellent resolution and sensitivity as radiation-sensitive compositions. Examples include metal compounds having ligands derived from 4-vinylbenzoic acid and 4-allyloxybenzoic acid. However, there are concerns that these may be insufficient as resist underlayer materials that require high heat resistance for resist materials. [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] Japanese Patent Publication No. 2004-205685 [Patent Document 2] Specification of Patent No. 6714493 [Patent Document 3] Specification of Patent No. 6189758 [Patent Document 4] Specification of Patent No. 6786391 [Patent Document 5] Specification of Japanese Patent No. 7050137 [Patent Document 6] Japanese Patent Publication No. 2020-201480 [Overview of the project] [Problems that the invention aims to solve]

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

[0014] To solve the above problems, the present invention provides (A) a metal-containing film-forming compound, The present invention provides a metal-containing film-forming compound characterized in that the (A) metal-containing film-forming compound is a compound derived from a metal-containing compound obtained by hydrolysis or condensation of a metal compound represented by the following formula (A-1), and further possesses a ligand derived from an organic compound represented by the following formula (1). M(OR 1A )4(A-1) R 2A COXCOOH (1) (In the formula, M is Ti, Zr, or Hf, and R 1A R is a monovalent organic group having 1 to 20 carbon atoms. 2A (where X is a divalent organic group having 2 to 20 carbon atoms and containing at least one bridging group represented by 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(where is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.)

[0015] Such metal-containing film-forming compounds contain ligands derived from the organic compound of formula (1) which includes one or more crosslinking groups represented by (a-1) to (a-4). When used in a metal-containing film-forming composition, it is possible to provide a metal-containing film-forming composition with small volume shrinkage during baking and excellent planarization and / or embedding properties even after high-temperature baking. Furthermore, since it is a compound derived from a metal-containing compound obtained by hydrolysis or condensation of the metal compound represented by formula (A-1), when used in a metal-containing film-forming composition, it is possible to form a dense metal-containing film, providing a metal-containing film with extremely excellent dry etching resistance to the substrate being processed.

[0016] The (A) metal-containing film-forming compound is One or more selected from the hydrolysis product of only the metal compound represented by formula (A-1), the condensate product of only the metal compound represented by formula (A-1), and the hydrolysis condensate product of only the metal compound represented by formula (A-1), The organic compound represented by formula (1) above and It is preferable that the reactant is a metal-containing compound.

[0017] With such a metal-containing film-forming compound, ligands derived from the organic compound of formula (1) can be efficiently introduced into the metal compound. Therefore, when used in a metal-containing film-forming composition, it is possible to provide a metal-containing film that has a high degree of both embedding properties and dry etching resistance.

[0018] In equation (1) above, R 2A It is preferable that the structure is represented by the following general formula (B-1). [ka] (In the above general formula (B-1), R A1has 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 the bonding part with the carbon atom of the carbonyl.)

[0019] In the above general formula (1), if R 2A has the structure represented by the above formula (B-1), it becomes possible to highly balance the thermal fluidity and thermosetting properties of the above metal-containing film-forming compound. When this is used in a metal-containing film-forming composition, it is possible to provide a metal-containing film-forming composition exhibiting more excellent planarization properties and / or embedding properties.

[0020] In the above formula (1), it is preferable that 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.

[0021] In the above formula (1), if the organic group X has such a structure, it becomes possible to further improve the thermal fluidity of the above metal-containing film-forming compound. When this is used in a metal-containing film-forming composition, it is possible to provide a metal-containing film-forming composition exhibiting more excellent planarization properties and / or embedding properties.

[0022] In the above formula (1), it is preferable that the organic group X is a group represented by any of the following formulas (2).

Chemical formula

[0023] In formula (1), if the organic group X has such a structure, it becomes possible to further improve the thermal fluidity of the 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 and / or embedding properties.

[0024] For example, the metal-containing film-forming compound (A) 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 of these independently corresponds to R in equation (A-1) above. 1A or COXCOR in formula (1) above 2A It is either R ae ~R de At least one of the above formulas ( 1 ) COXCOR 2A Here, n is between 1 and 20, and M is the same as M in equation (A-1) above.

[0025] (A) The metal-containing film-forming compound may include, for example, a compound having the structure described above, although this is not limited to the above.

[0026] Preferably, the (A) metal-containing film-forming compound further comprises, in addition to the ligand derived from the organic compound represented by formula (1), a ligand derived from the organic compound represented by formula (3) below, and at least one additional ligand selected from ligands derived from succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic acid anhydride, wherein the additional ligand does not contain the group represented by the general formulas (a-1) to (a-4) above. R 3A COOH (3) (In the formula, R 3A (It is a monovalent organic group with 1 to 20 carbon atoms.)

[0027] When such compounds are used in metal-containing film-forming compositions, it becomes possible to accelerate the crosslinking reaction during firing, and to operate at lower firing temperatures. Furthermore, the accelerated crosslinking reaction makes it possible to form a dense metal-containing film, thereby improving etching resistance.

[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] (R above) 3a R is a monovalent organic group having 1 to 20 carbon atoms that does not contain the bridging group shown in the above general formulas (a-1) to (a-4), or one of the structures shown in the following formulas, 1A R in the above equation (A-1) is 1A It is the same as R 2A R in equation (1) above 2A This is the same as the above equation (A-1), where n is between 1 and 20, and M is the same as M in equation (A-1). [ka] (In the above formula, R 3b (where * represents an alkyl group with 1 to 10 carbon atoms, and * represents the bond with the carbonyl carbon.)

[0029] When additional ligands are included, (A) the metal-containing film-forming compound may include, but is not limited to, compounds having the structure described above.

[0030] Furthermore, the present invention relates to a metal-containing film-forming composition, (A) Metal-containing film-forming compound and the present invention (B) Organic solvents The present invention provides a metal-containing film-forming composition characterized by containing the following:

[0031] Such a metal-containing film-forming composition contains a metal-containing compound with excellent heat resistance and thermal fluidity, and therefore provides a metal-containing film-forming composition that has superior dry etching resistance compared to conventional organic underlayer film materials, as well as superior embedding and / or planarization properties compared to conventional metal-containing underlayer film materials.

[0032] The aforementioned composition further, (C) Crosslinking agent, (D) Surfactants, and (E) Acid generator It may contain one or more of the following.

[0033] A metal-containing film-forming composition containing the above-mentioned additives will be a metal-containing film-forming composition with superior coatability, dry etching resistance, and embedding and / or planarization properties.

[0034] The (B) organic solvent preferably includes a (B-1) high-boiling point solvent, and the (B-1) high-boiling point solvent preferably consists of one or more organic solvents with a boiling point of 180 degrees or higher.

[0035] By imparting thermal fluidity to the above-mentioned metal-containing film-forming compound through the addition of a high-boiling-point solvent, the metal-containing film-forming composition acquires even more advanced embedding and / or planarization properties.

[0036] Preferably, the metal-containing film-forming composition further contains a fluidity enhancer (BP) having an organic group and an aromatic ring represented by the following general formula (bp1a). [ka] (In the formula, * represents the bonding site to the oxygen atom, R B R is a divalent organic group with 1 to 10 carbon atoms. A (This refers to a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.)

[0037] By adding a fluidity enhancer (BP) to the above-mentioned metal-containing film-forming compound, heat resistance and thermal fluidity are imparted, composition This also possesses more advanced embedding and / or planarization characteristics.

[0038] Preferably, the fluidity enhancer (BP) has at least one constituent unit represented by any of the following general formulas (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5). [ka] (In the above general formulas (BP-1) and (BP-2), W1 and W2 are independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. a1 is the group represented by the following general formula (4). Y is the group represented by the following general formula (5). n1 is 0 or 1, n2 is 1 or 2, and V independently represents a hydrogen atom or a linkage. [ka] (In the above general formula (BP-3), Z1 is the base shown in the following general formula (6) in Yes, R a1 The following general formula (4) is given by: n4 is 0 or 1, n5 is 1 or 2, and V independently represents a hydrogen atom or a bonding group. [ka] (* indicates a bond with an oxygen atom.) [ka] (* indicates a bond.) [ka] (In the above general formula (6), W1, W2, Y, and n1 are the same as described above.) [ka] (In the formula, m3 and m4 represent 1 or 2, and Z2 is either a single bond or a structure shown in the general formula (7) below. x (This is one of the structures shown in the following general formula (8).) [ka] (In the formula, * represents a bond, l represents an integer from 0 to 3, and R az ~R fz Each of these independently represents a hydrogen atom or a C1-C10 alkyl group, phenyl group, or phenylethyl group which may be substituted with fluorine, and R az and R bz (These two components may combine to form a cyclic compound.) [ka] (In the formula, * represents the bonding site to the aromatic ring, and Q1 is Number of carbon atoms It consists of 1 to 30 linear saturated hydrocarbon groups, or a structure represented by the general formula (9) below. [ka] (In the formula, * represents the bonding site to the carbonyl group, R i The above general formula( 4) R j These are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, halogen atoms, nitro groups, amino groups, nitrile groups, and carbon number 2 This represents an alkoxycarbonyl group with approximately 10 carbon atoms, or an alkanoyloxy group with 1 to 10 carbon atoms. 3z and n 4z n represents the number of substituents on the aromatic ring, each representing an integer from 0 to 7. 3z +n 4z n is between 0 and 7 (inclusive). 5z (This represents values ​​from 0 to 2.) [ka] (In the above general formula (BP-5), R 1R 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, and R a1 This is the general formula (4) above. p is an integer between 0 and 5, q1 is an integer between 1 and 6, p+q1 is an integer between 1 and 6 (inclusive), and q2 is either 0 or 1.

[0039] A metal-containing film-forming composition to which a flow enhancer (BP) having at least one of the constituent units shown in (BP-1) to (BP-5) above is added will be a metal-containing film-forming composition with superior embedding and / or planarization properties.

[0040] Furthermore, the present invention involves reacting one or more selected from the hydrolysis product of a metal compound represented by the following formula (A-1), the condensate product of a metal compound represented by the following formula (A-1), and the hydrolysis condensate product of 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 metal-containing film-forming compound, characterized by including hydrolysis or condensation of a metal compound represented by the following general formula (A-2), or hydrolysis-condensation. M(OR 1A )4(A-1) R 2A COXCOOH (1) (In the formula, M is Ti, Zr, or Hf, and R 1A R is a monovalent organic group having 1 to 20 carbon atoms. 2A (where X is a divalent organic group having 2 to 20 carbon atoms and containing at least one bridging group represented by 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 (where is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) (R 2A COXCOO) x M(OR 1A ) y(A-2) (In the formula, M is Ti, Zr, or Hf, and R 1A R is a monovalent organic group having 1 to 20 carbon atoms. 2A (where x is a divalent organic group having 2 to 20 carbon atoms and containing at least one bridging group represented by the general formulas (a-1) to (a-4) above, X is a divalent organic group having 2 to 20 carbon atoms, x + y = 4, and x and y are integers of 1 or greater.)

[0041] With this manufacturing method, it is possible to provide a metal-containing film-forming compound containing a ligand derived from an organic compound of formula (1) that includes one or more crosslinking groups represented by (a-1) to (a-4). When this is used in a metal-containing film-forming composition, it is possible to provide a metal-containing film-forming composition that exhibits small volume shrinkage during baking and excellent planarization and / or embedding properties even after high-temperature baking. Furthermore, since it is possible to provide a compound derived from a metal-containing compound obtained by hydrolysis or condensation of a metal compound represented by formula (A-1), when this is used in a metal-containing film-forming composition, it is possible to form a dense metal-containing film, providing a metal-containing film with extremely excellent dry etching resistance to the workpiece substrate.

[0042] Furthermore, the present invention relates to a method for forming a pattern on a substrate to be processed, (I-1) A step of forming a metal-containing film by applying the metal-containing film-forming composition of the present invention onto a substrate to be processed, and then heat-treating it. (I-2) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. The present invention provides a pattern forming method characterized by having the following features.

[0043] The pattern formation method using the two-layer resist process described above allows for the formation of fine patterns on the workpiece (workpiece substrate).

[0044] Furthermore, the present invention relates to a method for forming a pattern on a substrate to be processed, (II-1) A step of forming a metal-containing film by applying the metal-containing film-forming composition of the present invention onto a substrate to be processed, and then heat-treating it. (II-2) A step of forming a resist interlayer on the metal-containing film, (II-3) A step of forming a resist upper layer film on the resist interlayer film using a photoresist material, (II-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-5) A step of transferring the pattern to the resist interlayer by dry etching, using the resist upper layer on which the pattern is formed as a mask. (II-6) A step of transferring the pattern to the metal-containing film by dry etching using the resist interlayer on which the pattern has been transferred as a mask, and (II-7) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. The present invention provides a pattern forming method characterized by having the following features.

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

[0046] Furthermore, the present invention relates to a method for forming a pattern on a substrate to be processed, (III-1) A step of forming a metal-containing film by applying the metal-containing film-forming composition of the present invention onto a substrate to be processed, and then heat-treating it. (III-2) A step of forming an inorganic hard mask interlayer selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film. (III-3) A step of forming an organic thin film on the inorganic hard mask interlayer, (III-4) A step of forming a resist upper layer film on the organic thin film using a photoresist material, (III-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (III-6) A step of transferring the pattern to the organic thin film and the inorganic hard mask interlayer film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (III-7) A step of transferring the pattern to the metal-containing film by dry etching using the inorganic hard mask interlayer on which the pattern has been transferred as a mask, and (III-8) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. The present invention provides a pattern forming method characterized by having the following features.

[0047] The pattern formation method using the four-layer resist process described above allows for the formation of fine patterns on a workpiece with high precision.

[0048] In this case, it is preferable that the inorganic hard mask interlayer is formed by CVD or ALD.

[0049] When the above inorganic hard mask is formed by CVD or ALD, fine patterns can be formed on the workpiece with higher precision.

[0050] Furthermore, the present invention relates to a method for forming a pattern on a substrate to be processed, (IV-1) A step of forming a metal-containing film by applying the metal-containing film-forming composition of the present invention onto a substrate to be processed, and then heat-treating it. (IV-2) A step of forming an organic interlayer on the metal-containing film, (IV-3) A step of forming a combination of an organic thin film and an inorganic hard mask interlayer selected from a silicon-containing resist interlayer, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic interlayer. (IV-4) A step of forming a resist upper layer film on the silicon-containing resist interlayer film or the organic thin film using a photoresist material. (IV-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (IV-6) A step of transferring the pattern to a silicon-containing resist interlayer or the organic thin film and the inorganic hard mask interlayer by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (IV-7) A step of transferring the pattern onto an organic interlayer by dry etching, using the silicon-containing resist interlayer or inorganic hard mask interlayer on which the pattern has been transferred as a mask. (IV-8) The aforementioned pattern is transferred A step of using the aforementioned organic interlayer as a mask to transfer a pattern to the metal-containing film by dry etching, and (IV-9) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. The present invention provides a pattern forming method characterized by having the following features.

[0051] The pattern formation method using the multilayer resist process described above allows for the formation of fine patterns on a workpiece with high precision.

[0052] Furthermore, the present invention relates to a method for forming a pattern on a substrate to be processed, (V-1) A step of forming a resist underlayer film on the substrate to be processed. (V-2) A step of forming a resist interlayer, or a combination of an inorganic hard mask interlayer 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) A step of forming a resist upper layer film using a photoresist material on the resist interlayer film, or a combination of an inorganic hard mask interlayer film and an organic thin film. (V-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (V-5) A step of transferring the pattern to the resist interlayer, or the organic thin film and the inorganic hard mask interlayer, by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (V-6) A step of transferring the pattern to the resist underlayer film by dry etching, using the resist interlayer film on which the pattern has been transferred, or an inorganic hard mask interlayer film, as a mask. (V-7) A step of coating the resist underlayer film on which the pattern described above has been formed with the metal-containing film composition of the present invention, and then heat-treating it to coat it with a metal-containing film, thereby filling the 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, thereby exposing the upper surface of the resist underlayer film on which the pattern has been formed. (V-9) A step of removing the resist interlayer or hard mask interlayer remaining on the upper surface of the resist underlayer by dry etching. (V-10) A step of removing the resist underlayer film on which the exposed surface pattern is formed by dry etching, and forming an inverted pattern of the original pattern on the metal-containing film. (V-11) A process of processing the workpiece substrate using the metal-containing film on which the inverted pattern is formed as a mask to form the inverted pattern on the workpiece substrate. The present invention provides a tone-reversal pattern formation method characterized by having the following features.

[0053] The pattern formation method using the inversion process described above allows for the formation of fine patterns on the workpiece with even greater precision. [Effects of the Invention]

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

[0055] In particular, in the fine patterning process using the multilayer resist method in the semiconductor device manufacturing process, even on a workpiece substrate having areas that are difficult to embed and / or planarize, such as densely packed areas of high aspect ratio fine pattern structures represented by miniaturized DRAM memory, the metal-containing film-forming composition containing the metal-containing film-forming compound of the present invention can embed without causing defects such as voids or peeling. Furthermore, it has superior dry etching resistance compared to conventional coating-type resist underlayer materials, so that fine patterns can be formed on the workpiece with even greater precision compared to conventional resist underlayer films.

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

[0057] Furthermore, since the pattern forming method of the present invention uses the metal-containing film-forming composition of the present invention, it is possible to form fine patterns on the workpiece with even greater precision. [Brief explanation of the drawing]

[0058] [Figure 1] Figure 1 is an explanatory diagram of an example of the pattern formation method of the present invention (3-layer resist process). [Figure 2] Figure 2 is an explanatory diagram of an example of the tone inversion pattern formation method of the present invention (inversion of the SOC pattern of a 3-layer resist process). [Figure 3] Figure 3 is an explanatory diagram of the embedding characteristics evaluation method. [Figure 4] Figure 4 is an explanatory diagram of the method for evaluating planarization characteristics. [Modes for carrying out the invention]

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

[0060] The inventors focused on metal materials that exhibit superior etching resistance compared to conventional resist underlayer materials and conducted extensive research. On the other hand, conventional metal compounds for forming resist underlayer films have poor heat resistance and undergo rapid volume shrinkage during baking, making it difficult to fill in steps in the workpiece substrate and flatten it after high-temperature baking. The inventors hypothesized that if an organic group with excellent heat resistance properties were used, rapid volume shrinkage during baking could be reduced and thermal fluidity could be improved, making it possible to fill in steps in the workpiece substrate without generating voids even after high-temperature baking. Furthermore, they hypothesized that a structure containing crosslinking groups at the ends would exhibit superior thermosetting properties during baking, resulting in a metal-containing film-forming compound with even better heat resistance. Moreover, since there is a concern that introducing an organic ligand with excellent heat resistance may degrade the dry etching resistance of the metal-containing film, the inventors hypothesized that by hydrolyzing or condensing a metal compound, or by using a compound derived from a metal-containing compound obtained by hydrolysis and condensation, it would be possible to improve dry etching resistance without degrading the filling properties.

[0061] The inventors of the present invention have conducted further intensive studies and have found that a metal-containing film-forming compound derived from a metal compound obtained by hydrolysis or condensation of a metal compound represented by formula (A-1) below, or by hydrolysis-condensation, and containing a ligand derived from an organic compound represented by formula (1) that includes one or more crosslinking groups represented by (a-1) to (a-4), can provide a resist underlayer film that exhibits excellent thermosetting properties, thereby reducing rapid volume shrinkage during baking, has good thermal fluidity, enables advanced embedding and / or advanced planarization properties, and has excellent dry etching resistance, thus completing the present invention.

[0062] In other words, the present invention relates to (A) a metal-containing film-forming compound, The (A) metal-containing film-forming compound is a compound derived from a metal-containing compound obtained by hydrolysis or condensation of a metal compound represented by the following formula (A-1), and further possesses a ligand derived from an organic compound represented by the following formula (1). M(OR 1A )4(A-1) R 2A COXCOOH (1) (In the formula, M is Ti, Zr, or Hf, and R 1A R is a monovalent organic group having 1 to 20 carbon atoms. 2A (where X is a divalent organic group having 2 to 20 carbon atoms and containing at least one bridging group represented by 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 (where is a hydrogen atom or a monovalent organic group with 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 to these descriptions.

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

[0065] If a compound is derived from a metal-containing compound obtained by hydrolysis or condensation of a metal compound, or by hydrolysis-condensation, it will have at least one [metal]-[oxygen]-[metal] bond. Therefore, when a metal-containing film is formed using this compound, it is possible to provide a metal-containing film with high hardness and excellent density. Furthermore, by performing hydrolysis or condensation, or hydrolysis-condensation, during compound synthesis, the volume shrinkage associated with the condensation reaction during film firing can be reduced, thereby further improving the embedding properties.

[0066] In the above formula (A-1), R 1A The group is 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 the productivity of metal compounds.

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

[0068] In the above equation (1), R 2A This is a divalent organic group having 2 to 20 carbon atoms that contains at least one bridging group represented by any of the above general formulas (a-1) to (a-4).

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

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

[0071] The (A) metal-containing film-forming compound is One or more selected from the hydrolysis product of only the metal compound represented by formula (A-1), the condensate product of only the metal compound represented by formula (A-1), and the hydrolysis condensate product of only the metal compound represented by formula (A-1), The organic compound represented by formula (1) above and It is preferable that the reactant is a metal-containing compound.

[0072] With such a metal-containing film-forming compound, ligands derived from the organic compound of formula (1) can be efficiently introduced into the metal compound. Therefore, when used in a metal-containing film-forming composition, it is possible to provide a metal-containing film that has a high degree of both embedding properties and dry etching resistance.

[0073] In equation (1) above, R 2A It is preferable that the structure is represented by the following general formula (B-1). [ka] (In the above general formula (B-1), R A1 This is the structure shown by the general formula (a-1) above, and R A2 is one 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 (where is a divalent organic group with 1 to 20 carbon atoms, saturated or unsaturated with 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 to 6, r is 1 to 10, u is 0 or 1, m is 0 or 1, and * represents the bond with the carbon atom of the carbonyl group.)

[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. A more preferable structure is when r is 1 to 4, t is 1 to 2, s is 0 to 1, and m is 0.

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

[0076] In formula (1) above, it is preferable that 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.

[0077] Such a structure can further improve the thermal fluidity of the metal-containing film-forming compound (A) described above. When this is used in the metal-containing film-forming composition (A), it is possible to provide a metal-containing film-forming composition that exhibits superior planarization and / or embedding properties.

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

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

[0080] The following compounds are examples of preferred structures of formula (1), but the present invention is not limited to these.

[0081] [ka]

[0082] [ka]

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

[0084] The above-mentioned (A) metal-containing film-forming compound may contain one ligand derived from the organic compound represented by formula (1) or multiple ligands with different structures, and can be appropriately adjusted according to the required properties when used in a metal-containing film-forming composition. Furthermore, it may contain ligands other than those derived from the organic compound represented by formula (1). For example, it may contain ligands derived from alkyl groups having 1 to 10 carbon atoms.

[0085] (A) The 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 of these independently corresponds to R in equation (A-1) above. 1A or COXCOR in formula (1) above 2A It is either R ae ~R de At least one of the above formulas ( 1 ) COXCOR 2A Here, n is between 1 and 20, and M is the same as M in equation (A-1) above.

[0086] The (A) metal-containing film-forming compound is a compound derived from a metal-containing compound obtained by hydrolysis or condensation of the metal compound represented by formula (A-1), and more preferably further comprises, in addition to the ligand derived from the organic compound represented by formula (1), a ligand derived from the organic compound represented by formula (3) below, and at least one additional ligand selected from ligands derived from succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic acid anhydride, and more preferably the additional ligand does not contain a crosslinking group represented by the general formulas (a-1) to (a-4) above. R3A COOH (3) (In the formula, R 3A is a monovalent organic group having 1 to 20 carbon atoms.)

[0087] When a compound further containing such an additional ligand is used in a composition for forming a metal-containing film, it becomes possible to promote the crosslinking reaction during firing, and it also becomes possible to set the firing temperature in a low temperature range at that time. Further, since the crosslinking reaction is promoted, it becomes possible to form a dense metal-containing film, and it is preferable because the etching resistance can be improved.

[0088] The ligand derived from the organic compound represented by the formula (3) preferably contains at least one or more of an aromatic ring, a heteroaromatic ring, and an alicyclic structure. For example, the following can be exemplified.

[0089] [Chemical formula] (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 bonding part with the carbonyl carbon.)

[0090] The ligand derived from any 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, it is preferable because the deterioration of the embedding characteristics can be minimized and the dry etching resistance can be improved.

[0092] When the compound for forming a metal-containing film (A) contains at least one additional ligand selected from ligands derived from the organic compound represented by the above formula (3) and ligands derived from any one of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, it preferably contains a compound having any one of the structures shown below or a mixture of these compounds.

Chemical formula

Chemical formula

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

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

[0095] Examples of divalent or trivalent alcohols include the compounds described in paragraphs

[0055] to

[0060] of Japanese Patent No. 6189758, and among these, it is preferable that the alcohol be one of the following compounds described in paragraph

[0061] .

[0096] [ka]

[0097] The β-diketone is preferably structured as shown in formula (3-a) below.

[0098] [ka] (In the above formula, R 3A and R 3B Each of these is an independent monovalent organic group having 1 to 20 carbon atoms, and R 3c (This refers to a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.)

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

[0100] The above R 3c This 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] Examples of β-diketones include, for example, 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, acetoacetate, α-alkyl-substituted acetoacetate, β-ketopentanoate, benzoyl acetate, 1,3-acetonedicarboxylic acid, 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 preferably, 2,4-pentanedione, 3-methyl-2,4-pentanedione, acetate acetate, diethyl malonate, or di-tert-butyl malonate, with 2,4-pentanedione, 3-methyl-2,4-pentanedione, or di-tert-butyl malonate being even more preferred.

[0102] When such compounds are used in compositions for forming metal-containing films, it becomes possible to promote the crosslinking reaction during firing and to lower the firing temperature. This is preferable because the promoted crosslinking reaction makes it possible to form a dense metal-containing film, thereby improving etching resistance.

[0103] The above (A) metal-containing film-forming compound may contain, in addition to the ligand derived from the organic compound shown in formula (1), one ligand derived from the organic compound shown in formula (3), and additional ligands selected from succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic acid anhydride, or multiple ligands with different structures, and can be appropriately adjusted according to the required properties when used in a metal-containing film-forming composition. Furthermore, it may also contain ligands derived from the above divalent or trivalent alcohol and / or ligands derived from the above β-diketone, and can be appropriately adjusted according to the required properties when used in a metal-containing film-forming composition.

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

[0105] In the above (A) metal-containing film-forming compound, the content of ligands derived from the organic compound represented by formula (1) is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 50 mol% or more, with a preferred upper limit of 100 mol%. Ligands other than those derived from the organic compound represented by formula (1) are preferably 90 mol% or less, more preferably 70 mol% or less, even more preferably 50 mol% or less, with a preferred lower limit of 0 mol%. Ligands other than those described above, for example, ligands derived from alkyl groups having 1 to 10 carbon atoms, may also be further included, and their content is preferably 0 mol% to 50 mol%, with a preferred content of 0 mol% to 30 mol% of the total amount of ligands coordinating to the metal atom M.

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

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

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

[0109] In other words, the method for producing the metal-containing film-forming compound of the present invention is One or more of the hydrolysates of metal compounds represented by formula (A-1) below, condensates of metal compounds represented by formula (A-1) below, and hydrolysates of metal compounds represented by formula (A-1) below are reacted with the organic compound represented by formula (1) below, or Hydrolysis or condensation of the metal compound represented by the following general formula (A-2), or hydrolysis-condensation. Includes. M(OR 1A )4(A-1) R 2A COXCOOH (1) (In the formula, M is Ti, Zr, or Hf, and R 1A R is a monovalent organic group having 1 to 20 carbon atoms. 2A (where X is a divalent organic group having 2 to 20 carbon atoms and containing at least one bridging group represented by 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 (where is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) (R 2A COXCOO) x M(OR 1A ) y (A-2) (In the formula, M is Ti, Zr, or Hf, and R 1A R is a monovalent organic group having 1 to 20 carbon atoms. 2A (where x is a divalent organic group having 2 to 20 carbon atoms and containing at least one bridging group represented by the general formulas (a-1) to (a-4) above, X is a divalent organic group having 2 to 20 carbon atoms, x + y = 4, and x and y are integers of 1 or greater.)

[0110] If a compound is derived from one or more of the hydrolysates of metal compounds represented by formula (A-1), condensates of metal compounds represented by formula (A-1), and hydrolyzed condensates of metal compounds represented by formula (A-1), it will have at least one [metal]-[oxygen]-[metal] bond. Therefore, when a metal-containing film is formed using this compound, a metal-containing film with high hardness and excellent density can be provided. Furthermore, by performing hydrolysis, condensation, or hydrolysis-condensation during compound synthesis, volume shrinkage associated with the condensation reaction during film firing can be reduced, thereby further improving the embedding properties.

[0111] Hydrolysis or hydrolysis condensation of the metal compound represented by formula (A-1) or formula (A-2) (hereinafter referred to as metal monomer) can be carried out without a catalyst, or in the presence of an acid or alkali catalyst. In this case, one or more compounds selected from inorganic acids, aliphatic sulfonic acids, aromatic sulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids can be used as the acid catalyst to produce the target product. Specific examples of acid catalysts 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 catalyst used is preferably 1 × 10⁻¹⁶ per mole of metal M-containing monomer. -6 ~10 moles, comfort level 1 × 10 -5 ~5 moles, more preferably 1 × 10⁻⁶ moles -4 It is approximately 1 mole.

[0112] Alternatively, it may be produced by hydrolysis condensation of a metal M-containing monomer in the presence of an alkaline catalyst. The alkaline catalyst used in this case may be 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-diethylethanol Examples of catalysts include amines, 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, calcium hydroxide, etc. The amount of catalyst used is preferably 1 × 10⁻⁶ per mole of metal M-containing monomer. -6 Moles ~10 moles, comfortable 1 × 10 -5 5 moles, more preferably 1 × 10⁻⁶ moles -4 Moles is approximately equal to 1 mole.

[0113] When obtaining metal-containing compounds from these metal M-containing monomers by hydrolysis or hydrolysis condensation, the amount of water added is preferably 0.01 to 10 moles per mole of hydrolyzable substituents bonded to the metal M-containing monomer, more preferably 0.05 to 5 moles, even more preferably 0.1 to 3 moles, and particularly preferably 0.1 to 1 mole. Adding 10 moles or less is economical because it does not require excessive equipment for the reaction, and it does not impair the stability of the metal-containing compound, which is therefore preferable.

[0114] The procedure involves adding a metal M-containing monomer to an aqueous catalyst solution to initiate the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the metal M-containing monomer may be diluted with an organic solvent beforehand, or both may be done. The reaction temperature is preferably 0 to 200°C, more preferably 5 to 150°C. It is preferable to maintain the temperature at 5 to 150°C when adding the metal M-containing monomer dropwise, and then allow it to mature at 20 to 150°C.

[0115] Another reaction procedure involves adding water or an aqueous organic solvent to a metal M-containing monomer or an organic solvent containing a metal M-containing monomer to initiate the hydrolysis reaction. The catalyst may be added to the metal M-containing monomer or the organic solvent containing the metal M-containing monomer, or it may be added to the water or aqueous organic solvent beforehand. The reaction temperature is preferably 0 to 200°C, more preferably 5 to 150°C. A preferred method involves maintaining the temperature at 5 to 150°C during the dropwise addition of the metal M-containing monomer, followed by aging at 20 to 150°C.

[0116] Organic solvents that can be added to the catalyst aqueous solution or used to dilute metal-containing compounds 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 monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propylene glycol monot-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] Furthermore, the amount of organic solvent used is preferably 0 to 1,000 ml per mole of metal-containing compound, and particularly preferably 0 to 500 ml. Using 1,000 ml or less of organic solvent is economical because it avoids the need for an excessively large reaction vessel.

[0118] Subsequently, if necessary, a neutralization reaction of the catalyst is carried out, and the alcohol produced by the hydrolysis 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 becomes neutral is acceptable.

[0119] Next, it is preferable to remove by-products such as alcohol produced by the hydrolysis condensation reaction from the reaction mixture. The temperature at which the reaction mixture is heated depends on the type of organic solvent added and the type of alcohol produced by 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 type of organic solvent and alcohol to be removed, the exhaust device, the condensing device, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, and even more preferably 50 kPa or less in absolute pressure. It is difficult to know the exact amount of alcohol removed at this time, but it is desirable that approximately 80% or more by mass of the produced alcohol is removed.

[0120] Preferred final solvents to add 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, and 1-butanediol monomethyl ether. Examples include 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 metal-containing compounds, it is possible to provide a metal-containing film-forming composition that exhibits no change in properties over the long term and has excellent storage stability.

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

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

[0124] <Metal-containing film forming composition> Furthermore, the present invention provides a metal-containing film-forming composition characterized by containing (A) a metal-containing film-forming compound and (B) an organic solvent.

[0125] Such a metal-containing film-forming composition contains a metal-containing film-forming compound that achieves a high degree of both thermal fluidity and thermosetting properties. Therefore, it is possible to provide a metal-containing film material that has superior dry etching resistance compared to conventional organic underlayer film materials, as well as advanced embedding and / or advanced planarization properties.

[0126] The following describes the components included in the metal-containing film-forming composition of the present invention other than the metal-containing film-forming compound described above (A).

[0127] <(B) Organic solvents> The (B) organic solvents that can be used in the metal-containing film-forming composition of the present invention are not particularly limited, but the (A) metal-containing film-forming compounds described above, and if included therein, the (C) crosslinking agent, (D) surfactant, (E) acid generator, and (F) average primary particles of 100 nm or less. diameter It is preferable that the solution dissolves and / or disperses metal oxide nanoparticles having the properties of metal oxide nanoparticles, other additives, etc.

[0128] Specifically, the organic solvents described in paragraphs

[0091] to

[0092] of Japanese Patent Application Laid-Open No. 2007-199653 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, and γ-butyrolactone, or a mixture containing one or more of these is preferably used.

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

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

[0131] (B-1) There are no particular restrictions on the high-boiling point solvent, such as hydrocarbons, alcohols, ketones, esters, ethers, and chlorinated solvents, but it is preferable that the solvent can dissolve and / or disperse each component of the metal-containing film-forming composition of the present invention. (B-1) Specific examples of high-boiling point solvents 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 Dibutyl 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 thereof 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, dibutyl adipate, etc., and these may be used alone or in combination.

[0132] (B-1) The high-boiling solvent may be appropriately selected from the above-mentioned ones, for example, according to the temperature for heat-treating the metal-containing film-forming composition of the present invention. The boiling point of the high-boiling solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. With such a boiling point, there is no fear that the volatilization during baking (heat treatment) will be too fast, so sufficient thermal fluidity can be obtained during film formation, and it is considered that a resist underlayer film excellent in embedding / planarization characteristics can be formed. Also, with such a boiling point, it will not remain in the film without volatilizing even after baking, so there is no fear of adversely affecting the film physical properties such as etching resistance.

[0133] Also, ( B-1 ) When using a high-boiling solvent, the blending amount is preferably 1 to 30 parts by mass with respect to 100 parts by mass of an organic solvent having a boiling point of less than 180°C. With such a blending amount, sufficient thermal fluidity can be imparted during baking, and it does not remain in the film and does not lead to deterioration of film physical properties such as etching resistance, so it is preferable.

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

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

[0136] The following describes examples of components included in the metal-containing film-forming composition of the present invention other than (A) the metal-containing film-forming compound and (B) the organic solvent.

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

[0138] Examples of melamine-based crosslinking agents include hexamethoxymethylated melamine, hexasubtoxicmethylated melamine, alkoxy and / or hydroxy-substituted derivatives thereof, and partially self-condensed derivatives thereof.

[0139] As an example of an acrylate-based crosslinking agent, dipentaerythritol hexaacrylate can be cited.

[0140] Examples of glycoluryl crosslinking agents include tetramethoxymethylated glycoluryl, tetrabutoxymethylated glycoluryl, their alkoxy and / or hydroxy substituted derivatives, and their partial self-condensates.

[0141] Examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensed derivatives.

[0142] Examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy-substituted derivatives, and partially self-condensed derivatives thereof.

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

[0144] Examples of isocyanurate-based crosslinking agents include triglycidyl isocyanurate and triallyl isocyanurate.

[0145] Examples of aziridine-based crosslinking agents include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0146] Examples of oxazoline-based crosslinking agents 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 copolymers.

[0147] 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] Examples of polynuclear phenolic crosslinking agents include the compound 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 from 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 more preferably 2 or 3. Specific examples of Q include groups obtained by removing q 1 hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. 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 methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, octyl group, ethylhexyl group, decyl group, and eicosanyl group. R3 is preferably a hydrogen atom or a methyl group.

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

[0151] [Chemical formula]

[0152] [Chemical formula]

[0153] <(D) Surfactant> The metal-containing film-forming composition of the present invention may contain (D) a surfactant to improve the coatability in spin coating. As the surfactant, for example, those described in

[0142] to

[0147] of Japanese Patent Application Publication No. 2009-269953 can be used. When a surfactant is added, the amount added is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, per 100 parts by mass of the (A) metal-containing film-forming compound.

[0154] <(E) Acid Generator> In the metal-containing film-forming composition of the present invention, an acid generator can be added to further accelerate the curing reaction of the metal-containing film-forming compound (A) described above. Acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation, and either type can be added. Specifically, materials described in paragraphs

[0061] to

[0085] of Japanese Patent Application Publication No. 2007-199653 can be added, but are not limited to these.

[0155] The above acid generating agents can be used individually or in combination of two or more. When adding an acid generating agent, the amount to be added is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, per 100 parts by mass of the above (A) metal-containing film-forming compound.

[0156] <(F) Metal oxide nanoparticles> Furthermore, (F) metal oxide nanoparticles may be added to the metal-containing film-forming composition of the present invention to further improve dry etching resistance. 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 metal-containing films with superior dry etching resistance.

[0158] The (F) metal oxide nanoparticles are preferably those having 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 15 nm or less. The average primary particle size of the metal oxide nanoparticles before dispersion in the organic solvent can be determined by directly measuring the size of the primary particles from electron microscope images. Specifically, the short axis diameter and long axis diameter of each primary particle are measured, and their average is taken as the particle size. Next, for 100 or more particles, the volume (mass) of each particle is approximated by a rectangular parallelepiped with the determined particle size, and the volume-average particle size is determined and taken as the average particle size. The same results can be obtained using any of the electron microscopes: transmission electron microscope (TEM), scanning electron microscope (SEM), or scanning transmission electron microscope (STEM).

[0159] Within this particle size range, good dispersibility can be achieved in the metal-containing film-forming composition, and the dry etching resistance of the metal-containing film can be improved without degrading the embedding / planarization characteristics of the densely packed areas of the fine pattern structure.

[0160] (F) When 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 the metal-containing film-forming compound (A) described above.

[0161] <Liquid additives and pyrolytic polymers> Furthermore, the metal-containing film-forming composition of the present invention preferably uses, as an additive to impart embedding / planarization properties, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a pyrolytic 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. This pyrolytic polymer preferably contains repeating units having an acetal structure represented by the following general formula (DP1) or (DP1a).

[0162] [ka] (In the formula, R6 is a hydrogen atom or a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, which may be substituted. 1 (This refers to a saturated or unsaturated divalent organic group with 2 to 30 carbon atoms.)

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

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

[0165] <Flow enhancer (BP)> Furthermore, the metal-containing film-forming composition of the present invention may contain a flow promoter (BP) as an additive to impart embedding and / or planarization properties. The flow promoter (BP) preferably has an organic group and an aromatic ring represented by the following general formula (bp1a).

[0166] [ka] (In the formula, * represents the bonding site to the oxygen atom, R B R is a divalent organic group with 1 to 10 carbon atoms. A (This refers to a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.)

[0167] The aforementioned fluidity enhancer (BP) is the one specified in the general formula (b p1By having the organic group shown in a), the above (A) metal-containing film-forming compound can be imparted with thermal fluidity and thermosetting properties. Furthermore, the presence of an aromatic ring in the fluidity enhancer (BP) can mitigate the deterioration of the dry etching resistance of the (A) metal-containing film-forming compound.

[0168] The aforementioned fluidity enhancer (BP) preferably has at least one constituent unit represented by any of the following general formulas (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5).

[0169] (Component units: BP-1, BP-2, and BP-3) [ka] (In the above general formulas (BP-1) and (BP-2), W1 and W2 are independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. a1 The general formula is shown in (4) below. Y is the group represented by the general formula (5) below. n1 is 0 or 1, n2 is 1 or 2, and V independently represents a hydrogen atom or a linkage. [ka] (In the above general formula (BP-3), Z1 is the base shown in the following general formula (6) in Yes, R a1 The following general formula (4) is given by: n4 is 0 or 1, n5 is 1 or 2, and V independently represents a hydrogen atom or a bonding group. [ka] (* indicates a bond with an oxygen atom.) [ka] (* indicates a bond.) [ka] (In the above general formula (6), W1, W2, Y, and n1 are the same as described above.)

[0170] Resins having structural units represented by any of the above general formulas (BP-1), (BP-2), and (BP-3) have excellent heat resistance because they incorporate high-carbon-density condensed carbon rings including a cardi structure. Due to these characteristics, even when subjected to high-temperature baking treatment, they can form metal-containing films that can fill stepped substrates without generating voids. Furthermore, they also have excellent dry etching resistance, so when added to the metal-containing film-forming composition of the present invention, they can impart heat resistance and thermal fluidity without significantly degrading the excellent dry etching resistance of the metal-containing film-forming composition.

[0171] A resin having a constituent unit represented by any of the above general formulas (BP-1), (BP-2), and (BP-3) may be a compound represented by the following general formulas (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 for the general formulas (BP-1) and (BP-2) above.

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

[0173] Examples of resins having a constituent unit represented by any 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 respect to the above resins (bp-1), (bp-2), and (bp-3), the ratio Mw / Mn (i.e., degree of dispersion) of the weight-average molecular weight Mw to the number-average molecular weight Mn, calculated in terms of polystyrene by gel permeation chromatography, is preferably in the range of 1.00 ≤ Mw / Mn ≤ 1.25, and more preferably 1.00 ≤ Mw / Mn ≤ 1.10.

[0176] If the compound has a dispersion degree within this range, the thermal fluidity of the metal-containing film-forming composition will be even better, and when incorporated into a material, it will be possible to provide a metal-containing film-forming composition with superior embedding and / or planarization properties.

[0177] Alternatively, a resin having a constituent unit represented by any of the above general formulas (BP-1), (BP-2), and (BP-3) may be a polymer having repeating units represented by the following general formulas (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 described for the general formulas (BP-1) and (BP-2) above, and L1 is a divalent organic group with 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 described for the general formula (BP-3), and L1 is a divalent organic group having 1 to 40 carbon atoms.

[0179] These polymers are obtained using compounds represented by any of the above general formulas (bp-1), (bp-2), and (bp-3), and because they use these compounds, they exhibit excellent dry etching resistance and heat resistance. Furthermore, because they are polymers with repeating units rather than monomers, they have fewer outgassing components, and because they are polymers with a molecular weight distribution, their crystallinity is relaxed, and improved film-forming properties can be expected.

[0180] L1, which is a linking group that constitutes any of the repeating units of the above general formulas (bp-4), (bp-5), and (bp-6), is a divalent organic group having 1 to 40 carbon atoms, and the following are some specific examples.

[0181] [ka]

[0182] Furthermore, it is preferable that the linking group L1 of the polymer described above is of the following general formula (10). [ka] (In the above general formula (10), R1 is a hydrogen atom or a number of carbon atoms) 6 This is an organic group containing approximately 20 aromatic rings; the dashed lines represent bonding bonds.

[0183] The following are some specific examples of the above general formula (10), and among them, a methylene group, i.e., R1 being a hydrogen atom, is preferred due to the ease of obtaining the raw materials.

[0184] [ka]

[0185] Furthermore, the weight-average molecular weight of the polymer having repeating structural units represented by any of the above general formulas (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, solubility in organic solvents can be ensured, and sublimation during baking can be suppressed. Furthermore, because the metal-containing film-forming composition exhibits good thermal fluidity, when incorporated into materials, it is possible to provide a metal-containing film-forming composition with superior embedding and / or planarization properties.

[0187] (Component unit: BP-4) [ka] (In the formula, m3 and m4 represent 1 or 2, and Z2 is either a single bond or a structure shown in the general formula (7) below. x (This is one of the structures shown in the following general formula (8).) [ka] (In the formula, * represents a combination, l represents an integer from 0 to 3, and R az ~R fz Each of these independently represents a hydrogen atom or a C1-C10 alkyl group, phenyl group, or phenylethyl group which may be substituted with fluorine, and R az and R bz (These two components may combine to form a cyclic compound.) [ka] (In the formula, * represents the bonding site to the aromatic ring, and Q1 is Number of carbon atoms It consists of 1 to 30 linear saturated hydrocarbon groups, or a structure represented by the general formula (9) below. [ka] (In the formula, * represents the bonding site to the carbonyl group, R i The above general formula( 4) R j These are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, halogen atoms, nitro groups, amino groups, nitrile groups, and carbon number 2 This represents an alkoxycarbonyl group with approximately 10 carbon atoms, or an alkanoyloxy group with 1 to 10 carbon atoms. 3z and n 4z n represents the number of substituents on the aromatic ring, each representing an integer from 0 to 7. 3z +n 4z n is between 0 and 7 (inclusive). 5z (This represents values ​​from 0 to 2.)

[0188] From the viewpoint of dry etching resistance and heat resistance, in the above general formula (BP-4), Z2 is a single bond or the above formula ( 7 It is preferable that the structure be one of the structures shown in ). [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, the methylene group constituting Q1 may be substituted with an oxygen atom or a carbonyl group. From the viewpoint of dry etching resistance and heat resistance, the structure of Q1 shown in the above general formula (9) is preferred.

[0190] Compounds containing the constituent unit shown in the above general formula (BP-4) have a structure in which aromatic rings are linked by single bonds or general formula (7), and therefore have a high carbon density, resulting in metal-containing film-forming compositions containing these compounds having excellent heat resistance. Furthermore, as shown in the above formula (7), the linking group Z2 can be appropriately selected from various linking groups to match the desired performance. In particular, as the linking group Z2, the above formula ( 7 By introducing the structure shown in ), heat resistance and / or etching resistance can be provided without impairing film formation properties. In addition, the highly flexible end portion R xBecause it has a rigid aromatic ring structure, it is possible to form a thick film of the metal-containing film-forming composition without generating defects such as cracks. Furthermore, terminal portion R x The compound contains terminal groups Q1 that impart thermal fluidity, and as terminal groups Q1, a flexible hydrocarbon structure that contributes to improved thermal fluidity and a rigid aromatic ring structure that contributes to etching resistance and heat resistance can be introduced in any proportion to suit the required performance. As described above, metal-containing film-forming compositions to which these compounds are added can achieve a high level of both embedding and / or planarization properties and heat resistance, and thick films can be formed according to the required properties.

[0191] (Component unit: BP-5) [ka] (In the above general formula (BP-5), R 1 R 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, and R a1 This is the general formula (4) above. p is an integer between 0 and 5, q1 is an integer between 1 and 6, p+q1 is an integer between 1 and 6 (inclusive), and q2 is either 0 or 1.

[0192] In the above general formula (BP-5), the divalent organic group having 1 to 30 carbon atoms represented by X1 is, for example, an alkanediyl group such as methylene group, ethanediyl group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, octanediyl group, decanediyl group, etc.; a monocyclic cycloalkanediyl group such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclooctanediyl group, cyclodecanediyl group, methylcyclohexanediyl group, ethylcyclohexanediyl group, etc.; bicyclo[2.2.1]heptanediyl group, bicyclo[2.2.2]octanediyl group, tricyclo[5.2.1.0 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 Examples include polycyclic cycloalkanediyl groups such as dodecanediyl and adamantanediyl groups, and arenediyl groups such as phenylene and naphthylene groups.

[0193] Examples of the alkanediyloxy group represented by X1 above include a group formed by combining the alkanediyl group with an oxygen atom. Furthermore, examples of the cycloalkanediyloxy group represented by X1 above include a group formed by combining the cycloalkanediyl group with an oxygen atom.

[0194] Some or all of the hydrogen atoms in the above-mentioned alkanediyl group, cycloalkanediyl group, alkanediyloxy group, cycloalkanediyloxy group, and arenediyl group may be substituted, and examples of substituents include the above-mentioned R a Examples of substituents that the organic group represented by [the symbol] may have include groups similar to those mentioned above.

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

[0196] From the viewpoint of obtaining raw materials, a methylene group is preferably given as X1.

[0197] The following are specific examples of resins having the structural unit represented by the general formula (BP-5) above.

[0198] [ka]

[0199] [ka]

[0200] Polymers containing the constituent units shown in the above general formula (BP-5) have a structure in which aromatic rings are linked by organic groups (X1), resulting in a high carbon density. Therefore, metal-containing film-forming compositions containing these compounds exhibit high dry etching resistance and excellent heat resistance. Furthermore, because the organic groups of the structure shown in the above general formula (4), which contribute to improved thermal fluidity, are directly bonded to the aromatic rings, which are the core structure of the resin, via oxygen atoms, metal-containing film-forming compositions to which these polymers are added can achieve a high level of balance between embedding and / or planarization properties and heat resistance and / or etching resistance. In addition, because the aromatic ring structure of the core is not too rigid and forms a repeating structure via the organic groups (X1) that act as linking groups, it is possible to form metal-containing film-forming compositions without generating defects such as cracks.

[0201] In the metal-containing film-forming composition of the present invention, the fluidity enhancer (BP) is preferably contained in an amount of 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on 100 parts by mass of the metal-containing film-forming compound.

[0202] The amount of fluidity enhancer 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 you want to minimize the degradation of dry etching resistance, reduce the proportion of the fluidity enhancer. If you want to tolerate some degradation of dry etching resistance and further improve the embedding / planarization characteristics, increase the proportion of the fluidity enhancer.

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

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

[0205] Furthermore, in the resist underlayer film formation method using the metal-containing film-forming composition of the present invention, the metal-containing film-forming composition of the present invention can be coated onto a workpiece substrate by a spin coating method or the like, as described above, and the metal-containing film-forming composition can be cured by firing in an atmosphere with an oxygen concentration of 0.1% to 21% by volume to form a metal-containing film.

[0206] By firing the metal-containing film-forming composition of the present invention in such an oxygen atmosphere, a sufficiently hardened film can be obtained. While air may be used as the atmosphere during baking, it is preferable to seal in an inert gas such as N2, Ar, or He to reduce oxygen levels and prevent oxidation of the metal-containing film. To prevent oxidation, it is necessary to control the oxygen concentration, preferably 1000 ppm or less, more preferably 100 ppm or less (by volume). Preventing oxidation of the metal-containing film during baking is preferable because it prevents increased absorption and reduced etching resistance.

[0207] < Contains metal Pattern formation method using film-forming composition > Furthermore, the present invention provides a method for forming a pattern on a substrate using the above-mentioned metal-containing film-forming composition by a two-layer resist process, which involves forming a pattern on a substrate to be processed. (I-1) A step of forming a metal-containing film on a substrate to be processed by applying the above metal-containing film-forming composition and then heat-treating it, (I-2) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. The present invention provides a pattern forming method characterized by having the following features.

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

[0209] Furthermore, the present invention provides a method for forming a pattern on a workpiece substrate using the above-mentioned metal-containing film-forming composition in a three-layer resist process, (II-1) A step of forming a metal-containing film on a substrate to be processed by applying the above metal-containing film-forming composition and then heat-treating it, (II-2) A step of forming a resist interlayer on the metal-containing film, (II-3) A step of forming a resist upper layer film on the resist interlayer film using a photoresist material, (II-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-5) A step of transferring the pattern to the resist interlayer by dry etching, using the resist upper layer on which the pattern is formed as a mask. (II-6) A step of transferring the pattern to the metal-containing film by dry etching using the resist interlayer on which the pattern has been transferred as a mask, and (II-7) A process of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. The present invention provides a pattern forming method characterized by having the following features.

[0210] An example of a pattern formation method using a three-layer resist process will be explained with reference to Figure 1. In the present invention, as a pattern formation method using a three-layer resist process with the above-mentioned metal-containing film forming composition, as shown in Figure 1(A), a metal-containing film 3 is formed on the workpiece layer 2 of a workpiece substrate 1A, which has a workpiece layer 2 formed on a substrate 1, using the above-mentioned metal-containing film forming composition, a resist interlayer 4 is formed on the metal-containing film 3 using a resist interlayer material, and a resist upper layer 5 is formed on the interlayer 4 using a photoresist material. Subsequently, as shown in Figure 1(B), the exposed portion 6 of the resist upper layer is pattern-exposed. Next, as shown in Figure 1(C), development is performed with a developer to form a resist upper layer pattern 5a on the resist upper layer. Then, as shown in Figure 1(D), the resist upper layer with the pattern formed is used as a mask to transfer the pattern to the resist interlayer by dry etching to form a resist interlayer pattern 4a. Next, as shown in Figure 1(E), the pattern is transferred... Tare Using the dyst interlayer as a mask, a pattern is transferred to the metal-containing film by dry etching to form a metal-containing film pattern 3a. Next, as shown in Figure 1(F), the metal-containing film with the pattern formed on it is used as a mask to process the workpiece layer 2 of the workpiece substrate 1A to form a pattern 2a on the workpiece substrate 1A.

[0211] The silicon-containing resist interlayer, which can be used as an example of an interlayer in the above three-layer resist process, exhibits etching resistance to chlorine-based gases. Therefore, when using a silicon-containing resist interlayer as an interlayer in the above three-layer resist process, it is preferable to perform the dry etching of the metal-containing film, which is carried out using the silicon-containing resist interlayer as a mask, using an etching gas mainly composed of chlorine-based gases.

[0212] Polysiloxane-based interlayers are also preferably used as silicon-containing resist interlayers that can be used in the above three-layer resist process. By giving the silicon-containing resist interlayer an anti-reflective effect, reflection can be suppressed. In particular, for 193nm exposure, if a material containing many aromatic groups as an organic film and having high etching selectivity with the substrate is used, the k value will be high and substrate reflection will be high. However, by giving the silicon-containing resist interlayer an absorption that results in an appropriate k value, it is possible to suppress reflection, and substrate reflection can be reduced to 0.5% or less. As silicon-containing resist interlayers with an anti-reflective effect, anthracene is preferably used for 248nm and 157nm exposure, and polysiloxane is preferably used for 193nm exposure, with phenyl groups or absorbent groups having silicon-silicon bonds pendanted and crosslinked by acid or heat.

[0213] In addition, the present invention provides another embodiment of the pattern formation method by a four-layer resist process using the above-mentioned metal-containing film-forming composition, wherein a metal-containing film is formed on a workpiece substrate using the above-mentioned metal-containing film-forming composition, a silicon-containing resist interlayer is formed on the metal-containing film using a silicon-containing resist interlayer material, and an organic anti-reflective film (BARC) or adhesion film is formed on the silicon-containing resist interlayer, and the BARC or adhesive filmThe present invention provides a pattern formation method comprising the steps of: forming a resist upper layer film using a photoresist material; pattern exposure of the resist upper layer film; developing it with a developer to form a pattern on the resist upper layer film; using the resist upper layer film on which the pattern has been formed as a mask, transferring the pattern to the BARC or adhesion film and the silicon-containing resist interlayer film by dry etching; using the silicon-containing resist interlayer film on which the pattern has been transferred as a mask, transferring the pattern to the metal-containing film by dry etching; and 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.

[0214] Alternatively, an inorganic hard mask may be formed instead of a silicon-containing interlayer, in which case the method for forming a pattern on the substrate to be processed is as follows: (III-1) A step of forming a metal-containing film on a substrate to be processed by applying the above metal-containing film-forming composition and then heat-treating it, (III-2) A step of forming an inorganic hard mask interlayer selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film. (III-3) A step of forming an organic thin film on the inorganic hard mask interlayer, (III-4) A step of forming a resist upper layer film on the organic thin film using a photoresist material, (III-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (III-6) A step of transferring the pattern to the organic thin film and the inorganic hard mask interlayer film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (III-7) A step of transferring the pattern to the metal-containing film by dry etching using the inorganic hard mask interlayer on which the pattern has been transferred as a mask, and (III-8) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. A pattern forming method characterized by having [a specific feature] can form a pattern, such as a semiconductor device circuit pattern, on a substrate to be processed.

[0215] As described above, when forming an inorganic hard mask on a metal-containing film, silicon oxide films, silicon nitride films, and silicon oxynitride films (SiON films) can be formed by CVD or ALD methods. For example, an example of a method for forming a silicon nitride film is described in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The thickness of the inorganic hard mask is preferably 5 to 200 nm, and more preferably 10 to 100 nm. Furthermore, as the inorganic hard mask, a SiON film, which has a high effect as an anti-reflective film, is most preferably used. Since the substrate temperature when forming the SiON film is 300 to 500°C, the metal-containing film needs to withstand temperatures 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 it is possible to combine an inorganic hard mask formed by CVD or ALD with a metal-containing film formed by rotary coating.

[0216] As described above, a photoresist film may be formed as a resist top layer on an inorganic hard mask, or an organic anti-reflective coating (BARC) or adhesion film may be formed on the inorganic hard mask by spin coating, and then 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 layers of anti-reflective coatings, the SiON film and BARC, make it possible to suppress reflection even in immersion lithography with high NA values ​​exceeding 1.0. Another advantage of forming BARC is that it has the effect of reducing the trailing of the photoresist pattern directly above the SiON film.

[0217] For example, one aspect of the pattern forming method of the present invention is a method for forming a pattern on a substrate to be processed, (IV-1) A step of forming a metal-containing film on a substrate to be processed by applying the above metal-containing film-forming composition and then heat-treating it, (IV-2) A step of forming an organic interlayer on the metal-containing film, (IV-3) A step of forming a combination of an organic thin film and an inorganic hard mask interlayer selected from a silicon-containing resist interlayer, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic interlayer. (IV-4) A step of forming a resist upper layer film on the silicon-containing resist interlayer film or the organic thin film using a photoresist material. (IV-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (IV-6) A step of transferring the pattern to a silicon-containing resist interlayer or the organic thin film and the inorganic hard mask interlayer by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (IV-7) A step of transferring the pattern onto an organic interlayer by dry etching, using the silicon-containing resist interlayer or inorganic hard mask interlayer on which the pattern has been transferred as a mask. (IV-8) The aforementioned pattern is transferred A step of using the aforementioned organic interlayer as a mask to transfer a pattern to the metal-containing film by dry etching, and (IV-9) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. This is a pattern forming method characterized by having [a certain feature].

[0218] In the pattern formation method described above, the resist upper layer film may be either positive or negative type, and the same photoresist composition as commonly used can be used. Furthermore, 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, the method may be spin coating or deposition by CVD or ALD.

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

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

[0221] The metal oxide-containing film may be deposited by PECVD or PEALD using, for example, a Lam Vector® tool, and in the ALD example, the Sn oxide precursor is separated from the O precursor / plasma. 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 cm / m³, 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 frequency). The deposition thickness is preferably 100 to 2000 Å.

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

[0223] As a method for forming the pattern of the resist upper layer film described above, it is preferable to use photolithography with a wavelength of 5 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof to form the pattern.

[0224] Furthermore, it is preferable that the development method in the pattern formation method be alkaline development or development with 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 interlayer and inorganic hard mask is performed using a fluorocarbon gas with the upper resist pattern as a mask. This forms the silicon-containing resist interlayer pattern and the inorganic hard mask pattern.

[0226] Next, the metal-containing film is etched using the obtained silicon-containing resist interlayer pattern or inorganic hard mask pattern as a mask. It is preferable to use an etching gas mainly composed of chlorine-based gas for etching the metal-containing film.

[0227] The etching of the next workpiece can also be performed by conventional methods. For example, if the workpiece is made of SiO2, SiN, or silica-based low dielectric constant insulating film, etching is performed primarily using a fluorocarbon gas. When the substrate is etched with a fluorocarbon gas, the silicon-containing resist interlayer pattern in the three-layer resist process is peeled off simultaneously with the substrate processing.

[0228] The metal-containing films obtained using the metal-containing film-forming composition of the present invention have excellent etching resistance when these workpieces are etched.

[0229] The workpiece (workpiece substrate) is not particularly limited and can be any substrate such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, or a substrate on which the workpiece layer has been deposited. Various low-k films and their stopper films can be used as the workpiece layer, typically with a thickness of 50 to 10,000 nm, and especially 100 to 5,000 nm. When depositing the workpiece layer, the substrate and the workpiece layer are made of different materials.

[0230] This invention Contains metal In the pattern formation method using the film-forming composition, it is preferable to use a workpiece substrate having a structure or step with a height of 30 nm or more. As described above, the metal-containing film-forming composition of the present invention has excellent embedding / planarization characteristics, so even if the workpiece substrate has a structure or step (unevenness) with a height of 30 nm or more, a flat cured film can be formed. The height of the structure or step on the workpiece substrate is preferably 30 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. In the method of processing a stepped substrate having a pattern of the above height, by forming the metal-containing film-forming composition of the present invention and performing embedding / planarization, it is possible to make the film thickness of the resist interlayer and resist upper layer that are subsequently formed uniform, which makes it easier to secure the depth of exposure margin (DOF) during photolithography and is therefore very preferable.

[0231] Furthermore, in the present invention, as a pattern formation method by a four-layer resist process using the above-mentioned metal-containing film forming composition, a metal-containing film is formed on a workpiece substrate using the above-mentioned metal-containing film forming composition; an organic interlayer is formed on the metal-containing film using an organic interlayer material; a silicon-containing resist interlayer is formed on the organic interlayer using a silicon-containing resist interlayer material; and, if necessary, an organic anti-reflective film (BARC) or an adhesion film is formed on the silicon-containing resist interlayer. or adhesive filmThe present invention provides a pattern formation method comprising the steps of: forming a resist upper layer film using a photoresist material; pattern exposure of the resist upper layer film; developing it with a developer to form a pattern on the resist upper layer film; using the resist upper layer film on which the pattern has been formed as a mask, transferring the pattern to the BARC or adhesion film and the silicon-containing resist interlayer film by dry etching; using the silicon-containing resist interlayer film on which the pattern has been transferred as a mask, transferring the pattern to the organic interlayer film by dry etching; using the organic interlayer film as a mask, transferring the pattern to the metal-containing film; and 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.

[0232] As organic interlayer materials that can be used for the above-mentioned organic interlayer, in addition to those already known as underlayers for the 3-layer resist method or the 2-layer resist method using a silicon resist composition, a large number of resins including novolac resins can be used, such as the 4,4'-(9-fluorenylidene)bisphenol novolac resin (molecular weight 11,000) described in Japanese Patent Application Publication No. 2005-128509, as well as those known as underlayer materials for resists in the 2-layer resist method and the 3-layer resist method. Furthermore, if it is desired to increase the heat resistance compared to ordinary novolac, a polycyclic skeleton such as 6,6'-(9-fluorenylidene)-di(2-naphthol) novolac resin can be incorporated, and polyimide resins can also be selected (for example, Japanese Patent Application Publication No. 2004-153125).

[0233] The above organic interlayer can be formed on a substrate using a composition solution by a spin coating method or the like, similar to the photoresist composition. After forming the organic underlayer by a spin coating method 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 above-mentioned organic resist underlayer material, it is also possible to apply an organic hard mask formed by CVD or ALD.

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

[0236] <Tone-reversal pattern formation method using a metal-containing film-forming composition> Furthermore, the present invention provides a tone-reversal pattern formation method using the above-mentioned metal-containing film-forming composition, which is a method for forming a pattern on a substrate to be processed, (V-1) A step of forming a resist underlayer film on the substrate to be processed. (V-2) A step of forming a resist interlayer, or a combination of an inorganic hard mask interlayer 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) A step of forming a resist upper layer film using a photoresist material on the resist interlayer film, or a combination of an inorganic hard mask interlayer film and an organic thin film. (V-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (V-5) A step of transferring the pattern to the resist interlayer, or the organic thin film and the inorganic hard mask interlayer, by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (V-6) A step of transferring the pattern to the resist underlayer film by dry etching, using the resist interlayer film on which the pattern has been transferred, or an inorganic hard mask interlayer film, as a mask. (V-7) A step of coating the resist underlayer film on which the pattern is formed with the metal-containing film composition, then heat-treating it to coat it with a metal-containing film, thereby filling the gaps 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, thereby exposing the upper surface of the resist underlayer film on which the pattern has been formed. (V-9) A step of removing the resist interlayer or hard mask interlayer remaining on the upper surface of the resist underlayer by dry etching. (V-10) A step of removing the resist underlayer film on which the exposed surface pattern is formed by dry etching, and forming an inverted pattern of the original pattern on the metal-containing film. (V-11) A process of processing the workpiece substrate using the metal-containing film on which the inverted pattern is formed as a mask to form the inverted pattern on the workpiece substrate. The present invention provides a tone-reversal pattern formation method characterized by having the following features.

[0237] A tone-reversal pattern formation method using a metal-containing film-forming composition will be explained with reference to Figure 2. In this invention, as a tone-reversal pattern formation method using such a metal-containing film-forming composition, as shown in Figure 2(G), a resist underlayer film 7 is formed on the workpiece layer 2 of a workpiece substrate 1A on which a workpiece layer 2 has been formed on the substrate 1. A resist interlayer film 4, or a combination of an inorganic hard mask interlayer film selected from silicon oxide film, silicon nitride film, and silicon oxynitride film and an organic thin film is formed on the resist underlayer film 7. A resist upper layer film 5 is formed on the resist interlayer film 4, or the combination of an inorganic hard mask interlayer film and an organic thin film, using a photoresist material. Subsequently, as shown in Figure 2(H), the exposed portion 6 of the resist upper layer film is pattern-exposed. Next, as shown in Figure 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 Figure 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 interlayer film, or the organic thin film and the inorganic hard mask interlayer film, by dry etching to form a resist interlayer film pattern 4a or an inorganic hard mask interlayer film pattern. Next, as shown in Figure 2(K), the resist interlayer film or inorganic hard mask interlayer film on which the pattern has been transferred is used as a mask to transfer the pattern to the resist lower layer film by dry etching to form a resist lower layer film pattern 7a. Next, as shown in Figure 2(L), the resist lower layer film on which the pattern is formed is coated with a metal-containing film 8 using the metal-containing film forming composition, filling the gaps between the resist lower layer film patterns 7a with the metal-containing film 8. Next, the metal-containing film covering the resist lower layer 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 Figure 2(M). Next, the resist interlayer 4a or hard mask interlayer remaining on the upper surface of the resist underlayer pattern 7a is removed by dry etching to expose the upper surface of the resist underlayer pattern 7a, as shown in Figure 2(N). Then, the exposed resist underlayer pattern 7a is removed by dry etching to obtain a metal-containing film in which an inverted pattern 8a of the original pattern is formed, as shown in Figure 2(O).Next, as shown in Figure 2(P), the workpiece layer 2 is processed using the metal-containing film on which the inverted pattern is formed as a mask to form the inverted pattern 2b on the workpiece layer of the substrate.

[0238] As described above, when forming a resist underlayer film on a substrate to be processed, the resist underlayer film can be formed using a method with a coating-type organic underlayer film material, or by CVD or ALD methods. Examples of coating-type organic underlayer film materials include JP 2012-1687, JP 2012-77295, JP 2004-264710, JP 2005-043471, JP 2005-250434, JP 2007-293294, JP 2008-65303, and JP Japanese Patent Publication No. 2004-205685, Japanese Patent Publication No. 2007-171895, Japanese Patent Publication No. 2009-14816, Japanese Patent Publication No. 2007-199653, Japanese Patent Publication No. 2008-274250, Japanese Patent Publication No. 2010-122656, Japanese Patent Publication No. 2012-214720, Japanese Patent Publication No. 2014-29435, Examples of resins and compositions can be found in Japanese Patent Publication No. WO2012 / 077640, International Publication No. WO2010 / 147155, International Publication No. WO2012 / 077640, International Publication No. WO2010 / 147155, International Publication No. WO2012 / 176767, Japanese Patent Publication No. 2005-128509, Japanese Patent Publication No. 2006-259249, Japanese Patent Publication No. 2006-259482, Japanese Patent Publication No. 2006-293298, Japanese Patent Publication No. 2007-316282, Japanese Patent Publication No. 2012-145897, Japanese Patent Publication No. 2017-119671, Japanese Patent Publication No. 2019-44022, etc.

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

[0240] In the tone inversion pattern formation method described above, the resist underlayer film pattern preferably has structures or steps with a height of 30 nm or more. As described above, the metal-containing film-forming composition of the present invention has excellent embedding and / or planarization properties, so even if the film to be processed has structures or steps (unevenness) with a height of 30 nm or more, a flat cured film can be formed. The height of the structures or steps of the resist underlayer film pattern is preferably 30 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. In the method of inverting a resist underlayer film pattern having a pattern of the above height, it is highly preferable to form the metal-containing film-forming composition of the present invention and perform embedding and planarization, as this enables high-precision pattern inversion and transfer. Compared to resist underlayer films using conventional coating-type organic underlayer film materials, it has excellent dry etching resistance using fluorocarbon gases, so by inverting the resist underlayer film pattern with the metal-containing film-forming composition, a desired resist pattern can be formed on the film to be processed with high precision. [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] [Example of combination] The following synthesis and comparative synthesis examples used the organic group raw materials G: (G1) to (G14) and the silicon-containing organic group raw materials H: (H1) shown below.

[0243] The raw material group G: (G1) to (G14) is shown below. [ka]

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

[0245] The following metal compounds were used as the metal source M. (M1): Titanium tetraisopropoxide (Sigma-Aldrich Corp, 377996) (M2): Titanium butoxide tetramer (Fujifilm Wako Pure Chemical Corporation) (M3):Zr(OBu)4:Zirconium(IV) tetrabutoxide (80% by mass 1-butanol solution) (Tokyo Chemical Industries, 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, 40.5 g of n-butanol solution containing 28.4 g of titanium tetraisopropoxide (M1) was stirred, and 54.5 g of n-butanol solution containing 1.6 g of deionized water was added dropwise over 2 hours at room temperature. This resulted in the hydrolysis and condensation of metal compound M1. 26.4 g of organic raw material (G1) was added to the resulting solution and stirred at room temperature for 30 minutes. This solution was concentrated under reduced pressure at 30°C, then heated to 60°C, and continued under reduced pressure until no more distillate was observed. Once no distillate was observed, 69.0 g of PGMEA / PGME (weight ratio 70 / 30) solution was added, and the mixture was heated at 40°C under reduced pressure until no more IPA distilled, yielding a PGMEA / PGME solution of 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 2-12 and Comparative Synthesis Examples 13-16] Synthesis of metal-containing film-forming compounds (A-2)-(A-12) and comparative metal-containing film-forming compounds (R-1)-(R-4) Except for using the amounts shown in Table 1, and employing one of the above metal sources M and one or two of the above compound group G, the metal-containing film-forming compounds (A-2) to (A-12) and comparative metal-containing film-forming compounds (R-1) to (R-4) were obtained under the same reaction conditions as in Synthesis Example 1.

[0248] [Table 1]

[0249] [Comparative Synthesis Example 17] Synthesis of a 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 (70 / 30 by weight ratio) solution. The reaction temperature was raised to 50°C while stirring, and 20.4 g of compound H1 was added dropwise to the solution. After addition, the reaction temperature was increased to 60°C and stirring was continued for 2 hours. Next, a mixture of 29.6 g of compound G9 suspended in 24.8 g of PGMEA / PGME (70 / 30 by weight ratio) solution was added to the reaction system, and stirring was continued at a reaction temperature of 60°C for 1 hour. After cooling to room temperature, the resulting reaction solution was filtered through 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 organic film-forming resin (R-6) for comparative examples] Under a nitrogen atmosphere, 160.2 g of 1,5-dihydroxynaphthalene, 56.8 g of formaldehyde, and 300 g of PGME (propylene glycol monomethyl ether) were added and homogenized at an internal temperature of 100°C. Then, a mixture of 8.0 g of p-toluenesulfonic acid monohydrate and 8.0 g of PGME, which had been pre-mixed and homogenized, was slowly added dropwise, and the reaction was carried out at an internal temperature of 80°C for 8 hours. After the reaction was complete, the mixture was cooled to room temperature, 2,000 ml of MIBK was added, and the mixture was washed six times with 500 ml of pure water. The organic layer was dried under reduced pressure. 300 g of THF was added to the residue to make a homogenized solution, and then crystallized in 2,000 g of hexane. The precipitated crystals were separated by filtration, washed twice with 500 g of hexane, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain resin (R-6).

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

[0253] [ka]

[0254] (Synthesis of fluidity enhancers) For the synthesis of the fluidity enhancer, the following organic group raw materials G: (G19) to (G21) and modifying agents K: (K1) to (K2) were used.

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

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

[0257] [Synthesis of the fluidity enhancer (BPA-1)] Under a nitrogen atmosphere, 45.5 g of compound (G19) from the above organic raw material group G, 9.8 g of potassium carbonate, and 150 g of DMF were added, and a homogeneous dispersion was prepared 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 the separated aqueous layer was removed. The organic layer was then washed six times with 100 g of 3% nitric acid aqueous solution and 100 g of pure water, and the organic layer was dried under reduced pressure to obtain the fluidity enhancer (BPA-1).

[0258] The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (BPA-1): Mw=965, Mw / Mn=1.08

[0259] [ka]

[0260] [Synthesis of the fluidity enhancer (BPA-2)] 80.0 g of epoxy compound (G20) from the above organic raw material group G, 51.0 g of modifying agent (K2), and 600 g of 2-methoxy-1-propanol were mixed into a homogeneous solution under a nitrogen atmosphere at an internal temperature of 100°C. Then, 5.7 g of benzyltriethylammonium chloride was added and the mixture was 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 the fluidity enhancer (BPA-2).

[0261] The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (BPA-2): Mw=900, Mw / Mn=1.04

[0262] [ka]

[0263] [Synthesis of fluidity enhancer (BPA-3)] Under a nitrogen atmosphere, 20.0 g of resin (G21) from the above organic raw material group G, 34.5 g of potassium carbonate, and 100 g of DMF were added and a homogeneous dispersion was prepared 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 the separated aqueous layer was removed. The organic layer was then washed six times with 100 g of 3% nitric acid aqueous solution and 100 g of pure water, and the organic layer was dried under reduced pressure to obtain the fluidity enhancer (BPA-3).

[0264] The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (BPA-3): Mw=9,400, Mw / Mn=3.59

[0265] [ka]

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

[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 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 the one represented by the following formula (C-1). The acid generator (TAG) used was the one represented by the following formula (E-1). The high-boiling point solvent (B-1) used was ethylene glycol dibenzyl ether with a boiling point of 364°C.

[0268] [Crosslinking agent, acid generator] The crosslinking agent (C-1) and 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 Embedding Characteristics] The compositions prepared above (MUL-1 to 18, and Comparative Examples MUL-1 to 6) were each coated onto an 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, the compositions prepared above (MUL-1 to 18, and Comparative Examples MUL-1 to 6) were each coated onto an 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] Substrates A and B used are base substrates 9 (SiO2 wafer substrates) having a dense line and space pattern as shown in Figures 3(Q) (overhead view) and (R) (cross-sectional view). The cross-sectional shape of each wafer substrate obtained from the embedding evaluation was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. to confirm whether there were any voids (gaps) inside the metal-containing film filling the spaces between lines. The results are shown in Table 4. When a metal-containing film formation composition with poor embedding characteristics was used, voids were generated inside the metal-containing film filling the spaces between lines in this evaluation. When a metal-containing film formation composition with good embedding characteristics was used, a void-free metal-containing film 10 was filled inside the metal-containing film filling the spaces between lines of the base substrate 9 having a dense line and space pattern as shown in Figure 3(S) in this evaluation.

[0274] [Table 4]

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

[0276] On the other hand, unlike the metal-containing film-forming compounds of the present invention, comparative metal-containing film-forming compositions (Comparative Example MUL-1~) include metal-containing film-forming compounds having organic ligands that do not contain crosslinking groups of formulas (a-1) to (a-4). 2) In Comparative Examples 1-1 to 1-2, voids were observed at the bottom of the pattern after baking at 350°C on both substrate A and substrate B. It is presumed that these comparative metal-containing film-forming compositions had low heat resistance of the metal-containing film, resulting in large volume shrinkage due to high-temperature baking and thus the generation of voids.

[0277] On the other hand, Comparative Examples 1-3 to 5, which used comparative metal-containing film-forming compositions (Comparative Examples UDL-3 to 5) containing a metal-containing film-forming compound that includes crosslinking groups of formulas (a-1) to (a-4) but does not contain ligands derived from the organic compound shown in formula (1), were able to fill a dense line and space pattern on substrate A without generating voids. However, void generation was observed on substrate B, which contained a finer pattern. These comparative metal-containing film-forming compositions contain crosslinking groups of formulas (a-1) to (a-4) but do not contain ligands derived from the organic compound shown in formula (1) of the present invention. As a result, it is presumed that voids were generated on substrate B, which contains a finer pattern and is more susceptible to heat from the substrate, due to insufficient heat resistance.

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

[0279] [Table 5]

[0280] As shown in Table 5, Examples 2-1 to 2-18, using the metal-containing film-forming compositions (MUL-1 to 18) of the present invention, showed small differences in film height between patterned and unpatterned areas, and demonstrated planarization performance comparable to Comparative Example 2-1, which used an organic resist underlayer material. Furthermore, MDL-14, with the addition of a high-boiling point solvent (B-1), and MDL-16 to 18, with the addition of a fluidity enhancer (BPA-1 to 3), showed superior planarization characteristics compared to the composition without additives. It is presumed that the thermal fluidity of the metal-containing film-forming compositions could be further improved by using additives. On the other hand, the metal-containing film-forming compound (A-1), which contains only ligands derived from the organic compound shown in formula (1), showed superior flatness compared to the metal-containing film-forming compound (A-9), which further contains ligands other than those derived from the organic compound shown in formula (1).

[0281] [Example 3 and Comparative Example 3: Etching Resistance Evaluation] Metal-containing film-forming compositions (MUL-1 to 18, and comparative examples MUL-1 to 6) were each applied to 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 film thickness a was measured. Next, etching (condition 1 and condition 2) was performed using CF4 gas under the following conditions with a Tokyo Electron TE8500 etching system, and the film thickness b was measured. The etching rate (nm / min) was calculated from the film thickness etched over a specified time (film thickness a - film thickness b), which represents the film thickness etched per minute.

[0282] Under Condition 1, etching rates of 50 nm / min or less were judged as "Excellent (A)", rates between 50 nm / min and 60 nm / min were judged as "Good (B)", and rates greater than 60 nm / min were judged as "Poor (C)". Under Condition 2, etching rates of 35 nm / min or less were judged as "Excellent (A)", rates between 35 nm / min and 40 nm / min were judged as "Good (B)", and rates 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: 100 sccm Time: 20sec

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

[0285] [Table 6]

[0286] As shown in Table 6, Examples 3-1 to 3-18, using the metal-containing film-forming compositions (MUL-1 to 18) of the present invention, were found to exhibit excellent etching resistance to CF4 gas compared to an organic underlayer film material (Comparative Example 3-6, using a comparative metal-containing film-forming compound (R-6)). Furthermore, they also showed excellent dry etching resistance compared to Comparative Example 3-5, which used a metal-containing film-forming compound (R-5) that had not undergone hydrolysis condensation. In particular, the metal-containing film-forming compositions (MUL-1 to 18) of the present invention showed high resistance even under condition 2, which involves a high Ar flow rate. Therefore, it is considered that they will also exhibit excellent resistance to physical etching with high Ar flow rates, which is used in oxide film etching of advanced devices.

[0287] The metal-containing film-forming compound (A-9), which further contains ligands other than those derived from the organic compound shown in formula (1), showed improved dry etching resistance compared to the metal-containing film-forming compound (A-1), which contains only ligands derived from the organic compound shown in formula (1). In other words, in the present invention, by adjusting the proportion of ligands derived from the organic compound shown in formula (1) contained in the metal-containing film-forming compound, dry etching resistance and planarization characteristics can be appropriately adjusted according to the required characteristics of the application process.

[0288] [Example 4 and Comparative Example 4: Pattern Forming Method] The above metal-containing film-forming compositions (MUL-1 to MUL-18, comparative example MUL-6) were each applied to an 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 interlayer material (SOG-1) was applied on top of this and baked at 220°C for 60 seconds to form a resist interlayer with a thickness of 50 nm. An ArF single-layer resist, which is a resist top layer material, was applied on top of this 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 top of 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 atom-containing resist interlayer material (SOG-1) was prepared as follows. First, the polymer represented by ArF silicon-containing interlayer polymer (SiP1) and the thermal crosslinking catalyst (CAT1) were dissolved in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M) in the proportions shown in Table 7. The silicon atom-containing resist interlayer material (SOG-1) was prepared by filtering the mixture obtained in this way through a fluororesin filter with a pore size of 0.1 μm.

[0290] [Table 7]

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

[0292] [ka]

[0293] The resist top layer material (single-layer resist for ArF) was prepared as follows. First, the polymer (RP1), acid generator (PAG1), and basic compound (Amine1) were dissolved in a solvent containing 0.1% by mass of surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 8, and the mixture was filtered through a 0.1 μm fluororesin filter to prepare the resist top layer material.

[0294] [Table 8]

[0295] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) used in the resist upper layer material (single-layer resist for ArF) 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 proportions shown in Table 9 and filtering it through a 0.1 μm fluororesin 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 sample was exposed using an ArF immersion lithography system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s polarized illumination, 6% halftone phase shift mask), baked (PEB) at 100°C for 60 seconds, and developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 55 nm 1:1 positive-type line-and-space pattern (resist upper layer pattern).

[0301] Next, a hard mask pattern was formed by dry etching the resist interlayer using the resist upper layer pattern as a mask. A metal-containing film pattern was then formed by etching the metal-containing film using the obtained hard mask pattern as a mask. Finally, the SiO2 film was etched using the obtained metal-containing film pattern as a mask. Etching was performed using a ULVAC CE-300I etching system under the following conditions.

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

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

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

[0305] Table 10 shows the results of observing the pattern cross-section using an electron microscope (S-4700) manufactured by Hitachi, Ltd.

[0306] [Table 10]

[0307] As shown in Table 10, in Examples 4-1 to 4-18, which used the metal-containing film-forming compositions (MUL-1 to 18) of the present invention, the resist upper layer film pattern was successfully transferred to the substrate in all cases, confirming that the metal-containing film-forming compositions of the present invention are suitable for use in microfabrication using the multilayer resist method. On the other hand, in Comparative Example 4-1, which showed insufficient performance in the dry etching resistance evaluation, distortion of the pattern shape occurred during pattern processing, and a good pattern could not be obtained in the end.

[0308] [Example 5 and Comparative Example 5: SOC Pattern Inversion Method] A resist underlayer material (SOC-1) was applied to a silicon wafer substrate with an SiO2 film already formed on it, and baked at 350°C for 60 seconds to form a resist underlayer with a thickness of 150 nm. A silicon atom-containing resist interlayer material (SOG-1) was then applied on top of this and baked at 220°C for 60 seconds to form a resist interlayer with a thickness of 40 nm. An ArF single-layer resist, which is a resist toplayer material, was then applied on top of this 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 to 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 atom-containing resist interlayer material (SOG-1), resist top layer material (single-layer resist for ArF), and immersion protective film material on the photoresist film (TC-1) were the same materials used in the pattern formation method described above (Example 4).

[0310] The coating-type resist underlayer material (SOC-1) is a polymer represented by the resist underlayer polymer (SOP1). of, A coated resist underlayer material (SOC-1) was prepared by dissolving FC-4430 (manufactured by Sumitomo 3M) at the proportions shown in Table 11 in an organic solvent and filtering the mixture through a fluororesin filter with a pore size of 0.2 μm.

[0311] [Table 11]

[0312] Table 12 shows the structural formula of the polymer (SOP1) used for the resist underlayer film.

[0313] [Table 12]

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

[0315] Next, using the Telius etching system manufactured by Tokyo Electron, the resist interlayer was etched using the resist upper layer pattern as a mask by dry etching to form a hard mask pattern. Then, the resist lower layer (SOC-1) was etched using the obtained hard mask pattern as a mask to form an SOC-1 film pattern. The etching conditions are as follows.

[0316] Transfer conditions for the resist upper layer pattern to the resist interlayer. Chamber pressure: 50mT RF Power (Top): 500W RF Power (Bottom): 300W CF4 gas flow rate: 150 sccm CHF3 gas flow rate: 50 sccm Time: 20sec

[0317] Transfer conditions for hard mask patterns to the resist underlayer film. Chamber pressure: 10mT RF Power (Top): 1,000W RF Power (Bottom): 300W CO2 gas flow rate: 150 sccm CO gas flow rate: 50 sccm N2 gas flow rate: 50 sccm H2 gas flow rate: 150 sccm Time: 90sec

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

[0319] Etching back conditions (exposure of SOC-1 film pattern) for metal-containing films. Pressure: 1 Pa Antenna RF power: 320W Bias RF Power: 30W Cl2 gas flow rate: 25 sccm Time: 20sec

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

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

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

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

[0324] Table 13 shows the results of observing the pattern cross-section using an electron microscope (S-4700) manufactured by Hitachi, Ltd.

[0325] [Table 13]

[0326] As shown in Table 13, in Examples 5-1 to 5-18, which used the metal-containing film-forming compositions (MUL-1 to 18) of the present invention, the SOC-1 film pattern was accurately inverted in all cases, and the inverted pattern was successfully transferred to the substrate without any distortion. This confirms that the metal-containing film-forming compositions of the present invention are suitable for use in microfabrication using a tone-inversion etching method in multilayer resist processing. On the other hand, in Comparative Example 5-3, where the SOC-1 film pattern was directly transferred to the SiO2 film, distortion of the pattern shape was observed due to insufficient etching resistance of the SOC-1 film. Furthermore, in Comparative Examples 5-1 to 5-2, where insufficient performance was confirmed in the embedding characteristic evaluation (substrate B), the metal-containing film was not filled to the bottom between the SOC-1 film patterns, making it impossible to invert the pattern and ultimately obtain a good inverted pattern.

[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 is extremely useful as a metal-containing layer (resist underlayer film) material used in multilayer resist methods and as an inversion agent used in tone inversion etching methods, because it possesses both high embedding and planarization characteristics and dry etching resistance. Furthermore, it has become clear that the pattern formation method of the present invention using this method can form fine patterns with high precision even on substrates that have steps.

[0328] This specification includes the following embodiments: [1](A) A metal-containing film-forming compound, The metal-containing film-forming compound (A) is characterized in that it is a compound derived from a metal-containing compound obtained by hydrolysis or 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) R2A COXCOOH (1) (In the formula, M is Ti, Zr, or Hf, and R 1A R is a monovalent organic group having 1 to 20 carbon atoms. 2A (where X is a divalent organic group having 2 to 20 carbon atoms and containing at least one bridging group represented by 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 (where is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [2] The (A) metal-containing film-forming compound is One or more selected from the hydrolysis product of only the metal compound represented by formula (A-1), the condensate product of only the metal compound represented by formula (A-1), and the hydrolysis condensate product of only the metal compound represented by formula (A-1), The organic compound represented by formula (1) above and A metal-containing film-forming compound as described in [1], characterized in that it is a metal-containing compound that is a reactant of [1]. [3] In formula (1) above, R 2A A metal-containing film-forming compound according to [1] or [2], characterized in that the structure is represented by the following general formula (B-1). [ka] (In the above general formula (B-1), R A1 This is the structure shown by the general formula (a-1) above, and R A2 is one 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 (where is a divalent organic group with 1 to 20 carbon atoms, saturated or unsaturated with 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 to 6, r is 1 to 10, u is 0 or 1, m is 0 or 1, and * represents the bond with the carbon atom of the carbonyl group.) [4] The metal-containing film-forming compound according to any one of [1] to [3], characterized in that the organic group X in formula (1) is a saturated hydrocarbon group having 2 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms. [5] A metal-containing film-forming compound according to any one of [1] to [4], characterized in that the organic group X in formula (1) is a group represented by any of the following formulas (2). [ka] (In the above general formula (2), R a and R b R is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms. c R is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms. a and R b These may be bonded, forming a cyclic substituent. (*1 and *2 represent the bond with the carbonyl group, and *1 and *2 may be reversed.) [6] The metal-containing film-forming compound according to any one of [1] to [5], characterized in that the (A) metal-containing film-forming compound includes 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 of these independently corresponds to R in equation (A-1) above. 1A or COXCOR in formula (1) above 2A It is either R ae ~R de At least one of the above formulas ( 1 ) COXCOR 2A Here, n is between 1 and 20, and M is the same as M in equation (A-1) above. [7] The (A) metal-containing film-forming compound further comprises, in addition to the ligand derived from the organic compound represented by formula (1), a ligand derived from the organic compound represented by the following formula (3), and at least one additional ligand selected from any of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic acid anhydride, The metal-containing film-forming compound according to any one of [1] to [5], characterized in 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 (It is a monovalent organic group with 1 to 20 carbon atoms.) [8] The metal-containing film-forming compound according to [7], characterized in that the (A) metal-containing film-forming compound includes a compound having any one of the following structures. [ka] (R above) 3a R is a monovalent organic group having 1 to 20 carbon atoms that does not contain the bridging group shown in the above general formulas (a-1) to (a-4), or one of the structures shown in the following formulas, 1A R in the above equation (A-1) is 1A It is the same as R 2A R in equation (1) above 2A This is the same as the above equation (A-1), where n is between 1 and 20, and M is the same as M in equation (A-1). [ka] (In the above formula, R 3b (where * represents an alkyl group with 1 to 10 carbon atoms, and * represents the bond with the carbonyl carbon.) [9] A composition for forming a metal-containing film, (A) Metal-containing film-forming compounds as described in any one of items [1] to [8] and (B) Organic solvents A metal-containing film-forming composition characterized by containing the following:

[10] The composition further, (C) Crosslinking agent, (D) Surfactants, and (E) Acid generator The method described in [9] is characterized by containing one or more of the following: Contains metal Composition for film formation.

[11] The (B) organic solvent comprises (B-1) high-boiling point solvent, wherein the (B-1) high-boiling point solvent is one or more organic solvents having a boiling point of 180 degrees or higher, as described in [9] or

[10] . Contains metal Composition for film formation.

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

[11] , characterized in that the metal-containing film-forming composition further comprises a flow enhancer (BP) having an organic group represented by the following general formula (bp1a) and an aromatic ring. [ka] (In the formula, * represents the bonding site to the oxygen atom, R B R is a divalent organic group with 1 to 10 carbon atoms. A (This refers to 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 fluidity enhancer (BP) has at least one constituent unit represented by any of the following general formulas (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5). [ka] (In the above general formulas (BP-1) and (BP-2), W1 and W2 are independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. a1 is the group represented by the following general formula (4). Y is the group represented by the following general formula (5). n1 is 0 or 1, n2 is 1 or 2, and V independently represents a hydrogen atom or a linkage. [ka] (In the above general formula (BP-3), Z1 is the base shown in the following general formula (6) in Yes, R a1 The following general formula (4) is given by: n4 is 0 or 1, n5 is 1 or 2, and V independently represents a hydrogen atom or a bonding group. [ka] (* indicates a bond with an oxygen atom.) [ka] (* indicates a bond.) [ka] (In the above general formula (6), W1, W2, Y, and n1 are the same as described above.) [ka] (In the formula, m3 and m4 represent 1 or 2, and Z2 is either a single bond or a structure shown in the general formula (7) below. x (This is one of the structures shown in the following general formula (8).) [ka] (In the formula, * represents a combination, l represents an integer from 0 to 3, and R az ~R fz Each of these independently represents a hydrogen atom or a C1-C10 alkyl group, phenyl group, or phenylethyl group which may be substituted with fluorine, and R az and R bz (These two components may combine to form a cyclic compound.) [ka] (In the formula, * represents the bonding site to the aromatic ring, and Q1 is Number of carbon atoms It consists of 1 to 30 linear saturated hydrocarbon groups, or a structure represented by the general formula (9) below. [ka] (In the formula, * represents the bonding site to the carbonyl group, R i The above general formula( 4) R j These are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, halogen atoms, nitro groups, amino groups, nitrile groups, and carbon number 2 This represents an alkoxycarbonyl group with approximately 10 carbon atoms, or an alkanoyloxy group with 1 to 10 carbon atoms. 3z and n 4z n represents the number of substituents on the aromatic ring, each representing an integer from 0 to 7. 3z +n 4z n is between 0 and 7 (inclusive). 5z (This represents values ​​from 0 to 2.) [ka] (In the above general formula (BP-5), R 1 R 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, and R a1 This is the general formula (4) above. p is an integer between 0 and 5, q1 is an integer between 1 and 6, p+q1 is an integer between 1 and 6 (inclusive), and q2 is either 0 or 1.

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

[15] A method for forming a pattern on a substrate to be processed, (I-1) A step of forming a metal-containing film by applying a metal-containing film-forming composition described in any one of [9] to

[13] onto a substrate to be processed, and then heat-treating it, (I-2) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. A pattern forming method characterized by having the following features.

[16] A method for forming a pattern on a substrate to be processed, (II-1) A step of forming a metal-containing film by applying a metal-containing film-forming composition described in any one of [9] to

[13] onto a substrate to be processed, and then heat-treating it, (II-2) A step of forming a resist interlayer on the metal-containing film, (II-3) A step of forming a resist upper layer film on the resist interlayer film using a photoresist material, (II-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-5) A step of transferring the pattern to the resist interlayer by dry etching, using the resist upper layer on which the pattern is formed as a mask. (II-6) A step of transferring the pattern to the metal-containing film by dry etching using the resist interlayer on which the pattern has been transferred as a mask, and (II-7) A process of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. A pattern forming method characterized by having the following features.

[17] A method for forming a pattern on a substrate to be processed, (III-1) A step of forming a metal-containing film by applying a metal-containing film-forming composition described in any one of [9] to

[13] onto a substrate to be processed, and then heat-treating it, (III-2) A step of forming an inorganic hard mask interlayer selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film. (III-3) A step of forming an organic thin film on the inorganic hard mask interlayer, (III-4) A step of forming a resist upper layer film on the organic thin film using a photoresist material, (III-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (III-6) A step of transferring the pattern to the organic thin film and the inorganic hard mask interlayer film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (III-7) A step of transferring the pattern to the metal-containing film by dry etching using the inorganic hard mask interlayer on which the pattern has been transferred as a mask, and (III-8) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. A pattern forming method characterized by having the following features.

[18] A method for forming a pattern on a substrate to be processed, (IV-1) A step of forming a metal-containing film by applying a metal-containing film-forming composition described in any one of [9] to

[13] onto a substrate to be processed, and then heat-treating it, (IV-2) A step of forming an organic interlayer on the metal-containing film, (IV-3) A step of forming a combination of an organic thin film and an inorganic hard mask interlayer selected from a silicon-containing resist interlayer, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic interlayer. (IV-4) A step of forming a resist upper layer film on the silicon-containing resist interlayer film or the organic thin film using a photoresist material. (IV-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (IV-6) A step of transferring the pattern to a silicon-containing resist interlayer or the organic thin film and the inorganic hard mask interlayer by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (IV-7) A step of transferring the pattern onto an organic interlayer by dry etching, using the silicon-containing resist interlayer or inorganic hard mask interlayer on which the pattern has been transferred as a mask. (IV-8) The aforementioned pattern is transferred A step of using the aforementioned organic interlayer as a mask to transfer a pattern to the metal-containing film by dry etching, and (IV-9) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. A pattern forming method characterized by having the following features.

[19] A method for forming a pattern on a substrate to be processed, (V-1) A step of forming a resist underlayer film on the substrate to be processed. (V-2) A step of forming a resist interlayer, or a combination of an inorganic hard mask interlayer 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) A step of forming a resist upper layer film using a photoresist material on the resist interlayer film, or a combination of an inorganic hard mask interlayer film and an organic thin film. (V-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (V-5) A step of transferring the pattern to the resist interlayer, or the organic thin film and the inorganic hard mask interlayer, by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (V-6) A step of transferring the pattern to the resist underlayer film by dry etching, using the resist interlayer film on which the pattern has been transferred, or an inorganic hard mask interlayer film, as a mask. (V-7) A step of coating the resist underlayer film on which the pattern is formed with a metal-containing film composition according to any one of [9] to

[13] , then heat-treating it to coat it with a metal-containing film, thereby filling the gaps 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, thereby exposing the upper surface of the resist underlayer film on which the pattern has been formed. (V-9) A step of removing the resist interlayer or hard mask interlayer remaining on the upper surface of the resist underlayer by dry etching. (V-10) A step of removing the resist underlayer film on which the exposed surface pattern is formed by dry etching, and forming an inverted pattern of the original pattern on the metal-containing film. (V-11) A process of processing the workpiece substrate using the metal-containing film on which the inverted pattern is formed as a mask to form the inverted pattern on the workpiece substrate. A tone-reversal pattern forming method characterized by having the following features.

[0329] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention. [Explanation of Symbols]

[0330] 1...Substrate, 1A...Substrate to be processed, 2...Layer to be processed, 2a...Pattern (Pattern formed on the layer to be processed), 3...Metal-containing film, 3a...Metal-containing film pattern, 4...Resist interlayer, 4a...Resist interlayer pattern, 5...Resist upper layer, 5a...Resist upper layer pattern, 6...Exposed area, 7...Resist lower layer, 7a...Resist lower layer pattern, 8...Metal-containing film, 8a...Metal-containing film pattern with the resist lower layer pattern reversed, 9...Underlay substrate with dense lines and spaces, 10...Metal-containing resist lower layer, 11...Underlay substrate with dense lines and spaces, 12...Metal-containing resist lower layer, Delta12...Step difference between the patterned and non-patterned areas of the metal-containing resist lower layer 12.

Claims

1. (A) A compound for forming a metal-containing film, The metal-containing film-forming compound (A) is characterized in that it is a compound derived from a metal-containing compound obtained by hydrolysis or 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 C(=O)XC(=O)OH (1) (In the formula, M is Ti, Zr, or Hf, and R １Ａ R is a monovalent organic group having 1 to 20 carbon atoms. ２Ａ (where X is a monovalent organic group having 8 to 20 carbon atoms, containing at least one bridging group represented by the following general formula (a-2) or (a-3) and having the structure represented by the following general formula (B-1), and X is a saturated hydrocarbon group having 2 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms.) 【Chemistry 1】 (In the above general formulas (a-2) and (a-3), R ａ (where is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) 【Chemistry 2】 (In the above general formula (B-1), R A2 is one of the structures shown in 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, R A3 is a monovalent organic group having 1 to 20 carbon atoms or an unsaturated 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, u is 0 or 1, m is 0 or 1, and * represents the bond with the carbon atom of the carbonyl group.)

2. The (A) metal-containing film-forming compound is One or more selected from the hydrolysis product of only the metal compound represented by formula (A-1), the condensate product of only the metal compound represented by formula (A-1), and the hydrolysis condensate product of only the metal compound represented by formula (A-1), The organic compound represented by formula (1) above and The metal-containing film-forming compound according to claim 1, characterized in that it is a metal-containing compound that is a reactant of the above.

3. The metal-containing film-forming compound according to claim 1, characterized in that the hydrocarbon group X in formula (1) is a group represented by any of the following formulas (2). 【Transformation 3】 (In the above general formula (2), R ａ and R ｂ are 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 bonding part with a carbonyl group, and *1 and *2 may be reversed.)

4. The metal-containing film-forming compound according to claim 1, characterized in that the (A) metal-containing film-forming compound includes a compound having a structure represented by the following general formula (m-1). 【Chemistry 4】 (In the above formula (m-1), R ａｅ ~R ｄｅ Each of these independently corresponds to R in the above formula (A-1). １Ａ Or C(=O)XC(=O)R in the above formula (1) ２Ａ It is one of the following, R ａｅ ~R ｄｅ At least one of them is C(=O)XC(=O)R in the above formula (1). ２Ａ Here, n is between 1 and 20, and M is the same as M in equation (A-1) above.

5. The (A) metal-containing film-forming compound further comprises, in addition to the ligand derived from the organic compound represented by formula (1), a ligand derived from the organic compound represented by the following formula (3), and at least one additional ligand selected from any of succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and cyclohexanedicarboxylic acid anhydride. The metal-containing film-forming compound according to claim 1, characterized in that the additional ligand does not contain a group represented by the general formula (a-2) or (a-3). R ３Ａ C(=O)OH (3) (In the formula, R ３Ａ (It is a monovalent organic group with 1 to 20 carbon atoms.)

6. The metal-containing film-forming compound according to claim 5, characterized in that the (A) metal-containing film-forming compound includes a compound having any one of the following structures. 【Transformation 5】 (R above) ３ａ R is a monovalent organic group having 1 to 20 carbon atoms that does not contain a bridging group as shown in the general formula (a-2) or (a-3) above, or any of the structures shown in the following formulas, １Ａ R in the above formula (A-1) is １Ａ It is the same as R ２Ａ R in the above equation (1) is ２Ａ This is the same as above, where n is between 1 and 20, and M is the same as M in equation (A-1) above. 【Transformation 6】 (In the above formula, R ３ｂ (where * represents an alkyl group having 1 to 10 carbon atoms, and * represents the bond with the carbonyl carbon.)

7. A composition for forming a metal-containing film, (A) Metal-containing film-forming compound according to any one of claims 1 to 6 and (B) Organic solvents A metal-containing film-forming composition characterized by containing the following:

8. The aforementioned composition further, (C) Crosslinking agent, (D) Surfactants, and (E) Acid Generator The metal-containing film-forming composition according to claim 7, characterized in that it contains one or more of the following.

9. The metal-containing film-forming composition according to claim 7, characterized in that the (B) organic solvent includes (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 degrees or higher.

10. The metal-containing film-forming composition according to claim 7, further comprising a flow promoter (BP) having an organic group represented by the following general formula (bp1a) and an aromatic ring. 【Transformation 7】 (In the formula, * represents the bonding site to the oxygen atom, R Ｂ R is a divalent organic group having 1 to 10 carbon atoms. Ａ (This is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.)

11. The metal-containing film-forming composition according to claim 10, characterized in that the fluidity enhancer (BP) has at least one constituent unit represented by any of the following general formulas (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5). 【Transformation 8】 (In the above general formulas (BP-1) and (BP-2), W １ and W ２ Each of these is independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. ａ１ n is 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 (where V is either 1 or 2, and V independently represents a hydrogen atom or a bonding group.) 【Chemistry 9】 (In the above general formula (BP-3), Z １ R is a group represented by the following general formula (6), ａ１ n is given by the following general formula (4). ４ is 0 or 1, n ５ (where V is either 1 or 2, and V independently represents a hydrogen atom or a bonding group.) 【Chemistry 10】 (* indicates a bond with an oxygen atom.) 【Chemistry 11】 (* indicates a bonding action.) 【Chemistry 12】 (In the above general formula (6), W １ , W ２ , Y, n １ (This is the same as above.) 【Chemistry 13】 (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 (This is one of the structures shown in the following general formula (8).) 【Chemistry 14】 (In the formula, * represents a combination, l represents an integer from 0 to 3, and R ａｚ ~R ｆｚ Each of these independently represents a hydrogen atom or a C1-C10 alkyl group, phenyl group, or phenylethyl group which may be substituted with fluorine, and R ａｚ and R ｂｚ (These may combine to form a cyclic compound.) 【Chemistry 15】 (In the formula, * represents the bonding site to the aromatic ring, Q) １ (This refers to a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the general formula (9) below.) 【Chemistry 16】 (In the formula, * represents the bonding site to the carbonyl group, R ｉ This is the general formula (4) above. R ｊ n 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 2 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. ３ｚ and n ４ｚ n represents the number of substituents on the aromatic ring, and each integer is between 0 and 7. ３ｚ +n ４ｚ n is between 0 and 7. ５ｚ (This represents values ​​from 0 to 2.) 【Chemistry 17】 (In the general formula (BP-5), R １ X is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms. １ R is a divalent organic group having 1 to 30 carbon atoms. ａ１ This is the general formula (4) above. p is an integer from 0 to 5, q １ p+q are integers from 1 to 6. １ is an integer between 1 and 6, and q ２ (It is either 0 or 1.)

12. A method for forming a pattern on a substrate to be processed, (I-1) A step of forming a metal-containing film by applying the metal-containing film-forming composition described in claim 7 onto a substrate to be processed, and then heat-treating it. (I-2) A step of forming a resist upper 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 exposure followed by development with a developer solution. (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. A pattern forming method characterized by having the following features.

13. A method for forming a pattern on a substrate to be processed, (II-1) A step of forming a metal-containing film by applying the metal-containing film-forming composition described in claim 7 onto a substrate to be processed, and then heat-treating it. (II-2) A step of forming a resist interlayer on the metal-containing film, (II-3) A step of forming a resist upper layer film on the resist interlayer film using a photoresist material, (II-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-5) A step of transferring the pattern to the resist interlayer by dry etching, using the resist upper layer on which the pattern is formed as a mask. (II-6) A step of transferring the pattern to the metal-containing film by dry etching using the resist interlayer on 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 is formed as a mask to form a pattern on the substrate to be processed. A pattern forming method characterized by having the following features.

14. A method for forming a pattern on a substrate to be processed, (III-1) A step of forming a metal-containing film by applying the metal-containing film-forming composition described in claim 7 onto a substrate to be processed, and then heat-treating it. (III-2) A step of forming an inorganic hard mask interlayer selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film. (III-3) A step of forming an organic thin film on the inorganic hard mask interlayer, (III-4) A step of forming a resist upper 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 exposure followed by development with a developer solution. (III-6) A step of transferring the pattern to the organic thin film and the inorganic hard mask interlayer film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (III-7) A step of transferring the pattern to the metal-containing film by dry etching using the inorganic hard mask interlayer on 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 is formed as a mask to form a pattern on the substrate to be processed. A pattern forming method characterized by having the following features.

15. A method for forming a pattern on a substrate to be processed, (IV-1) A step of forming a metal-containing film by applying the metal-containing film-forming composition described in claim 7 onto a substrate to be processed, and then heat-treating it. (IV-2) A step of forming an organic interlayer on the metal-containing film, (IV-3) A step of forming a combination of an organic thin film and an inorganic hard mask interlayer selected from a silicon-containing resist interlayer, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic interlayer. (IV-4) A step of forming a resist upper layer film on the silicon-containing resist interlayer film or the organic thin film using a photoresist material. (IV-5) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (IV-6) A step of transferring the pattern to a silicon-containing resist interlayer or the organic thin film and the inorganic hard mask interlayer by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (IV-7) A step of transferring the pattern to an organic interlayer by dry etching, using the silicon-containing resist interlayer or inorganic hard mask interlayer on which the pattern has been transferred as a mask. (IV-8) A step of transferring the pattern to the metal-containing film by dry etching using the organic interlayer on which the pattern has been transferred as a mask, and (IV-9) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. A pattern forming method characterized by having the following features.

16. A method for forming a pattern on a substrate to be processed, (V-1) A step of forming a resist underlayer film on the substrate to be processed. (V-2) A step of forming a resist interlayer, or a combination of an inorganic hard mask interlayer 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) A step of forming a resist upper layer film using a photoresist material on the resist interlayer film, or a combination of an inorganic hard mask interlayer film and an organic thin film. (V-4) A step of pattern exposure of the resist upper layer film, followed by development with a developer to form a pattern on the resist upper layer film. (V-5) A step of transferring the pattern to the resist interlayer, or the organic thin film and the inorganic hard mask interlayer, by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (V-6) A step of transferring the pattern to the resist underlayer film by dry etching, using the resist interlayer film on which the pattern has been transferred, or an inorganic hard mask interlayer film, as a mask. (V-7) A step of coating the resist underlayer film on which the pattern is formed with the metal-containing film composition according to claim 7, and then heat-treating it to form a metal-containing film, thereby filling the gaps 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 chemical stripping or dry etching, thereby exposing the upper surface of the resist underlayer film on which the pattern has been formed. (V-9) A step of removing the resist interlayer or hard mask interlayer remaining on the upper surface of the resist underlayer by dry etching. (V-10) A step of removing the resist underlayer film on which the exposed surface pattern is formed by dry etching, and forming an inverted pattern of the original pattern on the metal-containing film. (V-11) A step of processing the workpiece substrate using the metal-containing film on which the inverted pattern is formed as a mask to form the inverted pattern on the workpiece substrate. A tone-reversal pattern forming method characterized by having the following features.

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