Compound for forming metal-containing films, composition for forming metal-containing films, and pattern forming method

Abstract

To provide a metal compound having better dry etching resistance than conventional resist underlayer film materials and also having high filling and planarizing properties; a composition for forming a metal-containing film that contains the compound; and a patterning process in which the composition is used.SOLUTION: The present invention is a compound for forming a metal-containing film to be incorporated into a composition for forming a metal-containing film, where the compound for forming a metal-containing film includes at least one metal atom selected from the group consisting of Ti, Zr, and Hf and one or more ligands derived from compounds represented by the following general formulae (1-A) to (1-D).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, and a method for forming a pattern using the composition. [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 thickness of the photoresist film used was kept the same while miniaturization was achieved, i.e., the pattern width was reduced, the resolution performance of the photoresist film decreased. Furthermore, when attempting to develop the photoresist film using a developer, the aspect ratio became too large, resulting in pattern collapse. For this reason, as patterns became smaller, the photoresist film was made thinner.

[0004] On the other hand, the processing of substrates typically involves using a photoresist film with a pattern formed on it as an etching mask and processing the substrate by dry etching. 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 lower layer film with different etching selectivity are interposed between the resist upper layer film and the substrate to be processed. After obtaining a pattern on the resist upper layer film, the resist upper layer film pattern is used as a dry etching mask to transfer the pattern to the resist lower layer film by dry etching, and then the resist lower layer film 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 resist underlayer 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 the advanced generation, and the applicability limits of conventional coated resist underlayer 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 underlayers 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 their 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 baking temperature used for the embedding property evaluations is a low 150°C. There are concerns that these may be insufficient for underlayers for resists that require heat resistance (for example, properties against heat treatments that may be applied after the underlayer is formed). [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] Japanese Patent Publication No. 2004-205685 [Patent Document 2] Patent No. 6714493 [Patent Document 3] Patent No. 6189758 [Patent Document 4] Patent No. 6786391 [Patent Document 5] Patent No. 7050137 [Overview of the project] [Problems that the invention aims to solve]

[0012] The present invention has been made in view of the above circumstances, and aims to provide a metal compound that has excellent dry etching resistance compared to conventional resist underlayer film materials, as well as advanced embedding / planarization characteristics, a metal-containing film formation composition using the compound, and a pattern formation method using the composition. [Means for solving the problem]

[0013] To solve the above problems, the present invention provides a metal-containing film-forming compound used in a metal-containing film-forming composition, The present invention provides a metal-containing film-forming compound that contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and one or more ligands derived from compounds represented by the following general formulas (1-A) to (1-D). [ka] (In general formulas (1-A) to (1-D), R1 to R3 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4). R4 to R5 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4). R6 to R9 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4). 10 R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms. Compounds of general formulas (1-A) to (1-D) contain one or more bridging groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4). In general formula (1-B), R4 and R5 may be bonded to each other, forming an unsaturated or saturated ring structure. [ka] (In general formulas (a-1) to (a-4), Ra is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [ka] (In general formulas (b-1) to (b-4), R' b R' is a hydrogen atom or a methyl group, and in the same formula they may be the same or different from each other. c (where * represents a hydrogen atom, a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, and * represents a bond.)

[0014] Such metal-containing film-forming compounds have a polydentate ligand containing one or more of the crosslinking groups shown in (a-1) to (a-4) and (b-1) to (b-4). When used in a metal-containing film-forming composition, it is possible to provide a metal-containing film-forming material with low volume shrinkage during baking and excellent planarization / embedding properties even after high-temperature baking.

[0015] Furthermore, in the present invention, it is preferable that the ligand derived from the compound represented by the general formulas (1-A) to (1-D) contains one or more structures selected from aromatic rings, heteroaromatic rings, and alicyclic structures.

[0016] Such metal compounds can improve the heat resistance of the metal-containing film-forming compound, and when used in a metal-containing film-forming composition, they can provide a metal-containing film-forming material that exhibits superior planarization / embedding properties.

[0017] Furthermore, in the present invention, it is preferable that the metal-containing film-forming compound further contains a ligand derived from a silicon compound represented by the following general formula (2). [ka] (In general formula (2), R 3A , R 3B and R 3CThis includes an organic group having 1 to 30 carbon atoms having a crosslinking group in any of the structures shown by the following general formulas (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a carbon number 6 (It is one of the organic groups selected from approximately 20 aryl groups.) [ka] (In general formulas (c-1) to (c-3), R'3 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.)

[0018] The stability of the metal compound in solution can be improved by further including a ligand derived from the silicon compound represented by the general formula (2) above in the aforementioned compound. Furthermore, if the silicon compound contains an organic group having 1 to 30 carbon atoms having a crosslinking group of any of the structures represented by the general formulas (c-1) to (c-3) above, it becomes possible to achieve a high degree of balance between the thermal fluidity and thermosetting properties of the 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 material that exhibits superior planarization / embedding properties.

[0019] Furthermore, the present invention provides a metal-containing film-forming composition used in semiconductor manufacturing, which contains (A) the metal-containing film-forming compound and (B) the organic solvent described above.

[0020] 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 material that has superior dry etching resistance compared to conventional resist underlayer materials, as well as advanced embedding / planarization characteristics compared to conventional resist underlayer materials.

[0021] In this case, it is preferable that the metal-containing film-forming composition further contains one or more of (C) a crosslinking agent, (E) a surfactant, and (F) an acid generator.

[0022] 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 / planarization properties.

[0023] Furthermore, in the present invention, it is preferable that the (B) organic solvent contains one or more organic solvents having a boiling point of 180°C or higher as (B1) high-boiling point solvent.

[0024] 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 / planarization properties.

[0025] Furthermore, in the present invention, it is preferable that the metal-containing film-forming composition further contains (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less.

[0026] In this case, it is preferable that the (G) metal oxide nanoparticles are selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles.

[0027] By using such metal oxide nanoparticles, it is possible to easily increase the metal content in the composition, thereby further improving the dry etching resistance of the metal-containing film-forming composition.

[0028] Furthermore, in the present invention, it is preferable that 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 (3). [ka] (In general formula (3), * represents a 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.)

[0029] By imparting heat resistance and thermal fluidity to the compound for forming the metal-containing film by adding a fluidity promoter (BP), the composition for forming the metal-containing film further has advanced embedding / planarization characteristics.

[0030] At this time, it is preferable that the fluidity promoter (BP) has at least one constitutional unit represented by the following general formulas (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0031] A metal-containing film-forming composition containing a flow promoter (BP) having at least one of the constituent units shown in (BP-1) to (BP-5) above will be a metal-containing film-forming composition with superior embedding / planarization properties.

[0032] Furthermore, the present invention provides 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 above-described metal-containing film-forming composition 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 having the following characteristics.

[0033] The pattern formation method using the two-layer resist process described above allows for the formation of fine patterns on the workpiece (workpiece substrate).

[0034] Furthermore, the present invention provides 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 above-described metal-containing film-forming composition onto a substrate to be processed and then heat-treating it, (II-2) A step of forming a silicon-containing resist interlayer on the metal-containing film, (II-3) A step of forming a resist upper layer film on the silicon-containing 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 silicon-containing 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 silicon-containing 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 having the following characteristics.

[0035] The pattern formation method using the above three-layer resist process makes it possible to form fine patterns on a workpiece with high precision.

[0036] Furthermore, the present invention provides 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 above-described metal-containing film-forming composition 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 having the following characteristics.

[0037] 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.

[0038] In this case, it is preferable that the inorganic hard mask interlayer is formed by CVD or ALD.

[0039] When the above inorganic hard mask interlayer is formed by CVD or ALD, fine patterns can be formed on the workpiece with higher precision.

[0040] Furthermore, the present invention provides 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 above-described metal-containing film-forming composition onto a substrate to be processed and then heat-treating it. (IV-2) A step of forming a resist underlayer film on the metal-containing film, (IV-3) A step of forming a silicon-containing 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, (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 the 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 the resist underlayer film by dry etching, using the silicon-containing resist interlayer film or inorganic hard mask interlayer film on which the pattern has been transferred as a mask. (IV-8) The above The pattern was transferred. A step of transferring a pattern to the metal-containing film by dry etching using the resist underlayer film 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. The present invention provides a pattern forming method having the following characteristics.

[0041] The pattern formation method using the multilayer resist process described above allows for the formation of fine patterns on a workpiece with high precision.

[0042] Furthermore, the present invention provides 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 described above, 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 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 inorganic 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 having the following characteristics.

[0043] 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]

[0044] As described above, the metal-containing film-forming compound of the present invention has a polydentate ligand containing one or more crosslinking groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4). Therefore, when used in a metal-containing film-forming composition, it is possible to provide a metal-containing film-forming material with small volume shrinkage during baking and excellent planarization / embedding properties even after high-temperature baking.

[0045] In particular, in the fine patterning process using the multilayer resist method in semiconductor device manufacturing processes, it is possible to embed the pattern without producing defects such as voids or peeling, even on workpiece substrates that have areas that are difficult to embed / planarize, such as densely packed areas of high aspect ratio fine pattern structures represented by miniaturized DRAM memory. Furthermore, because it has superior dry etching resistance compared to conventional coated resist underlayer materials, it is possible to form fine patterns on the workpiece with even greater precision compared to resist underlayer films. [Brief explanation of the drawing]

[0046] [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]

[0047] 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-forming composition with excellent embedding properties and flatness, a metal-containing film-forming compound useful for the composition, and a pattern formation method using the composition, which can be used to form a resist underlayer film that can transfer a resist pattern to the substrate with higher precision.

[0048] 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 substrate after high-temperature baking and flatten it. The inventors hypothesized that if an organic group with excellent heat resistance properties were present, rapid volume shrinkage during baking could be reduced and thermal fluidity could be improved, making it possible to fill in steps in the 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.

[0049] The inventors of the present invention conducted further intensive studies and discovered that a metal-containing film-forming compound containing a polydentate ligand which includes one or more crosslinking groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4) exhibits excellent thermosetting properties, thereby reducing rapid volume shrinkage during baking, and also has good thermal fluidity, enabling the realization of advanced embedding / planarization characteristics. This led to the completion of the present invention.

[0050] In other words, the present invention relates to a metal-containing film-forming compound used in a metal-containing film-forming composition, The aforementioned metal-containing film-forming compound is a metal-containing film-forming compound that contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and one or more ligands derived from compounds represented by the following general formulas (1-A) to (1-D). [ka] (In general formulas (1-A) to (1-D), R1 to R3 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4). R4 to R5 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4). R6 to R9 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4). 10 R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms. Compounds of general formulas (1-A) to (1-D) contain one or more bridging groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4). In general formula (1-B), R4 and R5 may be bonded to each other, forming an unsaturated or saturated ring structure. [ka] (In general formulas (a-1) to (a-4), Ra is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [ka] (In general formulas (b-1) to (b-4), R' b R' is a hydrogen atom or a methyl group, and in the same formula they may be the same or different from each other. c (where * represents a hydrogen atom, a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, and * represents a bond.)

[0051] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0052] <Compounds for forming metal-containing films> The metal-containing film-forming compound of the present invention is a metal-containing film-forming compound that contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and one or more ligands derived from compounds represented by the following general formulas (1-A) to (1-D). [ka] (In general formulas (1-A) to (1-D), R1 to R3 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4). R4 to R5 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4). R6 to R9 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4). 10 R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms. Compounds of general formulas (1-A) to (1-D) contain one or more bridging groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4). In general formula (1-B), R4 and R5 may be bonded to each other, forming an unsaturated or saturated ring structure. [ka] (In general formulas (a-1) to (a-4), Ra is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [ka] (In general formulas (b-1) to (b-4), R' b R' is a hydrogen atom or a methyl group, and in the same formula they may be the same or different from each other. c (where * represents a hydrogen atom, a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, and * represents a bond.)

[0053] In the above general formula (1-A), R1 to R3 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the above general formulas (a-1) to (a-4) and (b-1) to (b-4). R1 ​​and R3 are preferably monovalent organic groups having 1 to 20 carbon atoms, which contain an alkyl group having 1 to 10 carbon atoms or a bridging group represented by the above general formulas (a-1) to (a-4) and (b-1) to (b-4). R2 is preferably a monovalent organic group having 1 to 20 carbon atoms, which contains a hydrogen atom or a bridging group represented by the above general formulas (a-1) to (a-4) and (b-1) to (b-4).

[0054] In the above general formula (1-B), R4 to R5 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the above general formulas (a-1) to (a-4). Preferably, R4 is a hydrogen atom, R5 is a monovalent organic group having 1 to 20 carbon atoms containing a bridging group represented by the above general formulas (a-1) to (a-4), or the structure is as shown in the following formula. [ka] (In the formula, R5' is a monovalent organic group having 1 to 20 carbon atoms that contains the bridging group shown in the general formulas (a-1) to (a-4) above.)

[0055] In the above general formulas (1-C) to (1-D), R6 to R9 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the above general formulas (a-1) to (a-4) and (b-1) to (b-4). R6 and R8 are preferably hydrogen atoms, and R7 and R9 are preferably monovalent organic groups having 1 to 20 carbon atoms, which contain a bridging group represented by the above general formulas (a-1) to (a-4) and (b-1) to (b-4).

[0056] In the above general formula (1-C), R 10 This is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, with a hydrogen atom or a methyl group being preferred.

[0057] In the above general formula (1-D), Y is a divalent organic group having 1 to 10 carbon atoms, preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 5 carbon atoms from the viewpoint of raw material availability, even more preferably a methylene group or an ethylene group, and particularly preferably an ethylene group.

[0058] In the above general formulas (b-1) and (b-3), R' b R' is a hydrogen atom or a methyl group, and in the same formula they may be the same or different from each other, in the above general formulas (b-3) and (b-4), c R' is a hydrogen atom, a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. From the viewpoint of thermosetting and etching resistance, R' b , R' c Preferably, both are hydrogen atoms.

[0059] Among the structures of the general formulas (b-1) to (b-4) above, the following structures are examples of more preferred structures, but are not limited to these. From the viewpoint of thermosetting properties, the structures of the following formulas (Wa) or (Wb) are particularly preferred. [ka]

[0060] If the structure is of the above formula (Wa) or (Wb), it will have more crosslinking groups, resulting in a metal-containing film with superior thermosetting properties. When this is used in a composition for forming metal-containing films, it is possible to reduce volume shrinkage during high-temperature baking and provide a material for forming metal-containing films with excellent embedding / planarization properties.

[0061] Since the compounds represented by the above general formulas (1-A) to (1-D) contain one or more crosslinking groups represented by the above general formulas (a-1) to (a-4) and (b-1) to (b-4), when a metal-containing film-forming compound containing one or more polydentate ligands derived therefrom is used in a metal-containing film-forming composition, volume shrinkage during high-temperature baking can be reduced, and a metal-containing film-forming material with excellent embedding / planarization properties can be provided.

[0062] The following compounds are examples of ligand structures derived from the compound represented by the above general formula (1-A), but the present invention is not limited to these. [ka] (In the above formula, X1 and X2 represent hydrocarbon groups having 1 to 20 carbon atoms or alkoxy groups having 1 to 20 carbon atoms.)

[0063] [ka] (In the above formula, X1 and X2 represent hydrocarbon groups having 1 to 20 carbon atoms or alkoxy groups having 1 to 20 carbon atoms.)

[0064] [ka] (In the above formula, R 2 X1 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, while X1 and X2 represent a hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms.

[0065] [ka] (In the above formula, R' c X1 is a hydrogen atom, a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, while X1 and X2 represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

[0066] The following compounds are examples of ligand structures derived from the compound represented by the above general formula (1-B), but the present invention is not limited to these. [ka] (In the above formula, R d (This represents a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms.)

[0067] [ka]

[0068] The following compounds are examples of ligand structures derived from the compound represented by the above general formula (1-C), but the present invention is not limited to these. [ka] (In the above formula, X1 and X2 represent hydrocarbon groups having 1 to 20 carbon atoms or alkoxy groups having 1 to 20 carbon atoms.)

[0069] [ka] (In the above formula, X1 and X2 represent hydrocarbon groups having 1 to 20 carbon atoms or alkoxy groups having 1 to 20 carbon atoms.)

[0070] [ka] (In the above formula, R' c X1 is a hydrogen atom, a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, while X1 and X2 represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

[0071] The following compounds are examples of ligand structures derived from the compound represented by the above general formula (1-D), but the present invention is not limited to these. [ka] (In the above formula, Y is a divalent organic group having 1 to 10 carbon atoms.)

[0072] [ka] (In the above formula, Y is a divalent organic group having 1 to 10 carbon atoms.)

[0073] From the viewpoint of heat resistance, it is preferable that the ligand derived from the compound represented by the above general formulas (1-A) to (1-D) contains one or more structures selected from aromatic rings, heteroaromatic rings, and alicyclic structures.

[0074] By including one or more structures selected from aromatic rings, heteroaromatic rings, and alicyclic structures in the above ligand, the heat resistance of the metal-containing film-forming compound is improved, and a metal-containing film with excellent embedding properties can be formed.

[0075] A metal-containing film-forming compound is preferred in which the aforementioned metal-containing film-forming compound further contains a ligand derived from a silicon compound represented by the following general formula (2). [ka] (In general formula (2), R 3A , R 3B and R 3C This includes an organic group having 1 to 30 carbon atoms having a crosslinking group in any of the structures shown by the following general formulas (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a carbon number 6 (It is one of the organic groups selected from approximately 20 aryl groups.) [ka] (In general formulas (c-1) to (c-3), R'3 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.)

[0076] In the above general formula (2), R 3A , R 3B and R 3C This includes an organic group having 1 to 30 carbon atoms having a crosslinking group in any of the structures shown in the general formulas (c-1) to (c-3) above, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a carbon number 6 The organic group is one of the aryl groups selected from ~20, and is more preferably an organic group having 1 to 30 carbon atoms or an unsubstituted alkyl group having 1 to 10 carbon atoms having a crosslinking group in any of the structures represented by the general formulas (c-1) to (c-3) above. Among the unsubstituted alkyl groups having 1 to 10 carbon atoms, the methyl group or the ethyl group is more preferred.

[0077] In the general formulas (c-1) to (c-3) above, R'3 is independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and q is independently 0 or 1.

[0078] The storage stability of the metal-containing film-forming compound can be improved by including a ligand derived from the silicon compound represented by the general formula (2) above in the metal-containing film-forming compound.

[0079] From the viewpoint of thermosetting properties, it is more preferable that the ligand derived from the silicon compound represented by the above general formula (2) has one of the structures represented by the following general formula (2A). [ka] (In the above general formula (2A), R 3D and R 3E (where R'3 is an organic group selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms, with R'3 being the same as above and s being 1 to 10.)

[0080] In the above general formula (2A), R 3D and R3E From the perspective of raw material availability, it is more preferable that it be a methyl group.

[0081] In the aforementioned metal-containing film-forming compound, if both the ligand derived from the compound represented by the general formulas (1-A) to (1-D) and the ligand derived from the silicon compound contain crosslinking groups, the thermosetting properties of the metal-containing film-forming compound can be further improved. When this is used in a metal-containing film-forming composition, it becomes possible to form a metal-containing film with excellent embedding / planarization properties.

[0082] The above-mentioned metal-containing film-forming compound can be modified with ligands derived from multiple compounds represented by the above general formulas (1-A) to (1-D) with different structures, or ligands derived from silicon compounds, without any problems, and can be appropriately adjusted according to the required properties. Furthermore, the above-mentioned compound may have ligands other than polydentate ligands and ligands derived from silicon compounds. For example, it may contain ligands derived from alkyl groups having 1 to 10 carbon atoms.

[0083] In the above-mentioned metal-containing film-forming compound, the content of ligands derived from the compounds represented by the above general formulas (1-A) to (1-D) is preferably 10 mol% to 90 mol%, and more preferably 20 mol% to 80 mol%, of the total amount of ligands coordinating to the metal atom. The content of ligands derived from silicon compounds is preferably 10 mol% to 90 mol%, and more preferably 20 mol% to 80 mol%, of the total amount of ligands coordinating to the metal atom. Ligands other than those derived from the compounds represented by the above general formulas (1-A) to (1-D) and those derived from silicon compounds, such as ligands derived from alkyl groups having 1 to 10 carbon atoms, are preferably 0 mol% to 50 mol%, and more preferably 0 mol% to 20 mol%, of the total amount of ligands coordinating to the metal atom.

[0084] The metal-containing film-forming compound of the present invention only needs to contain a ligand derived from the compound represented by the general formula (1-A) to (1-D) above, which contains any of the crosslinking groups of the general formulas (a-1) to (a-4) and (b-1) to (b-4). The synthesis method is not particularly limited, but for example, the metal-containing film-forming compound can be produced from their metal alkoxides or acetylacetonates (acac). Do Alternatively, it can be obtained by reacting an acac metal with a polydentate ligand. Do Alternatively, the acac metal may be subjected to hydrolysis and condensation, followed by a reaction with a ligand derived from the compound represented by the general formulas (1-A) to (1-D) above, or an alkoxy Do Alternatively, the acac metal may be reacted with a ligand derived from the compound represented by the general formulas (1-A) to (1-D) above, followed by a hydrolysis condensation reaction. If controlling the hydrolysis condensation is difficult, the reaction may be carried out in a non-aqueous environment with a ligand derived from the compound represented by the general formulas (1-A) to (1-D) above. These should be appropriately adjusted according to the properties of the metal-containing film-forming compound and the properties required for the metal-containing film. When a ligand derived from a silicon compound is used, alkoxy Do Alternatively, it is preferable to react the acac metal with a silicon compound and then react it with a ligand derived from the compound represented by the general formulas (1-A) to (1-D) above. Furthermore, the metal compound containing the ligand derived from the compound represented by the general formulas (1-A) to (1-D) above and the ligand derived from the silicon compound may be subjected to hydrolysis condensation.

[0085] Any C1-C10 alkyl group that can constitute some of the ligands in the above-mentioned metal-containing film-forming compound is obtained as a result of using the remaining alkoxide or alkoxide metal precursor, or as a result of using a C1-C10 alcohol as an additional reagent in the preparation of the above-mentioned metal-containing film-forming compound. The reaction is carried out in a solvent capable of dissolving the alkoxide or acac precursor and other reagents. Typical solvents and solvent mixtures include those containing ester, ether, or alcohol functional groups, for example, a mixture of 70 / 30 by volume of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME). Other solvents that can be used include butanediol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, 1-butanol, 2-butanol, 2-methyl-1-butanol Examples include lopanol, 4-methyl-2-pentanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diamyl ether, isoamyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, and cyclopentyl methyl ether.

[0086] <Metal-containing film forming composition> Furthermore, the present invention provides a metal-containing film-forming composition used in semiconductor manufacturing, which contains (A) the metal-containing film-forming compound and (B) an organic solvent.

[0087] 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-forming material that has superior dry etching resistance compared to conventional resist underlayer film materials, as well as advanced embedding / planarization characteristics.

[0088] 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).

[0089] <(B) Organic solvents> The (B) organic solvent that can be used in the metal-containing film-forming composition of the present invention is not particularly limited as long as it dissolves or disperses the (A) metal-containing film-forming compound described above, and, if included, the (C) crosslinking agent, (E) surfactant, (F) acid generator, (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less, and other additives.

[0090] Specifically, in Japanese Patent Publication No. 2007-199653

[0091] ~

[0092] The organic solvents described in the paragraph may be added. More specifically, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and γ-butyrolactone, or a mixture containing one or more of these, are preferably used.

[0091] The amount of organic solvent blended is preferably in the range of 200 to 10,000 parts by mass, more preferably 250 to 5,000 parts by mass, per 100 parts by mass of (A) the metal-containing film-forming compound.

[0092] The metal-containing film-forming composition may optionally contain additives such as (C) a crosslinking agent, (E) a surfactant, (F) an acid generator, and (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less. That is, it is preferable that the metal-containing film-forming composition further contains one or more of (C) a crosslinking agent, (E) a surfactant, and (F) an acid generator, and it is preferable that the metal-containing film-forming composition further contains (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less. The following describes the 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.

[0093] <(B1) High boiling point solvent> In the metal-containing film-forming composition of the present invention, the (B) organic solvent may be used as a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher ((B1) high-boiling point solvents). That is, it is preferable that the (B) organic solvent contains one or more organic solvents having a boiling point of 180°C or higher as the (B1) high-boiling point solvent.

[0094] (B1) As for the high boiling point solvent, there are no particular restrictions on hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc., as long as it can dissolve or disperse each component of the metal-containing film-forming composition of the present invention, but specific examples 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 include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate, which may be used individually or in combination.

[0095] (B1) The high-boiling point solvent can be appropriately selected from the above, for example, according to the temperature at which the metal-containing film-forming composition of the present invention is heat-treated. The boiling point of the high-boiling point solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. With such a boiling point, there is no risk of excessive volatilization during baking (heat treatment), so sufficient thermal fluidity can be obtained during film formation, and it is thought that a metal-containing film with excellent embedding / planarization properties can be formed. Furthermore, with such a boiling point, there is no risk of residual solvent in the film after baking without volatilization, so there is no risk of adverse effects on film properties such as etching resistance.

[0096] Furthermore, when using (B1) a high-boiling point solvent, the amount blended is preferably 1 to 30 parts by mass per 100 parts by mass of an organic solvent with a boiling point of less than 180°C. Such a blending amount is preferable because it provides sufficient thermal fluidity during baking, does not remain in the film, and does not lead to deterioration of film properties such as etching resistance.

[0097] [(C) Crosslinking agent] Furthermore, the metal-containing film-forming composition of the present invention may also contain a (C) crosslinking agent in order to enhance the curability of the metal-containing film-forming compound and further suppress intermixing with the resist upper layer film. The (C) crosslinking agent is not particularly limited, and various known types of crosslinking agents 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 (for example, 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.

[0098] Examples of melamine-based crosslinking agents include hexamethoxymethylated melamine, hexasubtoxicmethylated melamine, alkoxy and / or hydroxy-substituted derivatives thereof, and partially self-condensed derivatives thereof. As an example of an acrylate-based crosslinking agent, dipentaerythritol hexaacrylate can be cited. Examples of glycoluryl crosslinking agents include tetramethoxymethylated glycoluryl, tetrabutoxymethylated glycoluryl, their alkoxy and / or hydroxy substituted derivatives, and their partial self-condensates. Examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensed derivatives. Examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy-substituted derivatives, and partially self-condensed derivatives thereof. A specific example of a β-hydroxyalkylamide crosslinking agent is N,N,N',N'-tetra(2-hydroxyethyl)adipamide. Examples of isocyanurate-based crosslinking agents include triglycidyl isocyanurate and triallyl isocyanurate. Examples of aziridine-based crosslinking agents include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Specifically, oxazoline crosslinking agents include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline) and 2,2'-isopropylidenebis(4-phenyl-2-oxazoline). 、2 Examples include copolymers of 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. 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.

[0099] Examples of polynuclear phenolic crosslinking agents include the compound represented by the following general formula (XL-1). [ka] (In the general formula (XL-1), Q is a single bond or a q'-valent hydrocarbon group having 1 to 20 carbon atoms. R''3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. q' is an integer from 1 to 5.)

[0100] Q is a single bond or a q'-valent hydrocarbon group having 1 to 20 carbon atoms. q' is an integer from 1 to 5, more preferably 2 or 3. Specific examples of Q include groups obtained by removing q' 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. R''3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosanyl groups, with hydrogen atoms or methyl groups being preferred.

[0101] As examples of compounds represented by the above general formula (XL-1), the following compounds can be specifically exemplified. Among these, triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and hexamethoxymethylated tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the viewpoint of improving the curability and uniformity of the metal-containing film. R"3 is the same as above. [ka]

[0102] [ka]

[0103] <(E) Surfactants> The metal-containing film-forming composition of the present invention may contain (E) surfactants to improve the coatability in spin coating. As the (E) surfactant, for example, those described in paragraphs

[0142] to

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

[0104] <(F) Acid Generator> In the metal-containing film-forming composition of the present invention, an acid generator (F) can be added to further promote the curing reaction of the metal-containing film-forming compound (A). The acid generator (F) can be one that generates acid by thermal decomposition or one that generates acid by light irradiation, and either type can be added. Specifically, the materials described in paragraphs

[0061] to

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

[0105] The above (F) acid generating agent can be used individually or in combination of two or more types. When adding the (F) acid generating agent, the amount to be added is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the above (A) metal-containing film-forming compound.

[0106] <(G) Metal oxide nanoparticles> Furthermore, the metal-containing film-forming composition of the present invention may contain (G) metal oxide nanoparticles 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.

[0107] By selecting the above-mentioned metal oxide nanoparticles, it is possible to form a metal-containing film with superior dry etching resistance.

[0108] The (G) metal oxide nanoparticles are preferably those having an average primary particle size of 100 nm or less, more preferably an average primary particle size of 50 nm or less, even more preferably an average primary particle size of 30 nm or less, and particularly preferably an average primary particle size of 15 nm or less. The average primary particle size of the (G) 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).

[0109] 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.

[0110] (G) When metal oxide nanoparticles are added, the amount added is preferably 5 to 50 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the metal-containing film-forming compound (A) described above.

[0111] <Other additives> 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 formulas (DP1) and (DP1a).

[0112] [ka] (In the general formula (DP1), R'6 is a hydrogen atom or a monovalent saturated or unsaturated organic group having 1 to 30 carbon atoms, which may be substituted. Y'' is a divalent saturated or unsaturated organic group having 2 to 30 carbon atoms.)

[0113] [ka] (In general formula (DP1a), 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.)

[0114] <Flow enhancer (BP)> Furthermore, the metal-containing film-forming composition of the present invention may contain a flow-promoting agent (BP) as an additive to impart embedding / planarization properties. The flow-promoting agent (BP) preferably has an organic group and an aromatic ring represented by the following general formula (3). That is, it is preferable that the metal-containing film-forming composition further contains a flow-promoting agent (BP) having an organic group and an aromatic ring represented by the following general formula (3). [ka] (In general formula (3), * represents a 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.)

[0115] The fluidity enhancer (BP) having the organic group of general formula (3) above can impart thermal fluidity and thermosetting properties to the metal-containing film-forming compound. Furthermore, the fluidity enhancer (BP) having an aromatic ring can mitigate the deterioration of the dry etching resistance of the metal-containing film-forming compound.

[0116] The aforementioned fluidity enhancer (BP) preferably has at least one constituent unit represented by the following general formulas (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5). (Component units: BP-1, BP-2, and BP-3) [ka] (In 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. a is the group represented by formula (4) below. Y' is the group represented by 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 general formula (BP-3), Z1 is the base shown in the general formula (6) below, R a This is the group represented by formula (4) below. n4 is 0 or 1, n5 is 1 or 2, and V independently represents a hydrogen atom or a linkage. [ka] (In formula (4), * represents the bond with the oxygen atom.) [ka] (In equation (5), * represents a bond.) [ka] (In general formula (6), W1, W2, Y', and n1 are the same as described above.)

[0117] Resins having the constituent units shown by 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.

[0118] The resin having the constituent units represented by the above general formulas (BP-1), (BP-2), and (BP-3) may be the compound represented by the following general formulas (bp-1), (bp-2), and / or (bp-3). [ka] (In general formulas (bp-1) and (bp-2), W1, W2, R a (Y', n1, and n2 are the same as above.)

[0119] In the above general formulas (bp-1) and (bp-2), W1, W2, R a Y', n1, and n2 are as explained above for general formulas (BP-1) and (BP-2).

[0120] [ka] (In general formula (bp-3), Z1, R a n4 and n5 are the same as above.

[0121] In the above general formula (bp-3), Z1, R a n4 and n5 are as explained above for the general formula (BP-3).

[0122] Examples of resins having the constituent units represented by the above general formulas (bp-1), (bp-2), and / or (bp-3) include, but are not limited to, the following compounds. [ka] (In the formula, R a (This is the same as above.)

[0123] The above resins (bp-1), (bp-2), and (bp-3) preferably have a ratio Mw / Mn (i.e., degree of dispersion) of weight-average molecular weight Mw to number-average molecular weight Mn, measured by gel permeation chromatography in terms of polystyrene, within the range of 1.00 ≤ Mw / Mn ≤ 1.25, and more preferably 1.00 ≤ Mw / Mn ≤ 1.10.

[0124] Compounds having a dispersion degree within this range will exhibit even better thermal fluidity in the metal-containing film-forming composition, thus providing a metal-containing film-forming composition with superior embedding and planarization properties when incorporated into a material.

[0125] The resin having the constituent units represented by 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), (bp-5), and / or (bp-6). [ka] (In general formulas (bp-4) and (bp-5), W1, W2, R a Y', n1, and n2 are the same as described above, and L is a divalent organic group with 1 to 40 carbon atoms.

[0126] In the above general formulas (bp-4) and (bp-5), W1, W2, R a Y', n1, and n2 are as explained above for general formulas (BP-1) and (BP-2).

[0127] [ka] (In general formula (bp-6), Z1, R a n4 and n5 are the same as described above, and L is a divalent organic group with 1 to 40 carbon atoms.

[0128] In the above general formula (bp-6), Z1, R a n4 and n5 are as explained above for the general formula (BP-3).

[0129] These polymers are obtained using compounds represented by 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.

[0130] The linking group L that constitutes 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. [ka]

[0131] Furthermore, it is preferable that the linking group L of the polymer is of the following general formula (10). [ka] (In general formula (10), R'1 is an organic group containing a hydrogen atom or an aromatic ring with 6 to 20 carbon atoms, and the dashed lines represent bonding.)

[0132] The following are some specific examples of the above general formula (10), and among them, a methylene group, i.e., R'1 being a hydrogen atom, is preferred due to the ease of obtaining the raw materials. [ka]

[0133] Furthermore, it is preferable that the weight average molecular weight (Mw) in terms of polystyrene of the polymer having the repeating structural units represented by the general formulas (bp-4), (bp-5) and (bp-6) by gel permeation chromatography is 1,000 to 12,000, and more preferably Mw is 2,000 to 10,000.

[0134] Within such a molecular weight range, solubility in an organic solvent can be ensured, and sublimates generated during baking can be suppressed. In addition, since the thermal fluidity of the composition for forming a metal-containing film becomes good, when blended with a material, a composition for forming a metal-containing film with more excellent embedding / flattening characteristics can be provided.

[0135] (Structural unit: BP-4) [Chemical formula] (In the general formula (BP-4), m3 and m4 each represent 1 or 2, and Z is either a single bond or a structure represented by the following general formula (7). R x is either a structure represented by the following general formula (8).) [Chemical formula] (In the general formula (7), * represents a bond, l represents an integer from 0 to 3, and R a ~R f each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be fluorine-substituted, a phenyl group, or a phenylethyl group, and R a and R b may combine to form a cyclic compound.) [Chemical formula] (In the general formula (8), * represents the bonding site to the aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9).) [Chemical formula] (In general formula (9), * represents the bonding site to the carbonyl group, R i R is the group shown in formula (4) above. 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 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, each an integer from 0 to 7. However, n3 + n4 is between 0 and 7. n5 represents 0 to 2.

[0136] In the above general formula (BP-4), m3 and m4 represent 1 or 2, and Z is either a single bond or one of the structures shown in the above general formula (7). x This is one of the structures shown in the general formula (8) above.

[0137] From the viewpoint of dry etching resistance and heat resistance, it is preferable that Z in the above general formula (BP-4) is either a single bond or a structure represented by the following general formula (4A). [ka] (In general formula (4A), * represents a bond, and l is the same as in general formula (7) above.)

[0138] In the above general formula (8), * represents a bonding site to an aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or the structure shown in the above general formula (9). 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 shown in the above general formula (9) is preferred for Q1.

[0139] In the above general formula (9), * represents the bonding site to the carbonyl group, and R i R is the group shown in formula (4) above. jn represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, each representing an integer from 0 to 7. However, n3 + n4 is between 0 and 7. n5 represents 0 to 2.

[0140] Compounds containing the constituent units 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. As a result, metal-containing film-forming compositions containing these compounds have excellent heat resistance. Furthermore, as shown in the above general formula (7), the linking group Z can be appropriately selected from various linking groups to match the desired performance. In particular, by introducing the structure shown in the above general formula (4A) as Z, heat resistance / etching resistance can be imparted without impairing film-forming properties. In addition, the highly flexible terminal portion R x Because 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. 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 with these compounds added can achieve a high level of both embedding / planarization properties and heat resistance, and thick films can be formed according to the required properties.

[0141] (Component unit: BP-5) [ka] (In general formula (BP-5), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X is a divalent organic group having 1 to 30 carbon atoms, and R ais the base shown in equation (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 0 or 1.

[0142] In the above general formula (BP-5), the divalent organic group having 1 to 30 carbon atoms represented by X 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.

[0143] Examples of the alkanediyloxy group represented by X above include a group formed by combining the alkanediyl group with an oxygen atom. Similarly, examples of the cycloalkanediyloxy group represented by X above include a group formed by combining the cycloalkanediyl group with an oxygen atom.

[0144] 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.

[0145] Examples of the organic group represented by X above include groups represented by the following formulae.

Chemical formula

[0146] From the perspective of raw material availability, the organic group represented by X above preferably includes a methylene group.

[0147] Specific examples of the resin having the structural unit represented by the general formula (BP-5) above include the following.

Chemical formula

[0148]

Chemical formula

[0149] Since the polymer containing the structural unit represented by the general formula (BP-5) above has a structure in which aromatic rings are connected by an organic group X, it has a high carbon density. Therefore, the metal-containing film-forming composition containing these compounds exhibits high dry etching resistance and excellent heat resistance. Furthermore, since the organic group having the structure represented by the above formula (4) that contributes to the improvement of thermal fluidity is directly bonded to the aromatic ring, which is the mother nucleus structure of the resin, through an oxygen atom, the metal-containing film-forming composition added with these polymers can achieve high-dimensional compatibility between the embedding / flattening characteristics and the heat resistance / etching resistance. In addition, since the aromatic ring structure of the mother nucleus is not too rigid and forms a repeating structure through the organic group X as a linking group, it is possible to form a metal-containing film without generating defects such as cracks.

[0150] 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 (A).

[0151] The amount of fluidity enhancer (BP) 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 fluidity enhancer (BP). If you want to tolerate some degradation of dry etching resistance and further improve the embedding / planarization characteristics, increase the proportion of fluidity enhancer (BP).

[0152] <Method for forming a resist underlayer film and a packing film> The present invention provides a method for forming a packing film that functions as a resist underlayer film for multilayer resist films used in lithography or as a planarization film for semiconductor manufacturing, using the above-described metal-containing film-forming composition.

[0153] 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.

[0154] 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 is coated onto a workpiece substrate by a spin coating method or the like, as described above, and the metal-containing film is formed as a resist underlayer film by firing and curing the metal-containing film-forming composition in an atmosphere with an oxygen concentration of 0.1 volume% to 21 volume%.

[0155] 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 1,000 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.

[0156] The method for forming the packing film can be the same as the method for forming the resist underlayer film described above.

[0157] <Method for forming patterns using a metal-containing film-forming composition> 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 two-layer resist process, (I-1) A step of forming a metal-containing film by applying the above-described metal-containing film-forming composition 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 having the following characteristics.

[0158] 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.

[0159] Furthermore, the present invention provides a method for forming a pattern on a workpiece substrate using a three-layer resist process with such a metal-containing film-forming composition, (II-1) A step of forming a metal-containing film by applying the above-described metal-containing film-forming composition onto a substrate to be processed and then heat-treating it, (II-2) A step of forming a silicon-containing resist interlayer on the metal-containing film, (II-3) A step of forming a resist upper layer film on the silicon-containing 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 silicon-containing 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 silicon-containing 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 having the following characteristics.

[0160] 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 such a metal-containing film-forming composition, a metal-containing film 3 is formed on a workpiece layer 2 on a workpiece substrate 1 using the above-mentioned metal-containing film-forming composition, as shown in Figure 1(A), a silicon-containing resist interlayer 4 is formed on the metal-containing film using a silicon-containing resist interlayer material, and a resist upper layer 5 is formed on the silicon-containing resist interlayer using a photoresist material. The present invention provides a pattern formation method in which, as shown in Figure 1(B), the exposed portion 6 of the resist upper layer film is pattern-exposed, and as shown in Figure 1(C), it is developed with a developer to form a resist upper layer film pattern 5a on the resist upper layer film, as shown in Figure 1(D), the silicon-containing resist interlayer film pattern 4a is transferred to the silicon-containing resist interlayer film by dry etching using the resist upper layer film on which the pattern has been formed as a mask, as shown in Figure 1(E), the metal-containing film pattern 3a is transferred to the metal-containing film by dry etching using the silicon-containing resist interlayer film on which the pattern has been transferred as a mask, and as shown in Figure 1(F), the workpiece layer on the workpiece substrate is processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern 2a on the workpiece substrate 1.

[0161] Since the silicon-containing resist interlayer in the above three-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 silicon-containing resist interlayer as a mask in the above three-layer resist process using an etching gas mainly composed of chlorine-based gases.

[0162] As the silicon-containing resist interlayer in the above three-layer resist process, a polysiloxane-based interlayer is also preferably used. 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.

[0163] In addition, the present invention provides a pattern formation method using a four-layer resist process with such a metal-containing film-forming composition, A metal-containing film is formed on the substrate to be processed using the above metal-containing film-forming composition. A silicon-containing resist interlayer is formed on the metal-containing film using a silicon-containing resist interlayer material. An organic anti-reflective film (BARC) or an adhesion film is formed on the silicon-containing resist interlayer. A resist upper layer film is formed on the BARC or the adhesion film using a photoresist material. After pattern exposure of the resist upper layer film, it is developed with a developer to form a pattern on the resist upper layer film. Using the resist upper layer film on which the pattern is formed as a mask, the pattern is transferred to the BARC or the adhesion film and the silicon-containing resist interlayer film by dry etching. Using the silicon-containing resist interlayer on which the pattern has been transferred as a mask, the pattern is transferred to the metal-containing film by dry etching. The present invention provides a pattern forming method comprising the step of processing a workpiece substrate using a metal-containing film on which the aforementioned pattern is formed as a mask to form a pattern on the workpiece substrate.

[0164] Alternatively, an inorganic hard mask interlayer may be formed instead of a silicon-containing resist interlayer, in which case at least, A metal-containing film is formed on a substrate using the metal-containing film-forming composition of the present invention. An inorganic hard mask interlayer, selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film, is formed on the aforementioned metal-containing film. A resist upper layer film is formed on the inorganic hard mask interlayer film using a photoresist composition, and a circuit pattern is formed on the resist upper layer film. The pattern is transferred to an inorganic hard mask interlayer using the resist upper layer film on which the aforementioned pattern is formed as a mask. The pattern is transferred to the metal-containing film using the inorganic hard mask interlayer on which the pattern is formed as a mask. Furthermore, by using the metal-containing film on which the pattern is formed as a mask to process the substrate and form a pattern on the substrate, a semiconductor device circuit pattern can be formed on the substrate.

[0165] The present invention provides 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 above-described metal-containing film-forming composition 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 having the following characteristics.

[0166] As described above, when forming an inorganic hard mask interlayer 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, 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 interlayer is preferably 5 to 200 nm, and more preferably 10 to 100 nm. Furthermore, as the inorganic hard mask interlayer, a SiON film with high anti-reflective properties 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 interlayer formed by CVD or ALD with a metal-containing film formed by rotary coating.

[0167] As described above, a photoresist film may be formed as a resist top layer on an inorganic hard mask interlayer, or an organic anti-reflective coating (BARC) or adhesion film may be formed on the inorganic hard mask interlayer 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 interlayer, 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.

[0168] In the pattern formation method described above, the resist upper layer film can be either positive or negative, 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.

[0169] When forming a photoresist upper layer film 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.

[0170] When a resist upper layer film is formed by vapor deposition using the CVD or ALD method, the photoresist composition is an EUV-sensitive metal oxide-containing film, the metal being 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., haloalkylSn, alkoxyalkylSn, or amidealkylSn). Some specific examples of suitable precursors include trimethyltin chloride, dimethyltin dichloride, methyltin trichloride, tris(dimethylamino)methyltin(IV), and (dimethylamino)trimethyltin(IV).

[0171] 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 6,000 mTorr. The flow rate of the metal oxide-containing film precursor liquid (e.g., organotin oxide precursor) may be 0.01 to 10 cm, and the gas flow rate (CO2, CO, Ar, N2) may be 100 to 10,000 sccm. The plasma power may be 200 to 1,000 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 2,000 Å.

[0172] 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.

[0173] 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.

[0174] Furthermore, it is preferable that the development method in the pattern formation method be alkaline development or development with an organic solvent.

[0175] 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 the inorganic hard mask interlayer is performed using a fluorocarbon gas with the resist upper layer pattern as a mask. This forms the silicon-containing resist interlayer pattern and the inorganic hard mask interlayer pattern.

[0176] Next, the obtained silicon-containing resist interlayer pattern or inorganic hard mask interlayer pattern is used as a mask to etch the metal-containing film. It is preferable to etch the metal-containing film using an etching gas mainly composed of chlorine-based gas.

[0177] The etching of the next substrate to be processed can also be carried out by conventional methods. For example, if the substrate to be processed is an SiO2, SiN, or silica-based low dielectric constant insulating film, etching is performed mainly 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.

[0178] The metal-containing films obtained using the metal-containing film-forming composition of the present invention have excellent etching resistance when these substrates are etched.

[0179] 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.

[0180] The pattern formation method using the metal-containing film-forming composition of the present invention preferably uses 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 metal-containing 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 highly preferable.

[0181] Furthermore, in the present invention, as a pattern formation method by a four-layer resist process using such a metal-containing film-forming composition, A metal-containing film is formed on the substrate to be processed using the above metal-containing film-forming composition. An organic underlayer film is formed on the metal-containing film using an organic resist underlayer film material. A silicon-containing resist interlayer is formed on the aforementioned organic underlayer using a silicon-containing resist interlayer material. If necessary, an organic anti-reflective coating (BARC) or an adhesion coating is formed on the silicon-containing resist interlayer. A resist upper layer film is formed on the silicon-containing resist interlayer film, on the BARC, or on the adhesion film using a photoresist material. After pattern exposure of the resist upper layer film, it is developed with a developer to form a pattern on the resist upper layer film. Using the resist upper layer film on which the pattern is formed as a mask, the pattern is transferred to the BARC or the adhesion film and the silicon-containing resist interlayer film by dry etching. Using the silicon-containing resist interlayer film on which the aforementioned pattern has been transferred as a mask, the pattern is transferred to the organic underlayer film by dry etching. Using the aforementioned organic underlayer film as a mask, a pattern is transferred to the metal-containing film. The present invention provides a pattern forming method comprising the step of processing a workpiece substrate using a metal-containing film on which the aforementioned pattern is formed as a mask to form a pattern on the workpiece substrate.

[0182] As organic resist underlayer materials that can be used for the above-mentioned organic underlayer, 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 resist underlayer materials for 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).

[0183] The above-mentioned organic underlayer film 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 film by a spin coating method or the like, it is desirable to bake it to evaporate the organic solvent. The bake temperature is preferably in the range of 80 to 400°C, and the bake time is preferably in the range of 10 to 300 seconds.

[0184] Instead of the organic underlayer film mentioned above, it is also possible to apply an organic hard mask formed by CVD or ALD.

[0185] 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.

[0186] Furthermore, the present invention provides a method for forming a pattern on a workpiece substrate using a four-layer resist process with such a metal-containing film-forming composition, (IV-1) A step of forming a metal-containing film by applying the above-described metal-containing film-forming composition onto a substrate to be processed and then heat-treating it. (IV-2) A step of forming a resist underlayer film on the metal-containing film, (IV-3) A step of forming a silicon-containing 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, (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 the 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 the resist underlayer film by dry etching, using the silicon-containing resist interlayer film or inorganic hard mask interlayer film on which the pattern has been transferred as a mask. (IV-8) The above The pattern was transferred. A step of transferring a pattern to the metal-containing film by dry etching using the resist underlayer film 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. The present invention provides a pattern forming method having the following characteristics.

[0187] <Tone-reversal pattern formation method using a metal-containing film-forming composition> Furthermore, the present invention provides a tone-reversal pattern formation method using such a metal-containing film-forming composition, which is a method for forming a pattern on a workpiece substrate, (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 described above, 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 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 inorganic 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 having the following characteristics.

[0188] 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, a resist underlayer film 7 is formed on a workpiece layer 2 on a workpiece substrate 1 as shown in Figure 2(G). 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 then formed on the resist interlayer film 4, or the combination of the inorganic hard mask interlayer film and the organic thin film, using a photoresist material.Next, as shown in Figure 2(H), the exposed portion 6 of the resist upper layer film is pattern-exposed, and then as shown in Figure 2(I), it is developed with a developer to form a resist upper layer film pattern 5a on the resist upper layer film. 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 resist interlayer film pattern 4a or the inorganic hard mask interlayer film pattern to the resist interlayer film, or the organic thin film and the inorganic hard mask interlayer film, by dry etching. As shown in Figure 2(K), the resist interlayer film or the inorganic hard mask interlayer film on which the pattern has been transferred is used as a mask to transfer the resist lower layer film pattern 7a to the resist lower layer film by dry etching. 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, between the resist lower layer film patterns 7a. The present invention provides a tone reversal pattern forming method comprising the steps of: filling the resist with the metal-containing film 8; as shown in Figure 2(M), etching back the metal-containing film covering the resist underlayer film on which the pattern is formed by a chemical stripper or dry etching to form an inverted metal-containing film pattern 8a; exposing the upper surface of the resist underlayer film on which the pattern is formed; as shown in Figure 2(N), removing the resist interlayer or inorganic hard mask interlayer remaining on the upper surface of the resist underlayer film pattern 7a by dry etching; as shown in Figure 2(O), removing the resist underlayer film on which the pattern is formed with the exposed surface by dry etching to form an inverted pattern of the original pattern on the metal-containing film; and as shown in Figure 2(P), processing the workpiece using the metal-containing film on which the inverted pattern is formed as a mask to form an inverted pattern 2b on the workpiece.

[0189] As described above, when forming a resist underlayer film on a substrate to be processed, the resist underlayer film can be formed using methods such as coating-type resist underlayer film materials, CVD, or ALD. Examples of coating-type resist underlayer materials include Japanese Patent Publication No. 2012-001687, Japanese Patent Publication No. 2012-077295, Japanese Patent Publication No. 2004-264710, Japanese Patent Publication No. 2005-043471, Japanese Patent Publication No. 2005-250434, Japanese Patent Publication No. 2007-293294, Japanese Patent Publication No. 2008-065303, Japanese Patent Publication No. 2004-205685, Japanese Patent Publication No. 2007-171895, Japanese Patent Publication No. 2009-014816, Japanese Patent Publication No. 2007-199653, Japanese Patent Publication No. 2008-274250, Japanese Patent Publication No. 2010-122656, and Japanese Patent Publication No. 2012 Examples of resins and compositions can be found in Japanese Patent Publication No. 214720, Japanese Patent Publication No. 2014-029435, International Publication No. 2012 / 077640, International Publication No. 2010 / 147155, International Publication No. 2012 / 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. 2019-044022, and others.

[0190] In the above tone inversion pattern formation method, 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 inorganic 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.

[0191] In the tone inversion pattern formation method described above, the resist underlayer pattern preferably has structures or steps with a height of 30 nm or more. As described above, the metal-containing film formation composition of the present invention has excellent embedding / planarization properties, so even if the workpiece has structures or steps (unevenness) with a height of 30 nm or more, a flat metal-containing film can be formed. The height of the structures or steps of the resist underlayer 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 pattern having a pattern of the above height, it is highly preferable to form the metal-containing film formation composition of the present invention and perform embedding / planarization, as this enables high-precision pattern inversion / transfer. Compared to resist underlayers using conventional coating-type resist underlayer materials, it has excellent dry etching resistance using fluorocarbon gases, so by inverting the resist underlayer pattern with the metal-containing film formation composition, a desired resist pattern can be formed on the workpiece with high precision. [Examples]

[0192] The present invention will be described in more detail below with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited thereto.

[0193] [Example of combination] The following synthesis examples used the organic group raw materials G: (G1) to (G18) and the silicon-containing organic group raw materials H: (H1) to (H5) shown below. The organic raw material group G: (G1) to (G18) is shown below. [ka]

[0194] The silicon-containing organic raw material group H:(H1)~(H5) is shown below. [ka]

[0195] The following metal compounds were used as the metal raw material 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) (M5):Ti(OBu)4:Tetrabutyl orthotitanate (Tokyo Chemical Industries, Ltd., B0742) (M6): Titanium(IV) diisopropoxybis(2,4-pentanedionate) (75% by mass isopropyl alcohol solution) (Tokyo Chemical Industries, Ltd., B3395)

[0196] [Synthesis Example 1] Synthesis of Metal-Containing Film-Forming Compound (A-1) Under a nitrogen atmosphere, 12.1 g of IPA solution containing 33.4 g of titanium tetraisopropoxide (M1) was stirred, and 24.2 g of IPA solution containing 1.6 g of deionized water was added dropwise over 2 hours at room temperature. 16.6 g of organic raw material group (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 (mass 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.

[0197] [Synthesis Examples 2-4] Synthesis of Metal-Containing Film-Forming Compounds (A-2)-(A-4) Except for using the above-mentioned metal raw material M and organic group raw material group G in the amounts shown in Table 1, the metal-containing film-forming compounds (A-2) to (A-4) shown in Table 1 were obtained under the same reaction conditions as in Synthesis Example 1. [Table 1]

[0198] [Synthesis Example 5] Synthesis of Metal-Containing Film-Forming Compound (A-5) Under a nitrogen atmosphere, 11.8 g of tetrabutyl orthotitanate (M5) was dissolved in 20.6 g of PGMEA / PGME (mass ratio 70 / 30) solution, and the reaction temperature was raised to 50°C while stirring. 6.5 g of silicon-containing organic raw material group (H1) was then 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 4.8 g of organic raw material group (G5) suspended in 8.6 g of PGMEA / PGME (mass ratio 70 / 30) 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 metal-containing film-forming compound (A-5). The concentration of components other than the solvent in the solution was 23% by mass.

[0199] [Synthesis Examples 6-20] Synthesis of Metal-Containing Film-Forming Compounds (A-6)-(A-20) Except for using the above-mentioned metal raw material M, above-mentioned organic group raw material group G, and above-mentioned silicon-containing organic group raw material group H in the amounts shown in Table 2, the metal-containing film-forming compounds (A-6) to (A-20) shown in Table 2 were obtained under the same reaction conditions as in Synthesis Example 5. [Table 2]

[0200] [Comparative example metal-containing film forming compound (R-1)] For comparative examples, the metal-containing film-forming compound (R-1) used was titanium(IV) diisopropoxybis(2,4-pentanedionate) (75% by mass in isopropyl alcohol solution).

[0201] [Comparative Synthesis Example 1] Synthesis of a metal-containing film-forming compound (R-2) for comparative examples A titanium compound reported in [Example 1] of Japanese Patent No. 6323456 was synthesized. Under a nitrogen atmosphere, 20 g of pure water was added dropwise over 10 minutes at room temperature to 180 g of a propylene glycol monoethyl ether solution of 51 g of a 75% by mass isopropyl alcohol solution of titanium(IV) diisopropoxybis(2,4-pentane dionate) (M6) while stirring. The reaction was then carried out at 60°C for 2 hours, followed by cooling to room temperature. After adding 250 g of propylene glycol monoethyl ether, the IPA was removed by vacuum concentration using a rotary evaporator to obtain a propylene glycol monoethyl ether solution of the comparative metal-containing film-forming compound (R-2). The concentration of components other than the solvent in the solution was 12% by mass.

[0202] [Comparative Synthesis Example 2] Synthesis of Metal-Containing Film-Forming Compound (R-3) for Comparative Example The titanium compound reported in [Example 1] of Japanese Patent Publication No. 6578092 was synthesized. Under a nitrogen atmosphere, 0.33 equivalents of tris(2-hydroxyethyl) isocyanurate (Tokyo Chemical Industries, Ltd., T0674) was added to 100 g of a 75% by mass isopropyl alcohol solution of titanium(IV) diisopropoxybis(2,4-pentane dionate) (M6), and the mixture was stirred at 120°C for 1 day. The solution was then concentrated under reduced pressure, crystallized in 500 g of heptane, and the resulting solid was vacuum dried to obtain a comparative example of a metal-containing film-forming compound (R-3).

[0203] [Comparative Synthesis Example 3] Synthesis of Metal-Containing Film-Forming Compound (R-4) for Comparative Example The titanium compound reported in [Synthesis Example A-II] of Japanese Patent Publication No. 6189758 was synthesized. Under a nitrogen atmosphere, 284 g of titanium tetraisopropoxide (M1) was added dropwise to 500 g of IPA solution with 27 g of deionized water in 500 g of IPA solution over 2 hours at room temperature while stirring. 120 g of 2-methyl-2,4-pentanediol 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, 1,200 g of PGMEA was added and heated at 40°C under reduced pressure until no more IPA distilled, yielding 1,000 g of a PGMEA solution (compound concentration 20% by mass) of the comparative metal-containing film-forming compound (R-4).

[0204] [Comparative Synthesis Example 4] Synthesis of Metal-Containing Film-Forming Compound (R-5) for Comparative Example The zirconium compound reported in [Synthesis Example 1-1] of International Publication No. 2020 / 241712 was synthesized. Under a nitrogen atmosphere, diethanolamine (molar ratio 2) was added dropwise over 30 minutes at room temperature to zirconium(IV) tetrabutoxide (80% by mass 1-butanol solution) (M3) (molar ratio 1) while stirring, and the mixture was stirred at 60°C for 2 hours. The reaction solution was then cooled to room temperature and diluted with 1-butanol (900 parts by mass). Water (molar ratio 0.75) was added dropwise over 10 minutes while stirring the cooled reaction solution at room temperature. The hydrolysis condensation reaction was then carried out at 60°C for 2 hours. After the reaction was complete, the resulting reaction solution was cooled to room temperature, propylene glycol monoethyl ether (1,000 parts by mass) was added, and then water and 1-butanol were removed using an evaporator to obtain a PGEE solution of the comparative metal-containing film-forming compound (R-5) (compound concentration 8.1% by mass).

[0205] [Comparative Synthesis Example 5] Synthesis of a metal-containing film-forming compound (R-6) for comparative examples A zirconium compound reported in [Synthesis Example 4] of Japanese Patent Publication No. 6311702 was synthesized. In a nitrogen atmosphere, zirconium(IV) tetrabutoxide (80% by mass 1-butanol solution) (M3) (38 g) and 50 g of propylene glycol monomethyl ether were mixed and stirred at room temperature for 10 minutes. Then, 9.2 g of glycerin was mixed in, and the mixture was heated and stirred at 100°C for 4 hours. After the reaction was complete, the mixture was cooled to room temperature, and 20 g of 1,3-acetonedicarboxylate diethyl and 200 g of γ-butyrolactone were added. Low-boiling point substances were removed using an evaporator to obtain a GBL solution of the comparative metal-containing film-forming compound (R-6) (compound concentration 9.8% by mass).

[0206] [Comparative Synthesis Example 6] Synthesis of Organic Film-Forming Resin (R-7) for Comparative Example 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 homogeneous 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 a comparative organic film-forming resin (R-7). 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-7): Mw=3,300, Mw / Mn=2.54 [ka]

[0207] (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. The organic raw material group G: (G19) to (G21) is shown below. [ka]

[0208] Modifying agents K: (K1) to (K2) are shown below. [ka]

[0209] [Synthesis of the fluidity enhancer (BPA-1)] Under a nitrogen atmosphere, 45.5 g of organic raw material group (G19), 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 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). 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 [ka]

[0210] [Synthesis of the fluidity enhancer (BPA-2)] 80.0 g of organic raw material group (G20), 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). 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 [ka]

[0211] [Synthesis of fluidity enhancer (BPA-3)] Under a nitrogen atmosphere, 20.0 g of organic raw material group (G21), 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 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). 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 [ka]

[0212] [Preparation of metal-containing film-forming composition (UDL-1)] A metal-containing film-forming compound (A-1) was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) containing 0.5% by mass of surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 3, and the mixture was filtered through a 0.02 μm membrane filter to prepare a metal-containing film-forming composition (UDL-1).

[0213] [Preparation of metal-containing film-forming compositions (UDL-2 to 24) and comparative metal-containing film-forming compositions (comparative examples UDL-1 to 7)] Each composition was prepared in the same manner as UDL-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 following formula (C-1) was used as the crosslinking agent, the following formula (F-1) was used as the acid generator (TAG), ethylene glycol dibenzyl ether (boiling point 364°C) was used as the high-boiling point solvent (B-1), and ZrO2 nanoparticles (5nm core, 915505 Sigma-Aldrich Corp) were used as the metal nanoparticles (G-1).

[0214] [Crosslinking agent, acid generator] The crosslinking agent (C-1) and acid generator (F-1) used in the metal-containing film-forming composition are shown below. [ka] [ka]

[0215] [Table 3]

[0216] [Evaluation of Embedding Characteristics (Examples 1-1 to 1-24, Comparative Examples 1-1 to 1-7)] The compositions prepared above (UDL-1 to 24, and Comparative Examples UDL-1 to 7) were each applied to an SiO2 wafer substrate 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. The substrate used was a base substrate 9 (SiO2 wafer substrate) having a dense line and space pattern as shown in Figure 3(Q) (overhead view) and (R) (cross-sectional view). The cross-sectional shape of each wafer substrate obtained in 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-forming composition with inferior 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-forming composition with good embedding properties is used, in this evaluation, as shown in Figure 3(S), a void-free metal-containing film 10 is filled inside the metal-containing film that fills the spaces between lines of the substrate 9 having a dense line and space pattern.

[0217] [Table 4]

[0218] As shown in Table 4, in Examples 1-1 to 1-24, which used the metal-containing film-forming compositions (UDL-1 to 24) of the present invention, it was possible to fill dense line and space patterns without generating voids even after baking at 350°C, confirming that they have good filling characteristics even under high-temperature baking conditions. On the other hand, in Comparative Examples 1-1 to 1-6, which used metal compounds that, unlike the metal-containing film-forming compounds of the present invention, do not contain any of the crosslinking groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4), voids were observed at the bottom of the pattern after baking at 350°C. It is presumed that these voids were generated because the organic ligands coordinating to the metal had low heat resistance, resulting in large volume shrinkage due to high-temperature baking.

[0219] [Evaluation of planarization characteristics (Examples 2-1 to 2-24, Comparative Example 2-1)] For the substrate 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 formation 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. [Table 5]

[0220] As shown in Table 5, Examples 2-1 to 2-24, using the metal-containing film-forming compositions (UDL-1 to 24) of the present invention, showed small differences in film height between patterned and unpatterned areas, and exhibited planarization performance comparable to Comparative Example 2-1, which used an organic resist underlayer material (Comparative Example UDL-7). When comparing UDL-5 to 7 with varying crosslinkable organic ligand content, it was found that compositions with higher crosslinkable organic ligand content exhibited superior planarization characteristics. Furthermore, UDL-3, 4, 6, 7, 8, 9, 13, 14, and 15, which contain aromatic ring-containing ligands, showed good flatness, possibly due to their superior heat resistance. In addition, UDL-21, with the addition of a high-boiling point solvent (B-1), and UDL-22 to 24, with the addition of a fluidity enhancer (BPA-1 to 3), showed even better planarization characteristics than the compositions without additives. It is presumed that the thermal fluidity of the metal-containing film-forming compositions could be further improved by using additives.

[0221] [Etching resistance evaluation (Examples 3-1 to 3-24, Comparative Example 3-1)] Metal-containing film-forming compositions (UDL-1 to 24, and comparative example UDL-7) were 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, each etching was performed using CF4 gas under the following conditions with an etching apparatus CE-300I manufactured by ULVAC, and the film thickness b was measured. Film thickness etched during the specified time (film thickness) a - film thickness b The etching rate (nm / min) was calculated as the film thickness etched per minute from the material. The results are shown in Table 6.

[0222] Dry etching conditions with CF4 gas Pressure: 1 Pa Antenna RF power: 100W Bias RF Power: 15W CF4 gas flow rate: 15 sccm Time: 30sec [Table 6]

[0223] As shown in Table 6, Examples 3-1 to 3-24, which used the metal-containing film-forming compositions of the present invention (UDL-1 to 24), were found to exhibit significantly better etching resistance to CF4 gas compared to Comparative Example 3-1, which used an organic resist underlayer material (Comparative Example UDL-7).

[0224] [Pattern formation method (Examples 4-1 to 4-24, Comparative Example 4-1)] The above metal-containing film-forming compositions (UDL-1 to 24, Comparative Example UDL-7) 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.

[0225] As a silicon atom-containing resist interlayer material (SOG-1), a polymer represented by ArF silicon-containing interlayer polymer (SiP1) and a thermal crosslinking catalyst (CAT1) were dissolved in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 7, and the mixture was filtered through a fluororesin filter with a pore size of 0.1 μm to prepare the silicon atom-containing resist interlayer material (SOG-1).

[0226] [Table 7]

[0227] The structural formulas of the ArF silicon-containing interlayer polymer (SiP1) and thermal crosslinking catalyst (CAT1) used are shown below. [ka]

[0228] The resist upper layer material (single-layer resist for ArF) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in the proportions shown in Table 8 in a solvent containing 0.1% by mass of the surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), and filtering the mixture through a 0.1 μm fluororesin filter.

[0229] [Table 8]

[0230] 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. [ka]

[0231] 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.

[0232] [Table 9]

[0233] The protective film polymer (PP1) used in the immersion protective film material (TC-1) is shown below. [ka]

[0234] 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).

[0235] Next, a hard mask pattern was formed by dry etching, using the resist upper layer pattern as a mask to etch the resist interlayer. A metal-containing film pattern was then formed by etching the metal-containing film using the resulting hard mask pattern as a mask. Finally, the SiO2 film was etched using the resulting metal-containing film pattern as a mask. The etching conditions are as follows.

[0236] 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

[0237] 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

[0238] 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

[0239] Table 10 shows the results of observing the pattern cross-section using an electron microscope (S-4700) manufactured by Hitachi, Ltd. [Table 10]

[0240] As shown in Table 10, in Examples 4-1 to 4-24, which used the metal-containing film-forming compositions of the present invention (UDL-1 to 24), 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 by the multilayer resist method. On the other hand, in Comparative Example 4-1, which used an organic resist underlayer film material (Comparative Example UDL-7) that showed insufficient performance in dry etching resistance evaluation, distortion of the pattern shape occurred during pattern processing, and a good pattern could not be obtained in the end.

[0241] [SOC pattern inversion method (Examples 5-1 to 5-24, Comparative Examples 5-1 to 5-8)] A silicon wafer substrate with a 300 nm SiO2 film was coated with a solution-type resist underlayer material (SOC-1) as a resist underlayer, and baked at 350°C for 60 seconds to form a resist underlayer with a thickness of 80 nm. A silicon atom-containing resist interlayer material (SOG-1) was then coated 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 coated 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 then coated on the photoresist film and baked at 90°C for 60 seconds to form a protective film with a thickness of 50 nm.

[0242] 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).

[0243] As the coating-type resist underlayer material (SOC-1), the polymer indicated as the polymer for resist underlayer (SOP1) and FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) were dissolved in an organic solvent in the proportions shown in Table 11, and the mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare the coating-type resist underlayer material (SOC-1).

[0244] [Table 11]

[0245] Table 12 shows the structural formula of the polymer (SOP1) used for the resist underlayer film. [Table 12]

[0246] 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).

[0247] 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.

[0248] 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

[0249] 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: 60sec

[0250] Next, the above-mentioned metal-containing film-forming compositions (UDL-1 to 24, Comparative Examples UDL-1 to 7) were applied to the obtained SOC-1 film pattern and baked in air at 350°C for 60 seconds to form a metal-containing film with a thickness of 80 nm. 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. The pattern was then inverted onto the metal-containing film, and the resulting metal-containing film pattern was 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 composition (Comparative Examples 5-8). The etching conditions are as shown below.

[0251] 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: 15sec

[0252] 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

[0253] 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: 30sec

[0254] 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

[0255] Comparative Example 5-8: Transfer conditions for SOC-1 film patterns to 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

[0256] Table 13 shows the results of observing the pattern cross-section using an electron microscope (S-4700) manufactured by Hitachi, Ltd. [Table 13]

[0257] As shown in Table 13, in Examples 5-1 to 5-24, which used the metal-containing film-forming compositions (UDL-1 to 24) of the present invention, the SOC-1 film pattern was accurately reversed in all cases, and the reversed pattern was successfully transferred to the substrate without any pattern distortion. This confirms that the metal-containing film-forming compositions of the present invention are suitable for use in microfabrication using a tone reversal etching method in multilayer resist processing. On the other hand, in Comparative Example 5-8, 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 5-6, which used Comparative Example UDL-1 to 6, which showed insufficient performance in the embedding characteristic evaluation, the metal-containing film was not filled to the bottom between the SOC-1 film patterns, making it impossible to reverse the pattern and ultimately obtain a good reversed pattern. Meanwhile, in Comparative Example 5-7, which used Comparative Example UDL-7, which showed insufficient performance in the dry etching resistance evaluation, distortion of the pattern shape occurred during pattern reversal processing, and ultimately a good reversed pattern could not be obtained.

[0258] 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 resist underlayer material used in multilayer resist methods and as an inversion agent used in tone inversion etching methods, because it possesses both high embedding / planarization characteristics and dry etching resistance. Furthermore, it has become clear that the pattern formation method of the present invention using this composition can form fine patterns with high precision even on substrates that have steps.

[0259] This specification includes the following embodiments: [1] A metal-containing film-forming compound used in a metal-containing film-forming composition, The metal-containing film-forming compound is characterized in that it contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and one or more ligands derived from compounds represented by the following general formulas (1-A) to (1-D). [ka] (In general formulas (1-A) to (1-D), R1 to R3 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4). R4 to R5 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4). R6 to R9 are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a bridging group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4). 10 R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms. Compounds of general formulas (1-A) to (1-D) contain one or more bridging groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4). In general formula (1-B), R4 and R5 may be bonded to each other, forming an unsaturated or saturated ring structure. [ka] (In general formulas (a-1) to (a-4), Ra is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [ka] (In general formulas (b-1) to (b-4), R' b R' is a hydrogen atom or a methyl group, and in the same formula they may be the same or different from each other. c (where * represents a hydrogen atom, a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, and * represents a bond.) [2]: The metal-containing film-forming compound according to [1], characterized in that the ligand derived from the compound represented by the general formulas (1-A) to (1-D) contains one or more structures selected from aromatic rings, heteroaromatic rings, and alicyclic structures. [3]: The metal-containing film-forming compound according to [1] or [2] above, characterized in that the metal-containing film-forming compound further contains a ligand derived from a silicon compound represented by the following general formula (2). [ka] (In general formula (2), R 3A , R 3B and R 3C This includes an organic group having 1 to 30 carbon atoms having a crosslinking group in any of the structures shown by the following general formulas (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a carbon number 6 (It is one of the organic groups selected from approximately 20 aryl groups.) [ka] (In general formulas (c-1) to (c-3), R'3 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [4]: A metal-containing film-forming composition used in semiconductor manufacturing, characterized in that it contains (A) a metal-containing film-forming compound and (B) an organic solvent, which are any one of the above [1] to [3]. [5]: The metal-containing film-forming composition according to [4], characterized in that the metal-containing film-forming composition further contains one or more of (C) a crosslinking agent, (E) a surfactant, and (F) an acid generator. [6]: The metal-containing film-forming composition according to [4] or [5] above, characterized in that the (B) organic solvent contains one or more organic solvents having a boiling point of 180°C or higher as (B1) high-boiling point solvent. [7]: The metal-containing film-forming composition according to any one of the above [4] to [6], characterized in that the metal-containing film-forming composition further contains (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less. [8]: The metal-containing film-forming composition according to [7] above, wherein the (G) metal oxide nanoparticles are selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles. [9]: The metal-containing film-forming composition according to any one of [4] to [8] above, wherein the metal-containing film-forming composition further contains a fluidity promoter (BP) having an organic group and an aromatic ring represented by the following general formula (3). [Chemical formula] (In general formula (3), * represents a bonding site to an oxygen atom, R B is a divalent organic group having 1 to 10 carbon atoms, and R A is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.)

[10] : The metal-containing film-forming composition according to [9] above, wherein the fluidity promoter (BP) has at least one structural unit represented by the following general formulas (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5). [Chemical formula] (In general formulas (BP-1) and (BP-2), W1 and W2 are each independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. R a is a group represented by the following formula (4). Y’ is a group represented by the following formula (5). n1 is 0 or 1, n2 is 1 or 2, and V is each independently a hydrogen atom or a linking part.) [Chemical formula] (In general formula (BP-3), Z1 is a group represented by the following general formula (6), and R a is a group represented by the following formula (4). n4 is 0 or 1, n5 is 1 or even 2, and V is each independently a hydrogen atom or a linking part.) [Chemical formula] (In formula (4), * represents the bonding portion with an oxygen atom.)

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[11] A method for forming a pattern on a substrate to be processed, (I-1) A step of forming a metal-containing film by applying one of the metal-containing film-forming compositions from [4] to

[10] above 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.

[12] A method for forming a pattern on a substrate to be processed, (II-1) A step of forming a metal-containing film by applying one of the metal-containing film-forming compositions from [4] to

[10] above onto a substrate to be processed, and then heat-treating it, (II-2) A step of forming a silicon-containing resist interlayer on the metal-containing film, (II-3) A step of forming a resist upper layer film on the silicon-containing 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 silicon-containing 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 silicon-containing 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. A pattern forming method characterized by having the following features.

[13] A method for forming a pattern on a substrate to be processed, (III-1) A step of forming a metal-containing film by applying one of the metal-containing film-forming compositions from [4] to

[10] above 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.

[14] : The pattern formation method of

[13] , characterized in that the inorganic hard mask interlayer is formed by a CVD method or an ALD method.

[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 one of the metal-containing film-forming compositions from [4] to

[10] above onto a substrate to be processed, and then heat-treating it. (IV-2) A step of forming a resist underlayer film on the metal-containing film, (IV-3) A step of forming a silicon-containing 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, (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 the 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 the resist underlayer film by dry etching, using the silicon-containing resist interlayer film or inorganic hard mask interlayer film on which the pattern has been transferred as a mask. (IV-8) The above The pattern was transferred. A step of transferring a pattern to the metal-containing film by dry etching using the resist underlayer film 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) 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 any one of the metal-containing film-forming compositions from [4] to

[10] above, 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 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 inorganic 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.

[0260] 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]

[0261] 1...Substrate to be processed, 2...Layer to be processed, 2a... Pattern (a pattern formed on the workpiece layer) 2b... Reversal pattern (reversal pattern formed on the processed layer), 3... Metal-containing film, 3a…Metal-containing film pattern, 4…Resist interlayer, 4a... Resist interlayer pattern, 5... Resist top layer, 5a…Resist upper layer pattern, 6…Exposed area, 7…Resist lower layer, 7a…Resist underlayer pattern, 8…Metal-containing film, 8a...Inverted metal-containing film pattern, 9…Substrate with dense line and space pattern, 10…Metal-containing film, 11…Substrate with dense line and space pattern, 12…Filling film, Delta 12…A step difference in the packing film between areas with dense line patterns and areas without line patterns.

Claims

1. A metal-containing film-forming compound used in a metal-containing film-forming composition, The metal-containing film-forming compound is characterized in that it contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, one or more ligands derived from a compound represented by any of the following general formulas (1-A1) to (1-A4), and further a ligand derived from a silicon compound represented by the following general formula (2). 【Chemistry 1】 (In the above formula, X1 and X2 represent hydrocarbon groups having 1 to 20 carbon atoms or alkoxy groups having 1 to 20 carbon atoms.) 【Chemistry 2】 (In the above formula, X1 and X2 represent hydrocarbon groups having 1 to 20 carbon atoms or alkoxy groups having 1 to 20 carbon atoms.) 【Transformation 3】 (In the above formula, R2 is a hydrogen atom, and X1 and X2 represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.) 【Chemistry 4】 (In the above formula, R'c is a hydrogen atom, a substituted or unsubstituted saturated or unsaturated monovalent alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, and X1 and X2 represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.) 【Transformation 5】 (In general formula (2), R ３Ａ , R ３Ｂ and R ３Ｃ This is one of the following groups selected from a C1-C30 alkyl group having a bridging group in any of the structures shown in the general formulas (c-1) to (c-3) below, a substituted or unsubstituted C1-C20 alkyl group, and an aryl group having C6-C20. 【Transformation 6】 (In general formulas (c-1) to (c-3), R' ３ (where is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.)

2. The metal-containing film-forming compound according to claim 1, characterized in that the ligand derived from the compound represented by any of the general formulas (1-A1) to (1-A4) contains one or more structures selected from aromatic rings, heteroaromatic rings, and alicyclic structures.

3. A metal-containing film-forming composition used in semiconductor manufacturing, characterized in that it contains (A) a metal-containing film-forming compound and (B) an organic solvent as described in claim 1 or claim 2.

4. The metal-containing film-forming composition according to claim 3, characterized in that the metal-containing film-forming composition further contains one or more of (C) a crosslinking agent, (E) a surfactant, and (F) an acid generator.

5. The metal-containing film-forming composition according to claim 3, characterized in that the (B) organic solvent contains one or more organic solvents having a boiling point of 180°C or higher as (B1) high-boiling point solvent.

6. The metal-containing film-forming composition according to claim 3, characterized in that the metal-containing film-forming composition further comprises (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less.

7. The metal-containing film-forming composition according to claim 6, characterized in that the (G) metal oxide nanoparticles are selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles.

8. The metal-containing film-forming composition according to claim 3, characterized in that the metal-containing film-forming composition further comprises a fluidity enhancer (BP) having a group represented by the following general formula (3) and an aromatic ring. 【Transformation 7】 (In general formula (3), * represents the bonding site to the oxygen atom, R Ｂ R is an alkylene group having 1 to 10 carbon atoms. Ａ (This is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

9. The metal-containing film-forming composition according to claim 8, 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 general formulas (BP-1) and (BP-2), W １ and W ２ are each independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. R ａ is a group represented by the following formula (4). Y' is a group represented by the following formula (5). n1 is 0 or 1, n2 is 1 or 2, and V each independently represents a hydrogen atom or a linking portion.) 【Chemistry 9】 (In general formula (BP-3), Z １ The group is represented by the following general formula (6), R ａ (This is the group represented by formula (4) below. n4 is 0 or 1, n5 is 1 or 2, and V independently represents a hydrogen atom or a linkage.) 【Chemistry 10】 (In formula (4), * represents the bond with the oxygen atom.) 【Chemistry 11】 (In equation (5), * represents a coupling.) 【Chemistry 12】 (In general formula (6), W １ , W ２ Y' and n1 are the same as described above. 【Chemistry 13】 (In the general formula (BP-4), m3 and m4 represent 1 or 2, and Z 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).) 【Chemistry 14】 (In general formula (7), * represents a combination, l represents an integer from 0 to 3, R ａ ~R ｆ Each of these independently represents a hydrogen atom, a C1-C10 alkyl group which may be fluorine-substituted, a phenyl group, or a phenylethyl group, R ａ and R ｂ (They may combine to form a cyclic compound.) 【Chemistry 15】 (In general formula (8), * represents the bonding site to the aromatic ring, Q １ (This is a structure consisting of 1 to 30 linear saturated hydrocarbon groups, or the structure represented by the general formula (9) below.) 【Chemistry 16】 (In general formula (9), * represents the bonding site to the carbonyl group, R ｉ R is the group represented by formula (4) above. 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 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, each representing an integer from 0 to 7. However, n3 + n4 is between 0 and 7. n5 represents 0 to 2. 【Chemistry 17】 (In general formula (BP-5), R １ is a saturated alkyl group having 1 to 30 carbon atoms or an unsaturated alkyl group having 2 to 30 carbon atoms, X is any of an alkanediyl group having 1 to 30 carbon atoms, a cycloalkanediyl group having 3 to 30 carbon atoms, an alkanediyloxy group having 1 to 30 carbon atoms, a cycloalkanediyloxy group having 3 to 30 carbon atoms, and an arenediyl group having 6 to 30 carbon atoms, R ａ is the base shown in 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.)

10. 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 3 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.

11. 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 3 onto a substrate to be processed, and then heat-treating it. (II-2) A step of forming a silicon-containing resist interlayer on the metal-containing film, (II-3) A step of forming a resist upper layer film on the silicon-containing 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 silicon-containing 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 silicon-containing 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.

12. 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 3 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.

13. The pattern forming method according to claim 12, characterized in that the inorganic hard mask interlayer is formed by CVD or ALD.

14. 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 3 onto a substrate to be processed, and then heat-treating it. (IV-2) A step of forming a resist underlayer film on the metal-containing film, (IV-3) A step of forming a silicon-containing 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, (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 the 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 the resist underlayer film by dry etching, using the silicon-containing resist interlayer film or inorganic hard mask interlayer film 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 resist underlayer film 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.

15. 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 3, and 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 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 inorganic 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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