Compound for forming metal-containing film, composition for forming metal-containing film, and patterning process

Abstract

To provide: a compound for forming a metal-containing film having excellent dry etching resistance and also having high film-formability, a high filling property, and a high tin content; a composition for forming a metal-containing film employing the compound; and a patterning process in which the composition is used as a resist underlayer film material.SOLUTION: A compound for forming a metal-containing film is a polymer containing one or both of repeating units represented by the general formula (P-1) or (P-2) in the figure.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] With the high integration and high speed of LSIs, the miniaturization of pattern rules has been rapidly progressing. As the most advanced miniaturization technology, ArF immersion lithography has been applied to the mass production of devices after the 45 nm node. In addition, together with ArF immersion exposure, a double patterning process has been put into practical use in generations after the 28 nm node, enabling the formation of narrow pitch patterns that exceed the optical limit.

[0003] Furthermore, in the manufacture of devices after the 20 nm node, a multi-patterning process for producing patterns with a narrower pitch by repeating exposure and etching three or more times is being studied. However, since the multi-patterning process increases the number of steps, productivity has decreased due to the lengthening of the manufacturing period and the increase in the frequency of defect occurrence, and the cost has increased significantly.

[0004] In recent years, extreme ultraviolet (EUV) lithography with a wavelength of 13.5 nm has attracted attention as a promising technology to replace the combined use of ArF immersion lithography and the multi-patterning process. By using this technology, it has become possible to form fine patterns with a half pitch of 25 nm or less in a single exposure.

[0005] On the other hand, in EUV lithography, in order to compensate for the insufficient output of the light source, high sensitivity is strongly required for the resist material. However, the increase in shot noise associated with high sensitivity leads to an increase in the edge roughness (LER, LWR) of the line pattern, and the compatibility between high sensitivity and low edge roughness is one of the important issues in EUV lithography.

[0006] As an attempt to increase the sensitivity of resists and reduce the influence of shot noise, using metal materials in resist materials has been considered in recent years. Compounds containing metal elements such as barium, titanium, hafnium, zirconium, and tin have a higher absorbance for EUV light compared to organic materials without metals, and an improvement in the photosensitivity of the resist and suppression of the influence of shot noise can be expected. In addition, a high selectivity etching process can be expected by combining a metal-containing resist pattern with an underlying film made of a non-metallic material.

[0007] For example, resist materials added with metal salts and organometallic complexes described in Patent Documents 1 and 2, and non-chemically amplified resist materials using metal oxide nanoparticles described in Patent Documents 3 and 4 have been studied.

[0008] Among them, molecules containing tin are excellent in absorbing electron beams and extreme ultraviolet rays, and thus active research is being conducted. In the case of an organotin polymer, which is one of them, the alkyl ligand is dissociated by light absorption or secondary electrons generated thereby, and negative tone patterning that cannot be removed with an organic developer through crosslinking through an oxo bond with the peripheral chain is possible. Such an organotin polymer can improve the sensitivity while maintaining the resolution and line edge roughness, but has not yet reached the level of commercialization (Patent Document 5). In addition, many problems remain, such as insufficient storage stability regarding changes in resist sensitivity.

[0009] Regarding the above problems, development using a material containing a metal element such as titanium, hafnium, zirconium, or tin in the resist underlying film has also been studied. Performance improvements such as improving the exposure sensitivity, which is a problem with metal-containing resist materials, and suppressing sensitivity changes in a storage environment are not required, and there is a possibility of providing a resist underlying film with excellent dry etching resistance by containing the above metal elements. Patent Document 7 reports that a material using a Ti compound exhibits excellent dry etching resistance against CHF3 / CF4-based gases and CO2 / N2-based gases.

[0010] On the other hand, when using a metal compound for a resist underlayer film, problems include film-forming properties and embedding properties. For example, in a compound assumed to be used in a photoresist such as Patent Document 6, heat resistance is not mentioned, but since high-temperature baking is not assumed, the heat resistance is insufficient, and there is a risk of poor embedding and film-forming properties. Also, in Patent Document 7, film-forming properties and embedding properties are not mentioned, but generally, metal oxide compounds have a large thermal shrinkage during baking and induce a significant deterioration in filling properties after high-temperature baking. Therefore, there is a concern that they are insufficient as a resist underlayer film material that requires heat resistance characteristics such as film-forming properties and embedding characteristics. In Patent Document 8, it is reported that a metal compound modified with a specific ligand has excellent embedding properties, but the baking temperature for the embedding property evaluation performed is as low as 150 °C, and there is a concern that it is insufficient as a resist underlayer film that requires heat resistance (for example, characteristics against heat treatment that may be performed after forming the resist underlayer film). In Patent Document 9, by mixing the metal compound reported in Patent Document 8 with an organic polymer having a specific structure, a resist underlayer film material excellent in embedding properties after baking at 400 °C is provided. However, since it is a mixed composition of an inorganic metal compound and an organic polymer, there are concerns about film-forming defects caused by poor compatibility, deterioration of storage stability, and deterioration of dry etching resistance.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Summary of the Invention

Problems to be Solved by the Invention

[0012] The present invention has been made in view of the above circumstances, and has excellent dry etching resistance against conventional organic underlayer film materials, and has high film forming properties, embedding characteristics, and a high tin content rate. An object of the present invention is to provide a compound for forming a metal-containing film, a composition for forming a metal-containing film using the compound, and a patterning method using the composition as a resist underlayer film material.

Means for Solving the Problems

[0013] In order to solve the above problems, the present invention provides a compound for forming a metal-containing film, wherein the compound is a polymer containing any one or both of the repeating units represented by the following general formula (P-1) or (P-2).

Chemical Formula

[0014] For a polymer containing such repeating units, radicals are generated by radical cleavage of the Sn-alkyl bond, and thus a crosslinking reaction by the radicals occurs. Further, since it is a polymer containing repeating units, it is less likely to become a decomposition product with a low molecular weight that sublimates immediately when the bond is cleaved, and thus it can participate in the crosslinking reaction before sublimation, resulting in a compound with excellent heat resistance. It is possible to suppress deterioration of film-forming properties and embedding properties, and thus it is possible to provide a resist underlayer film material excellent in film-forming properties and embedding characteristics even after high-temperature baking. Further, since at least one tin atom is contained in the repeating unit, the tin content is high. If the organic group of the repeating unit is designed compactly, the Sn content can be further increased, and a resist underlayer film material excellent in etching resistance can be provided.

[0015] In the above compound, (i) it is a polymer containing a repeating unit represented by the general formula (P-1), and in the general formula (P-1), W1 is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms which may contain a hydroxyl group or an amino group (the hydrocarbon group contains an oxygen atom, a nitrogen atom, a sulfur atom, and may form an ether bond, a carbonyl group, an ester group), or any of the groups represented by the following general formulas (W1-1) to (W1-4).

Chemical formula

[0016] In the above compound, (ii) a polymer containing a repeating unit represented by the general formula (P-2), wherein in the general formula (P-2), W2 is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms which may contain a hydroxyl group or an amino group, or a cyclic hydrocarbon group bonded to R3 (the hydrocarbon group may contain an oxygen atom, a nitrogen atom, a sulfur atom, and may form an ether bond, a carbonyl group, an ester group), or any of the groups represented by the following general formulas (W2-1) to (W2-4) is preferable.

Chemical formula

[0017] If W1 in the above general formula (P-1) and / or W2 in (P-2) have the above structures, the proportion of the organic group in the repeating unit can be suppressed, and the tin content rate can be increased.

[0018] Further, in R in the general formulas (W1-1) to (W1-4) of the above (i) and / or the general formulas (W2-1) to (W2-4) of the above (ii) W is preferably an unsaturated hydrocarbon group having 2 to 23 carbon atoms.

[0019] If R in the general formulas (W1-1) to (W1-4) and (W2-1) to (W2-4) W is an unsaturated hydrocarbon group having 2 to 23 carbon atoms, the thermosetting property of the above polymer can be further improved.

[0020] Further, in the present invention, R in the general formulas (W1-1) to (W1-4) of the above (i) and / or the general formulas (W2-1) to (W2-4) of the above (ii) W can be a group represented by the following general formula (1).

Chemical formula

[0021] In the general formulas (W1-1) to (W1-4) and (W2-1) to (W2-4), if R W is a group represented by the general formula (1), it is possible to achieve both thermosetting properties and a high tin content. When this is used in a composition for forming a metal-containing film, a resist underlayer film material having more excellent film-forming properties, embedding properties, and tin content can be provided.

[0022] Further, it is preferable that the terminal structure of the polymer having the repeating unit of the general formula (P-1) is the following general formula (T-1), or the terminal structure of the polymer having the repeating unit of the general formula (P-2) is the following general formula (T-2).

Chemical formula

[0023] If the terminal structure of the polymer having the repeating unit of the general formula (P-1) or (P-2) is the general formula (T-1) or (T-2), respectively, since all of the repeating unit and the terminal structure contain tin atoms, the tin content can be increased. In addition, since the tin-alkyl bond generates radicals by heat, the cross-linking reaction is promoted by the radicals, so the thermosetting properties can be enhanced, the sublimation product can be suppressed, and the suppression of volume shrinkage that induces deterioration of the embedding property can also be expected. Thereby, a resist underlayer film material excellent in film-forming properties, embedding properties, and etching resistance after high-temperature baking can be provided.

[0024] Moreover, it is preferable that the terminal structure of the polymer having the repeating unit of the general formula (P-1) or (P-2) is *-OC(=O)R (wherein R is a monovalent organic group, and * represents the bonding portion with the Sn atom in the polymer).

[0025] If the terminal structure of the polymer having the repeating unit of the general formula (P-1) or (P-2) is *-OC(=O)R (wherein R is a monovalent organic group, and * represents the bonding portion with Sn in the polymer), since R can be freely changed, solubility improvement can be expected by incorporating a bulky structure, and since it is also possible to have a crosslinked structure, sublimates can be further suppressed, and suppression of volume shrinkage that induces deterioration of embedding properties can also be expected. Thereby, even after high-temperature baking, a resist underlayer film material excellent in film-forming properties and embedding characteristics can be provided.

[0026] In this case, it is preferable that R in the terminal structure *-OC(=O)R is any of the groups represented by the following general formulas (A-1) to (A-4), the following general formula (3), and the following general formula (4).

Chemical formula

Chemical formula

[0027] When R has a structure represented by the above general formulas (A-1) to (A-4), since the structure contains an organic group in which a protecting group is eliminated by the action of either a bulky acid, heat, or both, the solvent solubility of the polymer can be increased. Further, when this is used in a composition for forming a metal-containing film, the protecting group is eliminated during baking, and a hydroxyl group or a carboxyl group is generated. The α-hydrogen of the OH or carboxylic acid thus generated easily reacts with the radicals generated by the cleavage of the tin-carbon bond during baking, causing a crosslinking reaction. Therefore, the compound of the present invention is excellent in thermosetting properties and can suppress the volume shrinkage that induces deterioration of film-forming properties and embedding properties. Furthermore, even during high-temperature baking, a resist underlayer film material excellent in film-forming properties and embedding characteristics can be provided.

[0028] Also, when R has a structure represented by the above general formula (3), it contains a hydroxyl group at the terminal or a crosslinking group having any of the structures represented by the above general formulas (B-1) to (B-3). Therefore, when these are used in a composition for forming a metal-containing film, during baking, not only the crosslinking reaction between radicals generated by the cleavage of the tin-carbon bond but also the reaction between radicals and crosslinking groups and the reaction between crosslinking groups occur, causing further crosslinking reactions. Thus, it is excellent in thermosetting properties and can suppress the volume shrinkage that induces deterioration of film-forming properties and embedding properties. Even after high-temperature baking, a resist underlayer film material excellent in film-forming properties and embedding characteristics can be provided.

[0029] And when R has a structure represented by the above general formula (4), it contains any of the structures represented by (C-1) to (C-4) at the terminal. Since the structure has a high crosslinking group density and is excellent in thermosetting properties, when this is used in a composition for forming a metal-containing film, the volume shrinkage during baking is small, and even after high-temperature baking, a resist underlayer film material excellent in film-forming properties and embedding characteristics can be provided.

[0030] Y in the general formulas (A-1) to (A-4) above A1 , X in the general formula (3), or X in the general formula (4) is preferably an unsaturated hydrocarbon group having 2 to 23 carbon atoms.

[0031] Y in the general formulas (A-1) to (A-4) above A1 , if X in the general formula (3) or X in the general formula (4) is an unsaturated hydrocarbon having 2 to 23 carbon atoms, the thermosetting property of the compound for forming a metal-containing film can be further improved.

[0032] In this case, Y in the general formulas (A-1) to (A-4) above A1 , X in the general formula (3), or X in the general formula (4) can be a group represented by the following general formula (1). [Chemical formula] (In the general formula (1), R a , R b and R c are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R a and R b may be bonded to form a cyclic substituent. *1 and *2 each represent a bonding portion with a carbonyl group, and *1 and *2 may be reversed.)

[0033] Y in the general formulas (A-1) to (A-4) above A1 , if X in the general formula (2), or X in the general formula (3) is the one represented by the general formula (1), it becomes possible to enhance the thermosetting property, and when this is used in a composition for forming a metal-containing film, a resist underlayer film material showing more excellent film-forming property and embedding characteristics can be provided.

[0034] Further, the present invention provides a composition for forming a metal-containing film that functions as a resist underlayer film material used in semiconductor manufacturing, which is characterized by containing (a) a compound for forming a metal-containing film of the present invention and (b) an organic solvent.

[0035] For such a composition for forming a metal-containing film, since it contains an organotin compound excellent in solvent solubility and heat resistance, it has excellent dry etching resistance with respect to conventional organic underlayer film materials and can provide a resist underlayer film material having a high degree of film-forming property.

[0036] The above composition is a composition for forming a metal-containing film that can be used as a resist underlayer film used in a multilayer resist method, and can further contain one or more of (c) a crosslinking agent, (d) a surfactant, (e) a fluidity promoter, and (f) an acid generator.

[0037] Further, it is preferable that the above (b) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

[0038] By imparting thermal fluidity to the above compound for forming a metal-containing film by adding a high-boiling solvent, the planarization characteristics of the composition for forming a metal-containing film can be further improved.

[0039] Further, the present invention is a method for forming a pattern on a substrate to be processed, comprising: (I-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film of the present invention on a substrate to be processed and then performing heat treatment; (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 and then developing with a developer; (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 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 above steps is provided.

[0040] By the pattern formation method using the above two-layer resist process, a fine pattern can be formed on a workpiece (substrate to be processed).

[0041] Further, the present invention is a method for forming a pattern on a substrate to be processed, comprising: (II-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film of the present invention on a substrate to be processed and then performing heat treatment; (II-2) A step of forming a resist intermediate film on the metal-containing film; (II-3) A step of forming a resist upper layer film using a photoresist material on the resist intermediate film; (II-4) A step of performing pattern exposure on the resist upper layer film and then developing with a developer to form a pattern on the resist upper layer film; (II-5) A step of transferring the pattern to the resist intermediate film by dry etching using the resist upper layer film having the pattern as a mask; (II-6) A step of transferring the pattern to the metal-containing film by dry etching using the resist intermediate film having the pattern transferred thereto as a mask, and (II-7) A step of processing the substrate to be processed using the metal-containing film having the pattern formed thereon as a mask to form a pattern on the substrate to be processed. A pattern formation method characterized by comprising the above steps is provided.

[0042] By the pattern formation method using the above three-layer resist process, a fine pattern can be formed on a workpiece with high precision.

[0043] Further, the present invention is a method for forming a pattern on a substrate to be processed, comprising: (III-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film of the present invention on a substrate to be processed and then performing heat treatment; (III-2) A step of forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist lower layer film; (III-3) A step of forming an organic thin film on the inorganic hard mask intermediate film; (III-4) Forming a resist upper layer film on the organic thin film using a photoresist material; (III-5) After pattern-exposing the resist upper layer film, developing it with a developer to form a pattern in the resist upper layer film; (III-6) Using the resist upper layer film with the pattern formed thereon as a mask, transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching; (III-7) Using the inorganic hard mask intermediate film with the pattern transferred thereon as a mask, transferring the pattern to the metal-containing film by dry etching; and (III-8) Using the metal-containing film with the pattern formed thereon as a mask to process the substrate to be processed and form a pattern on the substrate to be processed provided is a pattern formation method characterized by comprising the above steps.

[0044] By the pattern formation method using the above four-layer resist process, a fine pattern can be formed on the object to be processed with high precision.

[0045] In this case, it is preferable to form the inorganic hard mask intermediate film by CVD method or ALD method.

[0046] When the inorganic hard mask is formed by CVD method or ALD method, a fine pattern can be formed on the object to be processed with higher precision.

[0047] Further, the present invention is a method for forming a pattern on a substrate to be processed, comprising: (IV-1) Forming a resist lower layer film on the substrate to be processed; (IV-2) After applying the composition for forming a metal-containing film of the present invention on the resist lower layer film and performing heat treatment to form a metal-containing film; (IV-3) Forming a resist upper layer film on the metal-containing film using a photoresist material, or forming an organic adhesion film by spin coating on the metal-containing film and then forming a resist upper layer film on it using a photoresist material; (IV-4) After pattern-exposing the upper resist film, developing it with a developer to form a pattern in the upper resist film; (IV-5) Using the upper resist film on which the pattern has been formed as a mask, transferring the pattern to the metal-containing film, or the organic adhesion film and the metal-containing film by dry etching; (IV-6) Using the metal-containing film on which the pattern has been transferred as a mask, transferring the pattern to the lower resist film by dry etching; and (IV-7) Using the lower resist film on which the pattern has been formed as a mask to process the substrate to be processed and form a pattern on the substrate to be processed A pattern formation method characterized by comprising the above.

[0048] By the pattern formation method using the above multilayer resist process, a fine pattern can be formed on the object to be processed with high precision.

[0049] Further, the present invention is a method for forming a pattern on a substrate to be processed, comprising: (V-1) Forming a lower resist film on the substrate to be processed; (V-2) Forming a combination of a resist intermediate film, or an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the lower resist film; (V-3) Forming an upper resist film using a photoresist material on the resist intermediate film, or the combination of the inorganic hard mask intermediate film and the organic thin film; (V-4) After pattern-exposing the upper resist film, developing it with a developer to form a pattern in the upper resist film; (V-5) Using the upper resist film on which the pattern has been formed as a mask, transferring the pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching; (V-6) Using the resist intermediate film, or the inorganic hard mask intermediate film on which the pattern has been transferred as a mask, transferring the pattern to the lower resist film by dry etching; (V-7) On the resist underlayer film on which the pattern is formed, after applying the composition for forming a metal-containing film of the present invention and performing heat treatment, the metal-containing film is coated, and the space between the resist underlayer film patterns is filled with the metal-containing film. (V-8) The metal-containing film covering the resist underlayer film on which the pattern is formed is etched back by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern is formed. (V-9) The resist intermediate film or the hard mask intermediate film remaining on the upper surface of the resist underlayer film is removed by dry etching. (V-10) The resist underlayer film on which the pattern with the exposed surface is formed is removed by dry etching, and an inverted pattern of the original pattern is formed on the metal-containing film. (V-11) Provided is a pattern formation method characterized by having a step of processing the substrate to be processed using the metal-containing film on which the inverted pattern is formed as a mask to form an inverted pattern on the substrate to be processed.

[0050] By the pattern formation method using the above-described inversion process, a finer pattern can be formed on the object to be processed with higher precision.

[0051] Also in this case, it is preferable to form the inorganic hard mask intermediate film by a CVD method or an ALD method.

[0052] When the inorganic hard mask is formed by a CVD method or an ALD method, a finer pattern can be formed on the object to be processed with higher precision.

Advantages of the Invention

[0053] As described above, the compound for forming a metal-containing film of the present invention is a polymer containing repeating units represented by the above general formulas (P-1) to (P-2). Since radicals are generated by radical cleavage of the Sn-alkyl bond, a crosslinking reaction occurs due to the radicals. Further, since it is a polymer containing repeating units, it is less likely to become a decomposition product with a low molecular weight that sublimates immediately when the bond is cleaved. Therefore, it can participate in the crosslinking reaction before decomposition progresses and sublimation, resulting in a compound with excellent heat resistance and capable of suppressing volume shrinkage that induces deterioration of film-forming properties and embedding properties. Therefore, even after high-temperature baking, a resist underlayer film material excellent in film-forming properties and embedding characteristics can be provided. Further, since at least one tin atom is contained in the repeating unit, the tin content is high. If the organic group of the repeating unit is designed compactly, the Sn content can be further increased, and a resist underlayer film material excellent in etching resistance can be provided.

[0054] In particular, in a fine patterning process using a multilayer resist method in a semiconductor device manufacturing process, even on a substrate to be processed having a portion where embedding / planarization is difficult, such as a dense portion of a high aspect ratio fine pattern structure typified by a DRAM memory with increasing miniaturization, it is possible to embed without causing defects such as voids or peeling. Further, since it has excellent dry etching resistance compared to conventional coating-type organic resist underlayer film materials, a finer pattern can be formed on the workpiece with higher accuracy compared to the organic resist underlayer film. In addition, the composition for forming a metal-containing film containing the compound for forming a metal-containing film of the present invention contains a tin atom with a large EUV light absorption, so there is a sensitizing effect by secondary electrons generated during exposure. Further, since the tin atom has a large atomic weight, it has a high effect of suppressing acid diffusion from the upper layer resist into the resist underlayer film, and has the characteristic that it can be made highly sensitive while maintaining the LWR performance originally possessed by the upper layer resist film.

Brief Description of the Drawings

[0055]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0056] As described above, in a fine patterning process using a multilayer resist method, there has been a demand for the development of a composition for forming a metal-containing film having excellent film-forming properties and etching resistance, which is used to form a resist underlayer film capable of transferring a resist pattern to a substrate to be processed with higher accuracy.

[0057] The present inventors focused on an organotin compound expected to play an active role in the EUV exposure generation and conducted intensive studies. As described above, a tin atom having a large EUV light absorption has a sensitizing effect by secondary electrons that will be generated during exposure, and has a characteristic that it can be made highly sensitive while maintaining the LWR performance originally possessed by the upper resist film. On the other hand, the organotin compound being studied as the upper resist film has poor heat resistance and causes a rapid volume shrinkage during baking, so it is difficult to form a uniform film or embed the step of the substrate to be processed when baked at a high temperature. The present inventors considered that if an organic molecule having a diol structure (including catechol) and a carboxylate in the molecule reacts with tin and is polymerized, there is a high possibility that a sufficient molecular weight can be maintained even if the bond is broken during baking, sublimates can be suppressed, heat resistance can be improved, and excellent film-forming properties and embedding properties can be exhibited. In addition, since at least one tin atom is contained in the repeating unit, the tin content is high, and the tin content can be further increased by suppressing the organic component in the repeating unit, and it is considered to be a composition for forming a metal-containing film exhibiting excellent etching resistance. Therefore, the present inventors have conducted further intensive studies and found that a metal-containing film-forming compound having a repeating unit represented by the above general formulas (P-1) to (P-2) has excellent film-forming properties and can further increase the tin content, resulting in a metal-containing film-forming compound having excellent etching resistance, and thus completed the present invention.

[0058] That is, the present invention relates to a metal-containing film-forming compound, wherein the compound is a polymer containing any one or both of the repeating units represented by the following general formulas (P-1) or (P-2). This compound can be used in a metal-containing film-forming composition that functions as a resist underlayer film material used in semiconductor manufacturing. [Chemical formula] (In the general formulas (P-1) and (P-2), R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, 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. W1 is a substituted or unsubstituted linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 40 carbon atoms, and the hydrocarbon group contains an oxygen atom, a nitrogen atom or a sulfur atom as a heteroatom, and may form an ether bond, a carbonyl group, an ester group or an amide group, and may form a heterocyclic structure through the heteroatom. R2 represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a hydroxyl group, an amino group or a halogen atom, s1 is an integer of 0 to 1, and n1 is an integer of 0 to 1. In addition, a plurality of these elements in the repeating unit may include different ones. W2 is a substituted or unsubstituted linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 40 carbon atoms, and the hydrocarbon group contains an oxygen atom, a nitrogen atom or a sulfur atom as a heteroatom, and may form an ether bond, a carbonyl group, an ester group or an amide group, and may form a heterocyclic structure through the heteroatom. s2 is an integer of 0 to 1. s3 is 1 or 2. When s3 is 1, R3 is a hydrogen atom or a hydrocarbon group having a hydroxyl group with 1 to 10 carbon atoms. When s3 is 2, R3 is an oxygen atom and together with the carbon atom to which it is bonded forms a carbonyl group, and W2 and R3 may be bonded to each other to form a ring structure. In addition, a plurality of these elements in the repeating unit may include different ones.)

[0059] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto. Although catechol (1,2-benzenediol) is included in diols, in this specification, a compound having a 1,2-benzenediol structure may be referred to as catechol, and other diols may be simply referred to as "diols".

[0060] <Compound for forming metal-containing film> The compound for forming a metal-containing film of the present invention is a compound for forming a metal-containing film that can be used in a composition for forming a metal-containing film, and is characterized in that the compound for forming a metal-containing film is a polymer containing a repeating unit represented by the following general formulas (P-1) to (P-2). The compound can be used in a composition for forming a metal-containing film that functions as a resist underlayer film material used in semiconductor manufacturing.

Chemical formula

[0061] In the above general formulas (P-1) and (P-2), R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, 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. In general formula (P-1), W1 is a substituted or unsubstituted linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 40 carbon atoms (including an aromatic ring group), and the hydrocarbon group contains an oxygen atom, a nitrogen atom, or a sulfur atom as a hetero atom, and may form an ether bond, a carbonyl group, an ester group, or an amide group, and may form a heterocyclic structure through the hetero atom. R2 represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a hydroxyl group, an amino group, or a halogen atom, s1 is an integer of 0 to 1, and n1 is an integer of 0 to 1. Also, a plurality of these elements in the repeating unit may be different. In general formula (P-2), W2 is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 40 carbon atoms, which may be substituted or unsubstituted (including an aromatic ring group), and the hydrocarbon group contains an oxygen atom, a nitrogen atom, or a sulfur atom as a heteroatom, and may form an ether bond, a carbonyl group, an ester group, or an amide group, and may form a heterocyclic structure through the heteroatom. s2 is an integer from 0 to 1. s3 is 1 or 2. When s3 is 1, R3 is a hydrogen atom or a hydrocarbon group having a hydroxyl group with 1 to 10 carbon atoms. When s3 is 2, R3 is an oxygen atom, and together with the carbon atom to which it is bonded, it forms a carbonyl group, and W2 and R3 may be bonded to each other to form a ring structure. Also, a plurality of these elements in the repeating unit may include different ones.

[0062] In the above general formulas (P-1) to (P-2), R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, 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 raw material availability, it is preferably an n-butyl group, a t-butyl group, an n-octyl group, or a benzyl group, more preferably an n-butyl group. Also, considering the ease of radical cleavage of the Sn-alkyl bond, the t-butyl group and the benzyl group are also preferable. In the following, for representing a primary as an alkyl group name, it may be described as n, and for representing a secondary and a tertiary, it may be described as s, t, or sec-, tert-, etc., respectively.

[0063] In the above general formula (P-1), W1 is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 40 carbon atoms (including an aromatic group), which may be substituted or unsubstituted. The hydrocarbon group contains an oxygen atom, a nitrogen atom or a sulfur atom as a hetero atom, and may form an ether bond, a carbonyl group, an ester group or an amide group. It may form a heterocyclic structure through the hetero atom such as through an amide group or an ester group. However, from the viewpoints of heat resistance and increasing the Sn content, it is preferable that W1 is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms which may contain a hydroxyl group or an amino group (the hydrocarbon group contains an oxygen atom, a nitrogen atom or a sulfur atom as a hetero atom and may form an ether bond, a carbonyl group or an ester group). s1 is an integer of 0 to 1. From the viewpoint of increasing the Sn content, it is preferable that s1 is 0. From the viewpoints of thermal fluidity and embeddability, it is preferable that s1 is 1 because an organic chain is preferably contained. When s1 is 0, it means that a carbonyl group is singly bonded.

[0064] More specifically, W1 is preferably a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms which may contain a hydroxyl group or an amino group (the hydrocarbon group contains an oxygen atom, a nitrogen atom or a sulfur atom as a hetero atom and may form an ether bond, a carbonyl group or an ester group) or any one of the groups represented by the following general formulas (W1-1) to (W1-4). [Chemical formula] (In the above general formulas (W1-1) to (W1-4), R W is a divalent organic group having 1 to 23 carbon atoms, and #1 and #2 each represent a bonding portion with an ester or a benzene ring.)

[0065] In the general formula (P-1) above, R2 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a hydroxyl group, an amino group, or a halogen atom, and is preferably a hydroxyl group from the viewpoint of thermosetting and from the viewpoint of disrupting the symmetry of the molecule.

[0066] More specific examples of (P-1) including W1 include, but are not limited to, the following formulas. (In the following formulas, R1, R w represents the same group as above, and the parentheses represent a repeating unit.)

Chemical formula

[0067] In the general formula (P-2) above, W2 is a substituted or unsubstituted linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 40 carbon atoms (including an aromatic group), the hydrocarbon group may contain an oxygen atom, a nitrogen atom, or a sulfur atom, and may form an ether bond, a carbonyl group, an ester group, or an amide group, and may form a heterocyclic structure via an amide group, an ester group, etc., but from the viewpoints of heat resistance and increasing the Sn content, W2 is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms (including an aromatic group) that may contain a hydroxyl group or an amino group (the hydrocarbon may contain an oxygen atom, a nitrogen atom, or a sulfur atom and may form an ether bond, a carbonyl group, or an ester group), which is preferable.

[0068] More specifically, W2 is preferably a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms (including an aromatic ring group) that may contain a hydroxyl group or an amino group, or a cyclic hydrocarbon group bonded to R3 (the hydrocarbon group may contain an oxygen atom, a nitrogen atom, or a sulfur atom and may form an ether bond, a carbonyl group, or an ester group), or any of the groups represented by the following general formulas (W2-1) to (W2-4).

Chemical formula

[0069] In the general formula (P-2) above, s2 is an integer of 0 to 1, s3 is 1 or 2. When s3 is 1, R3 is a hydrogen atom or a hydrocarbon group having a hydroxyl group with 1 to 10 carbon atoms. When s3 is 2, R3 is an oxygen atom and together with the carbon atom to which it is bonded forms a carbonyl group. W2 and R3 may be bonded to each other to form a ring structure. From the viewpoint of increasing the tin content, it is preferable that S2 is 0. From the viewpoints of thermal fluidity and embedability, it is better to contain an organic chain, so it is preferable that S2 is 1. Note that when s2 is 0, it means that the carbonyl group is singly bonded.)

[0070] Specific examples of (P-2) including W2 include, but are not limited to, the following formulas. (In the following formulas, R1, R w represents the same group as above, and the parentheses represent a repeating unit.) [Chemical formula]

[0071] In the general formulas (W1-1) to (W1-4) and (W2-1) to (W2-4) above, R W is a divalent organic group having 1 to 23 carbon atoms. Preferred structures of R W include, but are not limited to, the following structures (where * each represents a bonding portion with the carbon atom of the carbonyl group). [Chemical formula]

[0072] Furthermore, in the general formulas (W1-1) to (W1-4) and (W2-1) to (W2-4), R W is preferably an unsaturated hydrocarbon having 2 to 23 carbon atoms.)

[0073] A compound for forming a metal-containing film having such a structure can further improve the thermosetting property.

[0074] In the general formulas (W1-1) to (W1-4) and (W2-1) to (W2-4) above, R W is preferably a structure represented by the following general formula (1) from the viewpoints of improving the thermosetting property and the tin content.

Chemical formula

[0075] The carboxylic acid raw material containing the above general formula (1) can be synthesized by ring-opening a cyclic acid anhydride. However, when an asymmetric cyclic anhydrous carboxylic acid is ring-opened, it becomes a mixture of two types, resulting in the bonding form as described above. The presence of such isomers can suppress crystallinity, and an improvement in embedding properties due to an improvement in solvent solubility and an improvement in thermal fluidity can be expected. For example, in the ring-opening reaction between itaconic anhydride derivative shown below and 4-(2-aminoethyl)pyrocatechol, the product is different depending on whether the nucleophilic reaction of the amine occurs at the carbonyl adjacent to the unsaturated methylene group (>C=CH2) or at the carbonyl adjacent to the saturated methylene group (>CH2), resulting in a mixture of two isomers.

Chemical formula

[0076] From the viewpoint of increasing the tin content, it is preferable that the terminal structure of the polymer having the repeating units of the general formulas (P-1) to (P-2) is the following general formulas (T-1) to (T-2).

Chemical formula

[0077] If the terminal structures of the polymers having the repeating units of the above general formulas (P-1) to (P-2) are the above general formulas (T-1) to (T-2), since all of the repeating units and the terminal structures contain tin atoms, the tin content can be increased. In addition, since the tin-alkyl bond generates radicals by heat, the crosslinking reaction is promoted by the radicals. And since the thermosetting property can be enhanced, sublimates can be suppressed, and suppression of volume shrinkage that induces deterioration of embedability can also be expected. Thereby, after high-temperature baking, a metal-containing film-forming compound used for a resist underlayer film material excellent in film-forming property and etching resistance can be provided.

[0078] A polymer containing the repeating units represented by the above general formulas (P-1) to (P-2) and having terminals represented by the following general formulas (T-1) to (T-2) can be synthesized by performing a condensation reaction (STEP1) using a compound (X) containing both a normal adjacent hydroxyl group (hydroxyl groups adjacent via two carbon atoms) and a carboxylic acid and an alkyltin trichloride (Y), and then further condensing the obtained condensate with a carboxylic acid (T) having the (T-1) to (T-2) structure (STEP2). (R, R1, R2, R3, n1, s1, s2, W1, W2 are the same as above. In the following, s3 is taken as 1.)

Chemical formula

Chemical formula

[0079] In addition, the compound of the unit represented by (T) used in the above (STEP2) can be synthesized by condensing 1 equivalent each of a compound (X) containing both a hydroxyl group adjacent to a tin compound such as dialkyltin dichloride or dialkyltin oxide (Z’) (a hydroxyl group adjacent via two carbon atoms) and a carboxylic acid (Reaction 1). (R1, R2, R3, n1, s1, s2, W1, W2 are the same as described above.)

[0080] General formula for the condensation of dialkyltin oxide (Z’) and catechol derivative (X)

Chemical formula

[0081] General formula for the condensation of dialkyltin dichloride (Z’) and diol derivative (X) (s3 = 1)

Chemical formula

[0082] Moreover, from the viewpoint of solubility, it is preferable that the terminal structure of the polymer having the repeating units of the above general formulas (P-1) to (P-2) is *-OC(=O)R (R is a monovalent organic group, and * represents the bonding part with the Sn atom in the polymer).

[0083] If the terminal structure of the polymer having the repeating units of the above general formulas (P-1) to (P-2) is *-OC(=O)R (R is a monovalent organic group, and * represents the bonding part with the Sn atom in the polymer), since R can be freely changed, if a bulky structure is incorporated, an improvement in solubility can be expected. Furthermore, since it is also possible to have a crosslinked structure, sublimates can be further suppressed, and suppression of volume shrinkage that induces deterioration of embedability can also be expected. Thereby, even after high-temperature baking, a resist underlayer film material excellent in film-forming properties can be provided.

[0084] The polymer containing the repeating units represented by the general formulas (P-1) to (P-2) and having a terminal of *-OC(=O)R (where R is a monovalent organic group and * represents the bonding part with the Sn atom in the polymer) can be synthesized by performing a condensation reaction (STEP1) using a compound (X) containing both a hydroxyl group (hydroxyl groups adjacent through two carbon atoms) and a carboxylic acid, and alkyltin trichloride (Y), and then further condensing the resulting condensate with a carboxylic acid (Z) (STEP2). (R, R1, R2, R3, n1, s1, s2, W1, W2 are the same as above.)

Chemical formula

Chemical formula

[0085] Also, the usage amount of (X) when performing the above (STEP1) is preferably 0.6 to 0.95 equivalents, more preferably 0.7 to 0.9 equivalents, relative to (Y). Therefore, after the completion of (STEP1), some of the Sn-Cl bonds not consumed in the polymerization will remain. Therefore, the usage amounts of (T) and (Z) are preferably an amount that can react with the remaining residues, so it is preferably 0.15 to 1.2 equivalents, more preferably 0.3 to 0.9 equivalents. For example, considering the reaction of 0.9 equivalents of 3,4-dihydroxybenzoic acid as (X) and 1.0 equivalent of alkyltin trichloride as (Y) as shown in the following formula, 0.3 equivalents of Sn-Cl bonds not consumed in the polymerization will remain. These remaining residues of Sn-Cl bonds can be further condensed by the above (STEP2). As an example of (STEP2), the reaction of the condensate of (STEP1) with methacrylic acid is shown. When the carboxylic acid used in (STEP2) is changed to (T), a polymer having a structure represented by (T-1) to (T-2) at the terminal is obtained.

Chemical formula

[0086] Also, the condensation reaction (STEP1) using the above (X) and (Y), and the condensation reaction (STEP2) using the condensate obtained in STEP1 and (T) or (Z) can usually be carried out without a solvent or in a solvent at room temperature or, if necessary, under cooling or heating. As the solvent to be used, ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, chlorine-based solvents such as methylene chloride, chloroform, dichloroethane, trichloroethylene, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene, nitriles such as acetonitrile, ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone, esters such as ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, lactones such as γ-butyrolactone, aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, etc. can be exemplified, and these can be used alone or in combination of two or more. These solvents can be used in the range of 0 to 3000 parts by mass with respect to 100 parts by mass of the reaction raw material.

[0087] Also, a base catalyst can be added as a catalyst. As the base catalyst to be used, inorganic salts such as potassium carbonate and sodium hydroxide can be used, but since it is difficult to remove them, it is preferable to use organic bases such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine. The amount of use is preferably 2.5 to 3.5 equivalents with respect to trichlorostannum, and more preferably 3.0 to 3.2 equivalents. The reaction temperature is preferably from -50°C to about the boiling point of the solvent, and more preferably from room temperature to 130°C.

[0088] As the condensation reaction method (STEP1), there are methods such as charging (X) and (Y) all at once, dropping (Y) into (X), or dropping (X) or a solution of (X) dissolved in a reaction solvent into (Y). After the completion of the condensation reaction in STEP1, in order to remove unreacted raw materials, catalysts, etc., the temperature of the reaction kettle is raised to 130 - 230 °C, and the volatile components are removed at about 1 - 50 mmHg, or steps such as fractionating the impurities and the obtained polymer using an appropriate poor solvent or good solvent can be added. Usually, however, after the completion of STEP1, the reaction in (STEP2) can also be carried out by continuously adding (T) or (Z) to the reaction system. After the completion of the condensation reaction in (STEP2), a step of removing impurities and the like can be added in the same manner as the above purification method.

[0089] If the terminal structure of the polymer having the repeating units of the above general formulas (P-1) - (P-2) is *-OC(=O)R (R is a monovalent organic group, and * represents the bonding part with the Sn atom in the polymer), since R can be freely changed, if a bulky structure is incorporated, improvement in solubility and thermal fluidity can be expected. Furthermore, since it is also possible to have a crosslinked structure, sublimates can be suppressed, and suppression of volume shrinkage that induces deterioration of embedability can also be expected. As the carboxylic acid raw material containing R, for example, a linear substituted or unsubstituted hydrocarbon group such as acetic acid, propionic acid, or glycine, or a branched substituted or unsubstituted hydrocarbon group such as pivalic acid or 2-aminoisobutyric acid, or a cyclic substituted or unsubstituted hydrocarbon group such as cyclopropanecarboxylic acid or 3,3-difluorocyclobutanecarboxylic acid, etc., any monofunctional carboxylic acid is not particularly limited. From the viewpoint of thermosetting properties, more preferably, it is a group containing an unsaturated hydrocarbon group, a group containing a hydroxyl group, a group in which a protecting group is eliminated by heat or an acid to generate a hydroxyl group or a carboxy group.

[0090] Also, in the above R, R is preferably represented by the following general formulas (A-1) - (A-4) or the following general formula (3) or the following general formula (4).

Chemical formula

[0091] In the general formulas (A-1) to (A-4) above, Y A1 , Y A2 may be the same as or different from each other, and is a substituted or unsubstituted divalent organic group having 1 to 23 carbon atoms and being saturated or having 2 to 23 carbon atoms and being unsaturated (preferably a hydrocarbon group), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkylene group having 7 to 31 carbon atoms. R A is a hydrogen atom, a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms and being saturated or having 2 to 20 carbon atoms and being unsaturated (such as an aliphatic hydrocarbon group), 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 R A1is an organic group in which the protecting group is eliminated by the action of either or both of the above general formula (2) acid and heat to generate one or more hydroxyl groups or carboxyl groups, preferably (A-4) in consideration of the heat fluidity, and preferably (A-1) from the viewpoint of increasing the tin content rate.

[0092] In the above general formulas (A-1) to (A-4), Y A2 Preferred structures thereof include, for example, the following structures, but are not limited thereto. (In the following formulas, * a is the bonding part with R A1 and * b represents the other bonding part.

Chemical formula

[0093] In the above general formula (A-3), R A is a hydrogen atom, a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms that is saturated or having 2 to 20 carbon atoms that is unsaturated (such as an aliphatic hydrocarbon group), 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 is preferably a hydrogen atom from the viewpoints of suppressing sublimates and increasing the Sn content rate.

[0094] In the above general formula (2), R A2 is an organic group in which a protecting group (thermoacid labile group) is eliminated by the action of either or both of an acid and heat, preferably a tertiary hydrocarbyl group or a group that forms an acetal structure together with an adjacent oxygen atom, and particularly preferably a tertiary hydrocarbyl group.

[0095] As the above tertiary hydrocarbyl group, those having 4 to 20 carbon atoms are preferable, and a tert-butyl group is particularly preferable from the viewpoints of suppressing sublimates by pyrolysis products and ease of raw material procurement. Specific examples include, but are not limited to, those shown below. In the following formulas, * represents a bond with an oxygen atom.

Chemical formula

[0096]

Chem.

[0097]

Chem.

[0098]

Chem.

[0099] Examples of the group forming the acetal structure include those represented by the following formula (L1) described later. Specific examples of the group forming the acetal structure include, but are not limited to, those shown below. In the following formulas, * represents a bond to an oxygen atom.

Chem.

[0100]

Chem.

[0101]

Chem.

[0102] Such a compound for forming a metal-containing film will be a compound for forming a metal-containing film excellent in solvent solubility and thermal fluidity. Also, R A1Since it contains an organic group in which a protecting group is eliminated by the action of either or both of a bulky acid and heat in the structure, when it is used in a composition for forming a metal-containing film, they are eliminated during baking, so the tin content increases, and it becomes a compound for forming a metal-containing film excellent in dry etching resistance. Further, the hydroxyl group and carboxyl group generated by the elimination easily react with the radicals generated by the cleavage of the tin-carbon bond during baking due to the presence of the terminal OH group and α-hydrogen, and a crosslinking reaction occurs, and since it is excellent in thermosetting, volume shrinkage can be suppressed, and even after high-temperature baking, a composition for forming a metal-containing film such as a resist underlayer film material excellent in film-forming property and embedding property can be provided.

Chemical formula

Chemical formula

Chemical formula

[0103] In the above general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, B is the above general formula (B), and * represents the bonding portion with the carbonyl group. In the above general formula (B), Y Bis a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms and being saturated or having 2 to 20 carbon atoms and being unsaturated (such as an aliphatic hydrocarbon group), a substituted or unsubstituted divalent arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent arylalkylene group having 7 to 31 carbon atoms, and R B is preferably a hydroxyl group or any of the structures represented by the above general formulas (B-1) to (B-3). Further, in the above general formulas (B-1) to (B-3), R B1 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and is preferably a hydrogen atom from the viewpoint of suppressing sublimation.

[0104] Preferred structures of the above general formula (B) include, for example, the following structures, but are not limited thereto. In the following formulas, * represents a bond to a carbonyl group. [Chemical formula]

[0105] For such a compound for forming a metal-containing film, it becomes a compound for forming a metal-containing film excellent in solvent solubility and thermal fluidity. Further, since R B contains a hydroxyl group or an unsaturated bond therein, when it is used in a composition for forming a metal-containing film, they undergo a crosslinking reaction during baking, so it is excellent in thermosetting properties. Furthermore, by reacting with radicals generated by the cleavage of the tin-carbon bond, the crosslinking reaction is promoted, and since it is excellent in thermosetting properties, volume shrinkage can be suppressed, and even after high-temperature baking, a composition for forming a metal-containing film excellent in film-forming properties and planarization / embedding properties can be provided.

[0106] [Chemical formula] (In the above general formula (4), X is a divalent organic group having 1 to 31 carbon atoms, C is the following general formulas (C-1) to (C-4), and * represents a bonding portion to a carbonyl group.) [Chemical formula] (In the above general formulas (C-1) and (C-3), RC1 is a hydrogen atom or a methyl group, and in the same formula, they may be the same as or different from each other. Among (C-3) to (C-4), R C2 is a hydrogen atom or a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms (such as an aliphatic hydrocarbon group), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. * represents the bonding part with the carbonyl group.)

[0107] In the general formula (4) above, X is a divalent organic group having 1 to 31 carbon atoms. Specifically, it includes a substituted or unsubstituted saturated divalent hydrocarbon group having 1 to 23 carbon atoms or an unsaturated divalent hydrocarbon group having 2 to 23 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkylene group having 7 to 31 carbon atoms, and the like. C is a group represented by the general formula (C-1) to (C-4). In (C-1) and (C-3), R C1 is preferably a methyl group from the viewpoint of thermal fluidity and preferably a hydrogen atom from the viewpoint of curability. Also, in (C-3) and (C-4), R C2 preferably has the structures described above other than a hydrogen atom from the viewpoint of thermal fluidity.

[0108] In the general formulas (C-1) to (C-4) above, R C2 As preferred structures, for example, the following structures can be given, but are not limited thereto. In the following formulas, * represents a bond with a nitrogen atom.

Chemical formula

[0109] For a metal-containing film-forming compound having such a structure, since it contains an organic group represented by the general formula (4) above, it becomes a metal-containing film-forming compound excellent in solvent solubility and heat resistance characteristics. Furthermore, since it contains any of the structures represented by the general formulas (C-1) to (C-4) at the terminal, the crosslinking group density is high, and a rapid volume shrinkage during baking can be reduced. Also, because of its good thermal fluidity, a metal-containing film-forming composition excellent in embedding / planarization characteristics can be provided.

[0110] (P-1) or a compound or polymer containing an Sn-C bond as in (P-2) generates radicals while the Sn-C bond dissociates, and the resulting radicals cause the curing reaction to proceed (Equation 1). On the other hand, since the recombination of radicals is necessary to promote the curing reaction, it takes time for curing, or it is necessary to increase the radical generation efficiency at high temperatures. The polymer of the present invention contains at least one tin atom in the repeating unit and contains an Sn-C bond, so multiple radicals are generated within one molecule, increasing the radical generation efficiency and the possibility of recombination, resulting in excellent curability. Furthermore, since it is a polymer, recombination of radicals occurs faster than decomposition into low molecules that would sublime, and it also has excellent heat resistance. Also, as described above, by introducing an organic group having an unsaturated group or a hydroxyl group at the terminal or in the main chain, not only do they serve as radical acceptors, but the unsaturated groups also undergo thermal crosslinking among themselves, resulting in a film with even better curability. (Equation 2). As a result, sublimates due to thermal decomposition can also be suppressed, and a resist underlayer film material excellent in film-forming properties and embedding properties can be provided.

Chemical formula

Chemical formula

[0111] Y in the general formulas (A-1) to (A-4) above A1 , Preferred structures for X in the general formula (3) above or X in the general formula (4) above include, for example, the following structures, but are not limited thereto. In the following formulas, * represents the bonding portion with the carbon atom of the carbonyl group or * in the general formulas (A-1) to (A-4), formula (3), and formula (4).

Chemical formula

[0112] Y in the general formulas (A-1) to (A-4) above A1It is preferable that the compound for forming a metal-containing film is such that X in the general formula (3) or X in the general formula (4) is an unsaturated hydrocarbon group having 2 to 23 carbon atoms.

[0113] Y in the general formulas (A-1) to (A-4) A1 If X in the general formula (3) or X in the general formula (4) is an unsaturated hydrocarbon group having 2 to 23 carbon atoms, the thermosetting property of the compound for forming a metal-containing film can be further improved.

[0114] Also, Y in the general formulas (A-1) to (A-4) A1 A metal-containing film-forming compound can be provided in which X in the general formula (3) or X in the general formula (4) is the following general formula (1). [Chemical formula] (In the general formula (1), R a , R b and R c are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R a and R b may be bonded to form a cyclic substituent. *1 and *2 each represent a bonding portion to a carbonyl group, and *1 and *2 may be reversed.)

[0115] The carboxylic acid raw material containing the general formula (1) can be synthesized by ring-opening an acid anhydride. However, when an asymmetric anhydrous carboxylic acid is ring-opened, a mixture of two types is formed, resulting in the bonding form as described above. The presence of such isomers can suppress crystallinity, and an improvement in flatness characteristics can be expected due to an improvement in solvent solubility and an improvement in thermal fluidity. [Chemical formula]

[0116] In the general formula (1), R a , R b and R c are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R a and R bmay combine to form a cyclic substituent, and from the viewpoint of suppressing sublimation products, it is particularly preferably a hydrogen atom.

[0117] The ratio Mw / Mn (i.e., dispersity) of the weight average molecular weight Mw and the number average molecular weight Mn in terms of polystyrene by gel permeation chromatography (GPC) method using tetrahydrofuran of the compound for forming a metal-containing film is preferably more than 1.50, and more preferably 1.80 or more. By definition, for a monomolecular compound, Mw / Mn is 1.00, but due to the separation property of GPC, the measured value may exceed 1.00. Generally, for a polymer having repeating units, it is extremely difficult to approach Mw / Mn = 1.00 unless a special polymerization method is used, and it has a distribution of Mw and Mw / Mn becomes a value exceeding 1. In the present invention, Mw / Mn > 1.50 is defined as an index indicating a polymer in order to distinguish between a monomolecular compound and a polymer. Note that the above index can also be applied to a mixture of two or more kinds of compounds for forming a metal-containing film.

[0118] <Composition for forming a metal-containing film> Further, the present invention can provide a composition for forming a metal-containing film that functions as a resist underlayer film material used in semiconductor manufacturing, which contains (a) the compound for forming a metal-containing film of the present invention and (b) an organic solvent.

[0119] For such a composition for forming a metal-containing film, since it contains an organotin compound excellent in heat resistance and thermal fluidity, it has excellent dry etching resistance against conventional organic underlayer film materials and can form a metal-containing film such as a resist underlayer film having high embedding / planarization characteristics.

[0120] Hereinafter, components contained in the composition for forming a metal-containing film of the present invention other than the above (a) compound for forming a metal-containing film will be described.

[0121] <(b) Organic solvent> As the (b) organic solvent that can be used in the composition for forming a metal-containing film of the present invention, there is no particular limitation as long as it can dissolve or disperse the above-mentioned (a) compound for forming a metal-containing film, (c) crosslinking agent, (d) surfactant, (e) fluidity promoter, (f) acid generator, and other additives.

[0122] Specifically, the organic solvents described in paragraphs

[0091] to

[0092] of JP-A-2007-199653 can be added. More specifically, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and γ-butyrolactone, or a mixture containing one or more of these is preferably used.

[0123] (High-boiling solvent) In the above composition for forming a resist underlayer film, the (b) organic solvent may be used as a mixture of one or more organic solvents having a boiling point (the value at 1 atmospheric pressure (1013 hPa)) of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher (high-boiling solvents).

[0124] As the high-boiling solvent, there are no particular restrictions as long as it can dissolve or disperse each component of the composition for forming a metal-containing film of the present invention, and examples include hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc. 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 butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples thereof include 6 - hexanediol diacetate, triethylene glycol diacetate, γ - butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc., and these may be used alone or in combination.,

[0125] The high - boiling solvent may be appropriately selected from the above - mentioned ones according to the temperature for heat - treating the above - mentioned resist underlayer film - forming composition, etc. The boiling point of the high - boiling solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. With such a boiling point, there is no fear that the volatilization during baking (heat - treatment) will be too fast, so sufficient thermal fluidity can be obtained during film formation, and it is considered that a resist underlayer film with excellent embedding / planarization characteristics can be formed. Also, with such a boiling point, it will not remain in the film without volatilizing after baking, so there is no fear of adversely affecting the film physical properties such as etching resistance.,

[0126] The blending amount of the organic solvent is preferably in the range of 200 to 10,000 parts, more preferably 250 to 5,000 parts, per 100 parts by mass of the compound for forming the metal - containing film (a).

[0127] Also, when using a high - boiling solvent, the blending amount is preferably 1 to 30 parts by mass per 100 parts by mass of the organic solvent having a boiling point of less than 180°C. With such a blending amount, sufficient thermal fluidity can be imparted during baking, and it does not remain in the film and does not lead to deterioration of film physical properties such as etching resistance, so it is preferable.,

[0128] <Resist underlayer film - forming composition> The above - mentioned composition is a composition for forming a metal - containing film that can be used as a resist underlayer film for the multilayer resist method, and can further be a resist underlayer film - forming composition containing one or more of (c) cross - linking agent, (d) surfactant, (e) fluidity promoter, and (f) acid generator., Hereinafter, the components contained in the above-mentioned (a) compound for forming a metal-containing film and the above-mentioned composition for forming a resist underlayer film other than the organic solvent will be described.

[0129] [(c) Crosslinking agent] The composition for forming a resist underlayer film may further contain (c) a crosslinking agent in order to enhance the film density and further suppress the intermixing with the resist upper layer film. The crosslinking agent is not particularly limited, and various known types of crosslinking agents can be widely used. As an example, melamine-based crosslinking agents, acrylate-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, phenol-based crosslinking agents (for example, methylol or alkoxymethyl type crosslinking agents of polynuclear phenols), epoxy-based crosslinking agents, and oxetane-based crosslinking agents can be exemplified. The content of the (c) crosslinking agent is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the (a) compound for forming a metal-containing film.

[0130] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxy-substituted products, and their partial self-condensates. Specific examples of the acrylate-based crosslinking agent include dipentaerythritol hexaacrylate. Specific examples of the glycoluril-based crosslinking agent include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, their alkoxy and / or hydroxy-substituted products, and their partial self-condensates. Specific examples of the benzoguanamine-based crosslinking agent include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy-substituted products, and their partial self-condensates. As the urea-based crosslinking agent, specifically, dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates can be exemplified. As the β-hydroxyalkylamide-based crosslinking agent, specifically, N,N,N’,N’-tetrakis(2-hydroxyethyl) adipic acid amide can be exemplified. As the isocyanurate-based crosslinking agent, specifically, triglycidyl isocyanurate and triallyl isocyanurate can be exemplified. As the aziridine-based crosslinking agent, specifically, 4,4’-bis(ethyleneiminocarbonylamino) diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl) propionate] can be exemplified. As the oxazoline-based crosslinking agent, specifically, 2,2’-isopropylidene bis(4-benzyl-2-oxazoline), 2,2’-isopropylidene bis(4-phenyl-2-oxazoline), 2,2’-isopropylidene bis(4-phenyl-2-oxazoline), 2,2’-methylene bis-4,5-diphenyl-2-oxazoline, 2,2’-methylene bis-4-phenyl-2-oxazoline, 2,2’-methylene bis-4-tert-butyl-2-oxazoline, 2,2’-bis(2-oxazoline), 1,3-phenylene bis(2-oxazoline), 1,4-phenylene bis(2-oxazoline), and 2-isopropenyl oxazoline copolymer can be exemplified.

[0131] As the polynuclear phenol-based crosslinking agent, specifically, the compound represented by the following general formula (XL-1) can be exemplified.

Chemical formula

[0132] S is a single bond or an s-valent hydrocarbon group having 1 to 20 carbon atoms. s is an integer of 1 to 5, and more preferably 2 or 3. Specific examples of S include groups obtained by removing s 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. R4 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, octyl group, ethylhexyl group, decyl group, and eicosanyl group, and a hydrogen atom or a methyl group is preferred.

[0133] As examples of the compound represented by the general formula (XL-1), specifically, the following compounds can be exemplified. Among these, hexamethoxymethylated compounds of triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the viewpoints of the curability of the organic film and the improvement of film thickness uniformity. R4 is the same as described above.

[0134]

Chemical formula

[0135]

Chemical formula

[0136] Examples of the epoxy-based crosslinking agent and oxetane-based crosslinking agent include monomer type and polymer type. Specific examples of the monomer type include those shown below, but are not limited thereto.

Chemical formula

[0137] Although the above compounds can be purchased, epoxy crosslinking agents and oxetane crosslinking agents can also be obtained by reacting hydroxyl groups with epibromohydrin, 3-bromomethyloxetane, etc. as shown in the following formula. In the following formula, R5 is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, saturated or 2 to 20 carbon atoms unsaturated, 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. Also, it is possible to leave some hydroxyl groups unreacted. At this time, it is preferable that the number of epoxy + oxetane > the number of hydroxyl groups, and more preferably the number of epoxy + oxetane > the number of hydroxyl groups × 2. Also, the content of these compounds is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass, based on 100 parts by mass of the compound for forming the metal-containing film in (a) above.

Chemical formula

[0138] Specific examples of the compound having a hydroxyl group that can be used in the above reaction include, but are not limited to, the following.

Chemical formula

[0139] As the polymer type, specifically, polymers in which the molar fraction of the repeating units represented by the following general formulas (XL-2) and (XL-3) is 20% or more can be mentioned. When the total molar fraction of the structural units represented by the general formulas (XL-2) and (XL-3) does not reach 100%, as other structural units, other acrylic acid esters, other methacrylic acid esters, other acrylamides, other methacrylamides, crotonic acid esters, maleic acid esters, itaconic acid esters, etc. α,β-unsaturated carboxylic acid esters; α,β-unsaturated carboxylic acids such as methacrylic acid, acrylic acid, maleic acid, itaconic acid; acrylonitrile; methacrylonitrile; α,β-unsaturated lactones such as 5,5-dimethyl-3-methylene-2-oxotetrahydrofuran; norbornene derivatives, tetracyclo[4.4.0.1 2,5 .1 7,10 dodecene derivatives and other cyclic olefins; α,β-unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride; allyl ethers; vinyl ethers; vinyl esters; any structural units derived from vinyl silanes can be used in combination. Further, these polymers preferably have a weight average molecular weight of 1,000 to 20,000 and a GPC dispersity (Mw / Mn) of 2.0 or less. Further, the content of these compounds is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the compound (A) for forming a metal-containing film. In addition, as the molecular weight and dispersity, the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene by GPC using tetrahydrofuran as an eluent may be determined, and the dispersity (Mw / Mn) may be determined.

Chemical formula

[0140] In the general formula (XL-2) above, R7 preferably has the number of groups of (2-1) to (2-3) > the number of hydrogen atoms from the viewpoint of curability, and more preferably, the number of groups of (2-1) to (2-3) > 2 × the number of hydrogen atoms.

Chemical formula

Chemical formula

[0141] <(d) Surfactant> In the above composition for forming a resist underlayer film, a (d) surfactant can be added to improve the coatability in spin coating. As the surfactant, for example, those described in JP-A-2009-269953 can be used.

[0142] ~ those described in

[0147] can be used. When adding a surfactant, the addition amount is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, based on 100 parts by mass of the above (a) metal-containing film-forming compound.

[0142] <(e) Fluidity promoter> Also, the above composition for forming a resist underlayer film can further blend another compound or polymer. The fluidity promoter is mixed with the metal-containing film-forming compound of the present invention and has the role of improving the film-forming property of spin coating and the embedding property on a substrate having a step. Also, as the fluidity promoter, a material having a high carbon atom density and high etching resistance is preferable.

[0143] Such materials include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-tert-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, pyrogallol, thymol, isothymol, 4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-dimethyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-diallyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-difluoro-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-diphenyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-dimethoxy-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,3,2',3'-tetrahydro-(1,1')-spirobiinden-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiinden-6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiinden-6,6'-diol, 2,3,2',3'-tetrahydro-(1,1')-spirobiinden-5,5'-diol, 5,5'-dimethyl-3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, and dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, methyl 3-hydroxynaphthalene-2-carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene, limonene, etc., novolak resins, polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly(meth)acrylate, and copolymers thereof. Further, a naphthol dicyclopentadiene copolymer described in JP-A-2004-205685, a fluorene bisphenol novolak resin described in JP-A-2005-128509, an acenaphthylene copolymer described in JP-A-2005-250434, a fullerene having a phenol group described in JP-A-2006-227391, a bisphenol compound and its novolak resin described in JP-A-2006-293298, a novolak resin of an adamantane phenol compound described in JP-A-2006-285095, a bisnaphthol compound and its novolak resin described in JP-A-2010-122656, a fluorene compound described in JP-A-2017-119671, a fullerene resin compound described in JP-A-2008-158002, etc. can also be blended. The blending amount of the above fluidity promoter is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 50 parts by mass, based on 100 parts by mass of the metal-containing film-forming compound of the present invention.,

[0144] In addition, in the composition for forming a resist underlayer film, as an additive for imparting embedding / planarization characteristics, for example, polyethylene glycol, a liquid additive having a polypropylene glycol structure, or a thermal decomposable polymer having a weight loss rate of 40% by mass or more between 30°C and 250°C and a weight average molecular weight of 300 to 200,000 is preferably used. This thermal decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formulas (DP1) and (DP1a).

[0145]

Chemical formula

[0146]

Chemical formula

[0147] <(f) Acid generator> In order to further promote the desorption reaction, a (f) acid generator can be added to the composition for forming a resist underlayer film. The (f) acid generator includes those that generate acid by thermal decomposition and those that generate acid by light irradiation, and any of them can be added. Specifically, the materials described in paragraphs

[0061] to

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

[0148] The above acid generator can be used alone or in combination of two or more. When adding the acid generator, the addition amount is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, based on 100 parts by mass of the above (a) compound for forming a metal-containing film.

[0149] <Method for forming a resist underlayer film> In the present invention, there is provided a method for forming a filling film that functions as a resist underlayer film of a multilayer resist film used in lithography or a planarizing film for semiconductor manufacturing, using the above-described composition for forming a metal-containing film.

[0150] In the method for forming a resist underlayer film using the composition for forming a metal-containing film of the present invention, the above-described composition for forming a metal-containing film is coated on 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 the resist intermediate film. The baking is preferably performed in the range of 100°C or higher and 600°C or lower, for 10 to 600 seconds, more preferably in the range of 200°C or higher and 500°C or lower, for 10 to 300 seconds. Considering the influence on device damage and wafer deformation, the upper limit of the heating temperature in the wafer process of lithography is preferably 600°C or lower, more preferably 500°C or lower.

[0151] Further, in the method for forming a resist underlayer film using the composition for forming a metal-containing film of the present invention, the composition for forming a metal-containing film of the present invention is coated on a substrate to be processed by the spin coating method or the like as described above, and the composition for forming a metal-containing film is baked and cured in an atmosphere having an oxygen concentration of 0.1% by volume or more and 21% by volume or less to form a metal-containing film.

[0152] By firing the composition for forming a metal-containing film of the present invention in such an oxygen atmosphere, a sufficiently cured film can be obtained. The atmosphere during baking may be air, but it is preferable to enclose an inert gas such as N2, Ar, or He to reduce oxygen in order to prevent oxidation of the metal-containing film. In order to prevent oxidation, it is necessary to control the oxygen concentration, preferably 1000 ppm or less, more preferably 100 ppm or less (volume basis). Preventing oxidation of the metal-containing film during baking is preferable because it does not cause an increase in absorption or a decrease in etching resistance.

[0153] <Pattern formation method using a composition for forming a resist underlayer film> Further, in the present invention, as a pattern formation method by a two-layer resist process using the above composition for forming a metal-containing film, a metal-containing film is formed on a substrate to be processed using the above composition for forming a metal-containing film, and a resist upper layer film is formed on the metal-containing film using a photoresist material. After the resist upper layer film is pattern-exposed, it is developed with a developer to form a pattern in the resist upper layer film. Using the resist upper layer film in which the pattern is formed as a mask, the pattern is transferred to the metal-containing film by dry etching, and the substrate to be processed is processed using the metal-containing film in which the pattern is formed as a mask to form a pattern on the substrate to be processed. A pattern formation method is provided.

[0154] Since the resist upper layer film of the two-layer resist process exhibits etching resistance to chlorine-based gases, in the two-layer resist process, it is preferable to perform dry etching of the metal-containing film using the resist upper layer film as a mask using an etching gas mainly composed of a chlorine-based gas.

[0155] In the present invention, as a pattern formation method by a three-layer resist process using such a composition for forming a metal-containing film, a metal-containing film is formed on a substrate to be processed using the composition for forming a metal-containing film, and a resist intermediate film (silicon-containing resist intermediate film) is formed on the metal-containing film using a resist intermediate film material such as a silicon-containing resist intermediate film. A resist upper layer film is formed on the resist intermediate film using a photoresist material. After the resist upper layer film is pattern-exposed, it is developed with a developer to form a pattern in the resist upper layer film. Using the resist upper layer film with the pattern formed as a mask, the pattern is transferred to the resist intermediate film by dry etching. Using the resist intermediate film with the pattern transferred as a mask, the pattern is transferred to the metal-containing film by dry etching. Using the metal-containing film with the pattern formed as a mask, the substrate to be processed is processed to form a pattern on the substrate to be processed. A pattern formation method is provided. Hereinafter, the case where a silicon-containing resist intermediate film is used as the resist intermediate film will be described as an example.

[0156] An example of the three-layer resist process will be specifically shown with reference to FIG. 1 as follows. In the case of the three-layer resist process, as shown in FIG. 1(A), after forming a metal-containing film (metal-containing resist lower layer film) 3 on a processed layer 2 laminated on a substrate to be processed 1 using the composition for forming a metal-containing film of the present invention, a silicon-containing resist intermediate film 4 is formed, and a resist upper layer film 5 is formed thereon.

[0157] Next, as shown in FIG. 1(B), the required portion (exposed portion) 6 of the resist upper layer film 5 is exposed, and PEB and development are performed to form a resist upper layer film pattern 5a (FIG. 1(C)). Using this obtained resist upper layer film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is etched using a CF-based gas to form a silicon-containing resist intermediate film pattern 4a (FIG. 1(D)). After removing the resist upper layer film pattern 5a, the metal-containing film 3 is chlorine plasma-etched using this obtained silicon-containing resist intermediate film pattern 4a as a mask to form a metal-containing film pattern (metal-containing resist lower layer film pattern) 3a (FIG. 1(E)). Further, after removing the silicon-containing resist intermediate film pattern 4a, the layer to be processed 2 is etched using the metal-containing film pattern 3a as a mask to form a pattern 2a in the layer to be processed (FIG. 1(F)).

[0158] Since the silicon-containing resist intermediate film of the above three-layer resist process exhibits etching resistance to chlorine-based gases and hydrogen-based gases, in the above three-layer resist process, it is preferable to perform dry etching of the metal-containing film using the silicon-containing resist intermediate film as a mask and using an etching gas mainly composed of a chlorine-based gas or a hydrogen-based gas.

[0159] As the silicon-containing resist intermediate film of the above three-layer resist process, a polysiloxane-based intermediate film is also preferably used. By giving the silicon-containing resist intermediate film an antireflection effect, reflection can be suppressed. In particular, for 193 nm exposure, when a material containing many aromatic groups as an organic film and having a high etching selectivity with respect to the substrate is used, the k value becomes high and the substrate reflection becomes high. However, by giving an absorption such that an appropriate k value is obtained as the silicon-containing resist intermediate film, it becomes possible to suppress reflection and the substrate reflection can be made 0.5% or less. As the silicon-containing resist intermediate film having an antireflection effect, polysiloxane having an anthracene for 248 nm and 157 nm exposure and a phenyl group or an absorptive group having a silicon-silicon bond pendent and crosslinking with an acid or heat is preferably used for 193 nm exposure.

[0160] In addition, in the present invention, as a pattern formation method by a four-layer resist process using such a composition for forming a metal-containing film, a metal-containing film is formed on a substrate to be processed using the composition for forming a metal-containing film, a silicon-containing resist intermediate film is formed on the resist lower layer film using a silicon-containing resist intermediate film material, an organic anti-reflection film (BARC) or an adhesion film is formed on the silicon-containing resist intermediate film, a resist upper layer film is formed on the BARC using a photoresist material, after the resist upper layer film is pattern-exposed, it is developed with a developer to form a pattern in the resist upper layer film, using the resist upper layer film in which the pattern is formed as a mask, the pattern is transferred to the BARC or the adhesion film and the silicon-containing resist intermediate film by dry etching, using the silicon-containing resist intermediate film in which the pattern is transferred as a mask, the pattern is transferred to the metal-containing film by dry etching, and using the metal-containing film in which the pattern is formed as a mask, the substrate to be processed is processed to form a pattern on the substrate to be processed, thereby providing a pattern formation method.

[0161] Alternatively, an inorganic hard mask may be formed instead of the silicon-containing resist lower layer film. In this case, at least, a metal-containing film is formed on the object to be processed using the composition for forming a metal-containing film of the present invention, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the metal-containing film, a resist upper layer film is formed on the inorganic hard mask using a photoresist composition, a circuit pattern is formed in the resist upper layer film, the inorganic hard mask is etched using the resist upper layer film in which the pattern is formed as a mask, the metal-containing film is etched using the inorganic hard mask in which the pattern is formed as a mask, and further, the object to be processed is etched using the metal-containing film in which the pattern is formed as a mask to form a pattern on the object to be processed, whereby a semiconductor device circuit pattern can be formed on the substrate.

[0162] As described above, when forming an inorganic hard mask on a metal-containing film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, as a method for forming a silicon nitride film, it is described in JP-A-2002-334869 and WO 2004 / 066377. The film thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. Further, as the inorganic hard mask, a SiON film having a high effect as an antireflection film is most preferably used. Since the substrate temperature when forming the SiON film is 300 to 500°C, the metal-containing film needs to withstand a temperature of 300 to 500°C. The composition for forming a metal-containing film used in the present invention has high heat resistance and can withstand a high temperature of 300°C to 500°C. Therefore, a combination of an inorganic hard mask formed by a CVD method or an ALD method and a metal-containing film formed by a spin coating method is possible.

[0163] As described above, a photoresist film may be formed as an upper resist film on the inorganic hard mask. However, an organic antireflection film (BARC) or an adhesion film may be spin-coated on the inorganic hard mask, and a photoresist film may be formed thereon. In particular, when a SiON film is used as the inorganic hard mask, it is possible to suppress reflection even in immersion lithography with a high NA exceeding 1.0 by the two-layer antireflection film of the SiON film and the BARC. Another merit of forming the BARC is that it has an effect of reducing the undercut of the photoresist pattern directly above the SiON film.

[0164] In addition, in the present invention, as a method for forming a pattern by a multilayer resist process using such a composition for forming a metal-containing film, a resist underlayer film is formed on a substrate to be processed, and after applying the composition for forming a metal-containing film of the present invention on the resist underlayer and performing heat treatment, a metal-containing film is formed. Then, a resist upper layer film is formed on the metal-containing film using a photoresist material. After pattern exposure of the resist upper layer film, development is performed with a developer to form a pattern in the resist upper layer film. Using the resist upper layer film on which the pattern is formed as a mask, a pattern is transferred to the metal-containing film by dry etching. Using the metal-containing film on which the pattern is transferred as a mask, a pattern is transferred to the resist underlayer film by dry etching. Further, using the resist underlayer film on which the pattern is formed as a mask, the substrate to be processed is processed to form a pattern on the substrate to be processed, whereby a semiconductor device circuit pattern can be formed on the substrate.

[0165] As described above, a photoresist film may be formed as the resist upper layer film on the metal-containing film, but an organic adhesion film may be formed by spin coating on the metal-containing film, and a photoresist film may be formed thereon. In this case, a pattern can be transferred to the organic adhesion film and the metal-containing film by dry etching.

[0166] As described above, when forming a resist underlayer film on a substrate to be processed, a resist underlayer film can be formed by a method using a coating-type organic underlayer film material, a CVD method, an ALD method, or the like. Examples of the coating-type organic underlayer film material include resins and compositions disclosed in JP-A-2012-001687, JP-A-2012-077295, JP-A-2004-264710, JP-A-2005-043471, JP-A-2005-250434, JP-A-2007-293294, JP-A-2008-065303, JP-A-2004-205685, JP-A-2007-171895, JP-A-2009-014816, JP-A-2007-199653, JP-A-2008-274250, JP-A-2010-122656, JP-A-2012-214720, JP-A-2014-029435, WO2012 / 077640, WO2010 / 147155, WO2012 / 077640, WO2010 / 147155, WO2012 / 176767, JP-A-2005-128509, JP-A-2006-259249, JP-A-2006-259482, JP-A-2006-293298, JP-A-2007-316282, JP-A-2012-145897, JP-A-2017-119671, JP-A-2019-044022, and the like.

[0167] The resist upper layer film in the above multilayer resist process may be either positive or negative, and the same photo resist composition as that commonly used can be used. After spin-coating the photo resist composition, pre-baking is performed, and a range of 60 to 180 °C for 10 to 300 seconds is preferred. Thereafter, exposure is performed according to a conventional method, and further, post-exposure baking (PEB) and development are performed to obtain a resist pattern. Note that the thickness of the resist upper layer film is not particularly limited, but a thickness of 30 to 500 nm is preferred, and particularly 50 to 400 nm is preferred.

[0168] As the exposure light, high-energy rays with a wavelength of 300 nm or less, specifically, excimer lasers of 248 nm, 193 nm, and 157 nm, soft X-rays of 3 to 20 nm, electron beams, X-rays, etc. can be mentioned.

[0169] As the method for forming the pattern on the resist upper layer film, it is preferable to form a pattern by photolithography with a wavelength of 5 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof.

[0170] Also, as the development method in the pattern formation method, it is preferable to perform development with an alkali or an organic solvent.

[0171] Next, etching is performed using the obtained resist pattern as a mask. For the etching of the silicon-containing resist intermediate film and the inorganic hard mask in the three-layer resist process, the upper layer resist pattern is used as a mask and performed using a fluorocarbon-based gas. Thereby, a silicon-containing resist intermediate film pattern and an inorganic hard mask pattern are formed.

[0172] Next, using the obtained silicon-containing resist intermediate film pattern or inorganic hard mask pattern as a mask, etching of the metal-containing film is performed. The etching of the metal-containing film is preferably performed using an etching gas mainly composed of a chlorine-based gas.

[0173] The etching of the next workpiece can also be performed by a conventional method. For example, if the workpiece is SiO2, SiN, or a silica-based low dielectric constant insulating film, etching mainly using a fluorocarbon-based gas is performed. When the substrate is etched with a fluorocarbon-based gas, the silicon-containing resist intermediate film pattern in the three-layer resist process is peeled off simultaneously with the substrate processing.

[0174] The metal-containing film obtained by the composition for forming a metal-containing film of the present invention is characterized by excellent etching resistance during the etching of these workpieces.

[0175] The workpiece (workpiece substrate) is not particularly limited, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., or those with a processed layer formed on the substrate are used. As the processed layer, various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc., and their stopper films are used, and can usually be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming the processed layer, the substrate and the processed layer are made of different materials.

[0176] In the pattern formation method using the composition for forming a metal-containing film of the present invention, it is preferable to use a workpiece substrate having a structure or step with a height of 30 nm or more. As described above, since the composition for forming a metal-containing film of the present invention has excellent embedding / planarization characteristics, even if the workpiece substrate has a structure or step (concavo-convex) with a height of 30 nm or more, a flat cured film can be formed. The height of the structure or step of 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 the above height pattern, by forming the composition for forming a metal-containing film of the present invention for embedding / planarization, it becomes possible to make the film thicknesses of the resist intermediate film and the resist upper layer film to be formed thereafter uniform. Therefore, it becomes easy to secure the exposure depth margin (DOF) during photolithography, which is very preferable.

[0177] <Tone inversion type pattern formation method using a composition for forming a metal-containing film> In the present invention, as a tone inversion type pattern forming method using such a composition for forming a metal-containing film, a resist underlayer film is formed on a substrate to be processed, and a resist intermediate film, or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film is formed on the resist underlayer film. A resist upper layer film is formed on the resist intermediate film, or the combination of the inorganic hard mask intermediate film and the organic thin film using a photoresist material. After pattern exposure of the resist upper layer film, development is performed with a developer to form a pattern in the resist upper layer film. Using the resist upper layer film having the pattern formed thereon as a mask, the pattern is transferred to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching. Using the resist intermediate film or the inorganic hard mask intermediate film having the pattern transferred thereto as a mask, the pattern is transferred to the resist underlayer film by dry etching. A metal-containing film is coated on the resist underlayer film having the pattern formed thereon using the above composition for forming a metal-containing film, and the space between the resist underlayer film patterns is filled with the metal-containing film. The metal-containing film covering the resist underlayer film having the pattern formed thereon is etched back by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film having the pattern formed thereon. The resist intermediate film, or the hard mask intermediate film remaining on the upper surface of the resist underlayer film is removed by dry etching, and the resist underlayer film having the pattern formed thereon with the surface exposed is removed by dry etching to form an inverted pattern of the original pattern on the metal-containing film. A tone inversion type pattern forming method is provided, which includes a step of processing the substrate to be processed using the metal-containing film having the inverted pattern formed thereon as a mask to form an inverted pattern on the substrate to be processed.

[0178] An example of the formation of a tone inversion type pattern is specifically shown as follows with reference to FIG. 2. As shown in FIG. 2(G), after forming a resist underlayer film 7 made of a coating type organic underlayer film material on a processed layer 2 laminated on a substrate to be processed 1, a silicon-containing resist intermediate film 4 is formed, and a resist upper layer film 5 is formed thereon.

[0179] Next, as shown in FIG. 2(H), the required portion (exposed portion) 6 of the resist upper layer film 5 is exposed, and PEB and development are performed to form a resist upper layer film pattern 5a (FIG. 2(I)). Using this obtained resist upper layer film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is etched using a CF-based gas to form a silicon-containing resist intermediate film pattern 4a (FIG. 2(J)). After removing the resist upper layer film pattern 5a, the resist lower layer film 7 made of a coating-type organic lower layer film material is etched with oxygen plasma using the obtained silicon-containing resist intermediate film pattern 4a as a mask to form a resist lower layer film pattern 7a made of a coating-type organic lower layer film material (FIG. 2(K)).

[0180] After applying the composition for forming a metal-containing film of the present invention onto the resist lower layer film pattern 7a made of a coating-type organic lower layer film material and performing heat treatment, the metal-containing film 8 is coated, and the space between the resist lower layer film patterns 7a made of a coating-type organic lower layer film material is filled with the metal-containing film (FIG. 2(L)). Next, the metal-containing film 8 covering the resist lower layer film pattern 7a made of a coating-type organic lower layer film material is etched back by a chemical stripper or dry etching to expose the upper surface of the resist lower layer film pattern 7a made of a coating-type organic lower layer film material (FIG. 2(M)). Further, the silicon-containing resist intermediate film pattern 4a remaining on the upper surface of the resist lower layer film pattern 7a made of a coating-type organic lower layer film material is removed by dry etching (FIG. 2(N)). Next, after removing the resist lower layer film pattern 7a made of a coating-type organic lower layer film material by dry etching and forming an inverted pattern of the original pattern on the metal-containing film (forming a metal-containing film pattern 8a with the resist lower layer film pattern inverted) (FIG. 2(O)), the substrate to be processed is processed using the metal-containing film pattern 8a with the resist lower layer film pattern inverted as a mask to form a tone-inverted pattern on the substrate to be processed (FIG. 2(P)).

[0181] As described above, when forming a resist underlayer film on a substrate to be processed, a resist underlayer film can be formed by a method using a coating-type organic underlayer film material, a CVD method, an ALD method, or the like. Examples of the coating-type organic underlayer film material include resins and compositions disclosed in JP-A-2012-1687, JP-A-2012-77295, JP-A-2004-264710, JP-A-2005-043471, JP-A-2005-250434, JP-A-2007-293294, JP-A-2008-65303, JP-A-2004-205685, JP-A-2007-171895, JP-A-2009-14816, JP-A-2007-199653, JP-A-2008-274250, JP-A-2010-122656, JP-A-2012-214720, JP-A-2014-29435, International Publication WO2012 / 077640, International Publication WO2010 / 147155, International Publication WO2012 / 077640, International Publication WO2010 / 147155, International Publication WO2012 / 176767, JP-A-2005-128509, JP-A-2006-259249, JP-A-2006-259482, JP-A-2006-293298, JP-A-2007-316282, JP-A-2012-145897, JP-A-2017-119671, JP-A-2019-44022, and the like.

[0182] In the above-described tone inversion pattern forming method, after coating a composition for forming a metal-containing film on the obtained resist underlayer film pattern, it is preferable to remove the metal-containing film using a dry etching gas mainly composed of a chlorine-based gas in order to expose the upper surface of the resist underlayer film pattern. Thereafter, the resist intermediate film or the hard mask intermediate film remaining on the resist underlayer film is removed by dry etching with a fluorocarbon-based gas, the exposed resist underlayer film pattern on the surface is removed by dry etching with an oxygen-based gas, and a metal-containing film pattern is formed.

[0183] In the above-described tone inversion type pattern forming method, the resist underlayer film pattern preferably has a structure or step with a height of 30 nm or more. As described above, since the composition for forming a metal-containing film of the present invention has excellent embedding / planarizing properties, even if the film to be processed has a structure or step (unevenness) with a height of 30 nm or more, a flat cured film can be formed. The height of the structure or step of the resist underlayer film pattern is preferably 30 nm or more, more preferably 50 nm or more, and still more preferably 100 nm or more. In the method of inverting the resist underlayer film pattern having the above height pattern, by forming the composition for forming a metal-containing film of the present invention and performing embedding / planarization, it becomes possible to perform pattern inversion / transfer with high precision, which is very preferable. Since it has excellent dry etching resistance using a chlorofluorocarbon gas with respect to a resist underlayer film using a conventional coating type organic underlayer film material, by inverting the resist underlayer film pattern with the above composition for forming a metal-containing film, a desired resist pattern can be formed on the film to be processed with high precision.

Example

[0184] Hereinafter, the present invention will be described more specifically by showing synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited thereto. As for the molecular weight and dispersity, the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, and the dispersity (Mw / Mn) was determined.

[0185] [Synthesis Example] In the following synthesis examples and comparative examples, the following tin compounds Sn: (Sn-1) to (Sn-5), raw material group X: (X1) to (X14), raw material group T: (TT1) to (TT5), and raw material group Z: (Z1) to (Z7) were used. Each raw material group is shown below. Note that for the following raw material compounds, there may be isomers, but one structure is shown as a representative.

[0186] Tin compound Sn:

Chemical formula

[0187] Raw material group X:

Chemical formula

[0188] Raw material group T:

Chemical formula

[0189] Raw material group Z:

Chemical formula

[0190] [Production example] Synthesis of raw material group T A tin compound Sn and 1 equivalent of raw material X were added to toluene, and the mixture was reacted for 5 hours while removing water at 130 °C. Then, the temperature was returned to room temperature, and if necessary, additional tin compound was added, and the reaction was continued for another 5 hours while removing water at 130 °C. Toluene was removed under reduced pressure, and the resulting product was suspended in methanol, filtered, and washed to obtain the compound of raw material group T. Compound (TT1) was synthesized from tin compound (Sn-3) and the compound represented by the following formula (X-15), compound (TT2) was synthesized from tin compound (Sn-1) and compound (X-2), compound (TT3) was synthesized from tin compound (Sn-2) and compound (X-6), compound (TT4) was synthesized from tin compound (Sn-2) and compound (X-11), and compound (TT5) was synthesized from tin compound (Sn-4) and compound (X-2), respectively.

Chemical formula

[0191] [Synthesis example 1] Synthesis of compound (P1) for forming a metal-containing film (Reaction 1) 5.0 g of normal butyltin trichloride (Sn-5), 2.5 g of raw material (X-1) and 100 g of toluene were added, and the mixture was reacted at 130 °C for 5 hours. Then, 2.7 g of raw material (TT1) was added and the reaction was continued for an additional 3 hours. After completion of the reaction, toluene was removed under reduced pressure, and the residue was suspended in methanol, filtered, and washed to obtain compound (P1).

[0192] [Synthesis Example 2-14] Synthesis of Compounds (P2) to (P14) for Metal-Containing Film Formation The raw material group X and the raw material group T or the raw material group Z were changed as shown in Table 1, and the same operations as in Synthesis Example 1 were carried out to obtain compounds (P2) to (P14) for metal-containing film formation.

Table 1

[0193]

Chemical formula

[0194] [Synthesis of Compound (R-1) for Metal-Containing Film Formation for Comparative Example] 5.0 g of tin compound (Sn-1), 8.6 g of raw material group P (Z-1) and 100 g of toluene were added, and the mixture was reacted at 130 °C for 7 hours while removing water. After the reaction, the solvent was removed under reduced pressure to obtain (R-1).

Chemical formula

[0195] [Synthesis of Compound (R-2) for Metal-Containing Film Formation for Comparative Example] 5.0 g of tin compound (Sn-1), 6.8 g of raw material group X (X-14) and 50 g of toluene were added, and the mixture was reacted at 130 °C for 7 hours while removing water. After the reaction, the solvent was removed under reduced pressure to obtain (R-2).

Chemical formula

[0196] [Weight-Average Molecular Weight and Dispersion Degree] The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the above compounds (P1) to (P14), (R-1) and (R-2) were determined. The results are shown in Table 2. The weight average molecular weight Mw and number average molecular weight Mn are values in terms of polystyrene conversion by the GPC method using tetrahydrofuran, and the dispersity was determined therefrom.

Table 2

[0197] [Synthesis of the metal-containing compound (R-3) for comparative example for forming a metal-containing film] A tin compound reported in [Synthesis Example 8] of Japanese Patent No. 702894 was synthesized as a metal-containing compound assumed to be used in a photoresist. 3 g of isopropyltriphenyltin, 1.4 g of succinic acid were dissolved in 20 ml of acetonitrile, and the mixture was refluxed for 24 hours. After the reaction, the solvent was removed under reduced pressure to obtain the tin-containing compound (R-3).

Chemical formula

[0198] [Synthesis of the metal-containing compound (R-4) for comparative example for forming a metal-containing film] 10 g of catechol, 6.6 g of formaldehyde, and 30 g of PGME (propylene glycol monomethyl ether) were added and homogenized at an internal temperature of 100°C. Then, a mixed solution of 0.2 g of p-toluenesulfonic acid monohydrate and 3.0 g of PGME, which had been previously mixed and homogenized, was slowly added dropwise, and the reaction was carried out at an internal temperature of 120°C for 8 hours. After the reaction was completed, the temperature was returned to room temperature, 150 g of ultrapure water was added while stirring, and after standing for 1 hour, the upper layer was fractionated. Further, it was dissolved in 30 g of PGME, and the same operation was repeated twice. Then, 300 ml of MIBK (methyl isobutyl ketone) was added, and it was washed 4 times with 200 ml of pure water, and the organic layer was dried under reduced pressure. Then, 20 g of a tin raw material (Sn-1) and 300 g of toluene were added, and the mixture was stirred at 130°C for 8 hours. After the reaction, the solvent was removed under reduced pressure to obtain (R-4).

Chemical formula

[0199] [Synthesis of Metal-Containing Film-Forming Compound (R-5) for Comparative Example] 5 g of glycerol monomethacrylate, 0.7 g of V-601 and 20 g of MEK (methyl ethyl ketone) were added, and after nitrogen bubbling, the mixture was stirred at 79 °C for 20 hours. After cooling to room temperature, the polymer solution was added to 100 g of IPE (diisopropyl ether), and the upper layer was decanted. 30 g of DMF and 7.4 g of (Sn-1) were added, and the reaction was carried out at 130 °C for 8 hours. After the reaction, DMF was removed under reduced pressure, and IPE was added and filtered to obtain (R-5). [Chemical Formula]

[0200] [Synthesis of Metal-Containing Film-Forming Compound (R-6) for Comparative Example] As a compound having a metal different from the metal-containing film-forming compound of the present invention, a titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758 was synthesized. While stirring a solution of 284 g of titanium tetraisopropoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) in 500 g of IPA (isopropanol), a solution of 27 g of deionized water in 500 g of IPA was added dropwise at room temperature over 2 hours. 120 g of 2-methyl-2,4-pentanediol was added to the resulting solution, and the mixture was stirred at room temperature for 30 minutes. This solution was concentrated under reduced pressure at 30 °C, then further heated to 60 °C, and heating was continued under reduced pressure until no distillate came out. When no distillate was seen, 1,200 g of PGMEA was added, and the mixture was heated at 40 °C under reduced pressure until no IPA distilled out, to obtain 1,000 g of a PGMEA solution of a titanium-containing compound (R-6) (compound concentration 20% by mass).

[0201] [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 mixed solution of 8.0 g of p-toluenesulfonic acid monohydrate and 8.0 g of PGME, which had been previously 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 completed, it was cooled to room temperature, 2,000 ml of MIBK was added, and it was washed 6 times with 500 ml of pure water, and the organic layer was dried under reduced pressure. After adding 300 g of THF to the residue to form a homogeneous solution, it was crystallized in 2,000 g of hexane. The precipitated crystals were separated by filtration, washed twice with 500 g of hexane, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain resin (R-7). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R-7): Mw = 3,300, Mw / Mn = 2.54

Chemical formula

[0202] "Evaluation of Solvent Solubility and Heat Resistance" The solvent solubility and heat resistance of the metal-containing compounds were evaluated. The compounds (P1) to (P14) synthesized in Synthesis Examples 1 to 14 and the comparative example compounds (R-1) to (R-6) were each prepared to be a 15.0 wt% solution of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (CyHO). After stirring for 24 h, those that were completely dissolved were marked as 〇, those with partial undissolution were marked as △, and those that were completely suspended were marked as ×. Also, 3.0 mg of each was weighed, and using Rigaku's Thermo plus EVO2, the temperature was raised from 30°C to 300°C at 10°C / min in the atmosphere. At this time, those with a weight loss of 40% or less when the temperature was raised to 300°C were marked as A, those with a weight loss of 40 - 60% were marked as B, and those with a weight loss of more than 60% were marked as C. These results are shown in Table 3.

Table 3

[0203] As shown in Table 3, all of the compounds (P1) to (P14) for forming a metal-containing film of the present invention can be prepared in cyclohexanone, and it was confirmed that the solubility was sufficient. Also, those containing many organic chains in the main chain or those having the ends sealed with organic groups could be prepared in PGMEA, and it was confirmed that they exhibited excellent solvent solubility. Similarly, although the comparative example compounds, which are a group of compounds excluding some elements of the present invention, showed the same solubility results, (R-4) and (R-5) with a structure in which tin was introduced into all of the repeating units of the polymer had no solubility. Also, in TG-DTA measurement, all of the compounds of the present invention had a weight loss of 40% or less when the temperature was raised to 300°C, but in the comparative example compounds, the weight loss was 49% for (R-2), 68% for (R-3), and 56% for (R-6). It was confirmed that the compounds of the present invention were superior in heat resistance compared to these.

[0204] [Composition UDL-1 for forming a metal-containing film] The compound (P1) for forming a metal-containing film was dissolved in a solvent of cyclohexanone (CyHO) containing 0.5 mass% of surfactant FC-4430 (manufactured by Sumitomo 3M Limited) at the ratio shown in Table 4, and filtered through a 0.2 μm membrane filter to prepare a composition (UDL-1) for forming a metal-containing film.

[0205] [Preparation of compositions (UDL-2 to 21) for forming a metal-containing film, compositions for forming a metal-containing film for comparative examples (comparative example UDL-1 to 5)] Except that the types and contents of the respective components were as shown in Table 4, the same operations as for UDL-1 were performed to prepare each chemical solution. In Table 4, "-" indicates that the corresponding component was not used. The crosslinking agent shown by the following formula (C-1) was used, 1,6-diacetoxyhexane: boiling point 260°C was used as the high-boiling solvent (B2-1), the polymer (E-1) for promoting fluidity was used, and the thermal acid generator (TAG) shown by the following formula (F-1) was used.

[0206] [Crosslinking agent] The crosslinking agent (C-1) used in the composition for forming a metal-containing film is shown below. [Chemical formula]

[0207] [Synthesis Example of Polymer for Fluidity Promoter] Synthesis of Polymer (E-1) for Fluidity Promoter Under a nitrogen atmosphere, 20.0 g of cresol novolak, 27.6 g of potassium carbonate, and 100 g of DMF were added and made into a homogeneous dispersion at an internal temperature of 50°C. 11.9 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and then the separated aqueous layer was removed. Further, the organic layer was washed 6 times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, and then the organic layer was dried under reduced pressure to obtain resin (E-1). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (E-1): Mw = 8,500, Mw / Mn = 3.46 [Chemical formula]

[0208] [Thermal Acid Generator] The thermal acid generator (F-1) used in the composition for forming a metal-containing film is shown below. [Chemical formula]

[0209] [Table 4]

[0210] [Film Forming Property Test] The composition for forming a metal-containing film (UDL-1 to 21, Comparative Example UDL-1 to 4) prepared above was applied onto a silicon substrate, baked at 180 °C for 60 seconds, and then the film thickness (a [nm]) after additional baking at 250 °C for 60 seconds was measured. Further, the film thickness from the center part to the outer peripheral part of the substrate was measured, the film thickness difference between the maximum film thickness and the minimum film thickness among them, Range (b [nm]) was calculated, and the in-plane uniformity ((b / a)×100) was determined. Furthermore, PGMEA solvent was dispensed thereon, left standing for 30 seconds, spin-dried, baked at 100 °C for 60 seconds to evaporate (Rework) PGMEA, and the film thickness (c [nm]) was measured. The film thickness difference before and after PGMEA treatment (remaining film ratio: (c / a)×100) was determined. The results are shown in Table 5 below.

Table 5

[0211] As shown in Table 5, the composition for forming a metal-containing film (Examples 1-1 to 1-21) of the present invention has an in-plane uniformity of 5.0% or less after the high-temperature additional baking treatment at 250 °C, and it was confirmed that the film has excellent film-forming properties. On the other hand, in Comparative Examples 1-1 to 1-2 using the comparative example compounds (R-1) and (R-2) which are monomolecular tin compounds, the in-plane uniformity was relatively good, but the results were inferior to those of the examples using the compound group of the present invention. This is considered to be because the radical crosslinking does not occur efficiently due to the small number of radical active units of the Sn-alkyl bond, and the film is uneven due to sublimates and decomposition products. Also, although there are a plurality of tin atoms in one molecule, in Comparative Example 1-3 using the comparative example compound (R-3) which is composed only of esters without a diol unit, the film was uneven due to the influence of insufficient molecular weight. In Comparative Example 1-4 using Comparative Example UDL-4 containing the titanium compound (R-6) reported in [Synthesis Example A-II] of Japanese Patent No. 6189758, a film with many irregularities with an in-plane uniformity exceeding 5.0% was formed after the baking treatment, and the film-forming properties were poor. This is presumably because the titanium compound has poor heat resistance, a large amount of sublimates, and a large volume shrinkage. In addition, Examples 1-15 to 1-18 using UDL-15 to 18 with the crosslinking agent (C-1) added showed a tendency of improved in-plane uniformity compared to Examples 1-1, 5, 7, and 13 using UDL-1, 5, 7, and 13 without the addition. This is presumably because the crosslinking reaction proceeded more efficiently due to the crosslinking agent, and the generation of sublimates and decomposition products could be suppressed. Also, Example 1-20 using UDL-20 with the acid generator (F-1) added had a higher residual film rate after rework compared to Example 1-12 without the addition, suggesting that the crosslinking reaction proceeded further. In addition, it was also confirmed that there was no significant difference in the in-plane uniformity and the residual film rate after rework when comparing the examples with and without the addition of the fluidity promoter and the high-boiling solvent.

[0212] [Evaluation of Embedding Characteristics] Each of the above metal-containing film-forming compositions (UDL-1 to 21) and Comparative Examples UDL-3 and 4 was applied onto a SiO2 wafer substrate having a dense line & space pattern (line width 40 nm, line depth 120 nm, distance between the centers of two adjacent lines 80 nm), and heated at 250 °C for 60 seconds using a hot plate to form a metal-containing film with a film thickness of 100 nm. The substrate used was a base substrate 9 (SiO2 wafer substrate) having a dense line & space pattern as shown in FIGS. 3(Q) (plan view) and (R) (cross-sectional view). The cross-sectional shape of each obtained wafer substrate was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the possibility of embedding into the stepped substrate was confirmed. The results are shown in Table 6. When using a metal-containing film-forming composition with poor embedding characteristics, in this evaluation, the stepped substrate cannot be embedded well. When using a metal-containing film-forming composition with good embedding characteristics, in this evaluation, as shown in FIG. 3(S), the space between the lines of the base substrate 9 having a dense line & space pattern can be filled without gaps. 〇 indicates that it can be embedded without large voids, △ indicates that it can be embedded but large voids are generated, and × indicates that it cannot be embedded.

[0213]

Table 6

[0214] As shown in Table 6, in Examples 2-1 to 2-21 using the resist metal-containing film-forming composition of the present invention, when baked at 250 °C, it was possible to fill the dense line & space pattern without generating voids, and it was confirmed that they had good embedding characteristics. On the other hand, in Comparative Example 2-1 using Comparative Example UDL-3 with poor film-forming properties and Comparative Example 2-2 using the titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758, in Comparative Example 2-1, embedding was not possible, and in Comparative Example 2-2, voids were observed at the bottom of the pattern. This is because, as observed in the above heat resistance evaluation and film-forming property evaluation of the compounds of the present invention, there are few sublimates due to high-temperature baking and the volume shrinkage is small, so it is possible to fill the step without generating voids. On the other hand, Comparative Examples UDL-3 and 4 with poor heat resistance have many sublimates and large volume shrinkage, etc., resulting in the generation of voids or the inability to embed.

[0215] [Tin content and etching resistance test] The metal-containing film-forming compositions (UDL-1, 2, 5, 7, 13, 15, 16, 17, 19) prepared above and Comparative Examples UDL-1 to 2 and 5 with relatively good in-plane uniformity were applied onto silicon substrates, heated at 250 °C for 60 seconds using a hot plate to form metal-containing films, and the elemental ratios on the surfaces were calculated using XPS K-ALPHA Surface Analysis (manufactured by Thermo SCIENTIFIC) and converted to mass %. Further, an etching test was conducted with a CF-based gas and an O2-based gas under the following conditions, and the film thickness difference of the organic film before and after etching was determined. The results are shown in Table 7. Also, a dry etching apparatus TE-8500 manufactured by Tokyo Electron Limited was used for etching.

[0216] The CF4-based gas etching conditions are as shown below. Chamber pressure 200 mT RF power 300 W CF4 gas flow rate 100 sccm Time 20 sec

[0217] The O2-based gas etching conditions are as shown below. Chamber pressure 500 mT RF power 100 W O2 gas flow rate 30 sccm N2 gas flow rate 270 sscm Time 20 sec

[0218]

Table 7

[0219] As shown in Table 7, in Examples 3-1 to 3-9 using the composition for forming a metal-containing film of the present invention, it was confirmed that the tin content rate of the film after firing exceeded 60 wt% regardless of the presence or absence of the additive. On the other hand, in Comparative Examples 3-1 and 3-2 using Comparative Examples UDL-1 and 2 in which only one tin atom exists in one molecule, the tin content rate was less than 55 wt%, and it was confirmed that they were inferior in tin content rate. Furthermore, Examples 3-1 to 3-5 using UDL-1, 2, 5, 7, and 13 without an additive had a tin content rate of 65 wt% or more, and it was also confirmed that the high one exceeded 70 wt%. It was found that the film after firing has a high tin content rate, and it was confirmed that a film having a high tin content rate is obtained by containing a plurality of tin atoms in one molecule, and it was shown that secondary electron emission due to EUV light absorption can be expected. Furthermore, in the etching resistance evaluation, the higher the tin content rate, the better the etching resistance for both CF-based gas and O2-based gas. Particularly, regarding O2 etching, the etching resistance was greatly improved compared to Comparative Example 3-3 of an organic underlayer film not containing tin.

[0220] From the above, since the compound for forming a metal oxide film of the present invention is an organotin compound that highly combines heat resistance and a high tin content rate, the composition for forming a metal-containing film using this has excellent dry etching resistance compared to conventional organic underlayer film materials, and can provide a resist underlayer film material having both film-forming properties and embedding properties. It is extremely useful as a resist underlayer film material used in the multilayer resist method and as a reversing agent used in the tone inversion etching method.

[0221] This specification includes the following aspects. [1]: A compound for forming a metal-containing film, characterized in that the compound is a polymer containing any one or both of the repeating units represented by the following general formula (P-1) or (P-2). [Chemical formula] (In the general formulas (P-1) and (P-2), R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, 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. W1 is a substituted or unsubstituted linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 40 carbon atoms, and the hydrocarbon group contains an oxygen atom, a nitrogen atom or a sulfur atom as a hetero atom, and may form an ether bond, a carbonyl group, an ester group or an amide group, and may form a heterocyclic structure via the hetero atom. R2 represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a hydroxyl group, an amino group or a halogen atom, s1 is an integer of 0 to 1, and n1 is an integer of 0 to 1. Also, a plurality of these elements in the repeating unit may be different. W2 is a substituted or unsubstituted linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 40 carbon atoms, and the hydrocarbon group contains an oxygen atom, a nitrogen atom or a sulfur atom as a hetero atom, and may form an ether bond, a carbonyl group, an ester group or an amide group, and may form a heterocyclic structure via the hetero atom. s2 is an integer of 0 to 1. s3 is 1 or 2. When s3 is 1, R3 is a hydrogen atom or a hydrocarbon group having a hydroxyl group with 1 to 10 carbon atoms. When s3 is 2, R3 is an oxygen atom and together with the carbon atom to which it is bonded forms a carbonyl group, and W2 and R3 may be bonded to each other to form a ring structure. Also, a plurality of these elements in the repeating unit may be different.) [2]: The metal-containing film-forming compound is a polymer containing a repeating unit represented by the general formula (P-1). In the general formula (P-1), W1 is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms which may contain a hydroxyl group or an amino group (the hydrocarbon group contains an oxygen atom, a nitrogen atom, a sulfur atom and may form an ether bond, a carbonyl group, an ester group), or any of the groups represented by the following general formulas (W1-1) to (W1-4). The metal-containing film-forming compound of [1] is characterized by this. [Chemical formula] (In the above general formulas (W1-1) to (W1-4), R W is a divalent organic group having 1 to 23 carbon atoms, #1 represents a bonding part with an ester, and #2 represents a bonding part with a benzene ring.) [3]: The metal-containing film-forming compound is a polymer containing a repeating unit represented by the general formula (P-2). In the general formula (P-2), W2 is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms which may contain a hydroxyl group or an amino group, or a cyclic hydrocarbon group bonded to R3 (the hydrocarbon group contains an oxygen atom, a nitrogen atom, a sulfur atom and may form an ether bond, a carbonyl group, an ester group), or any of the groups represented by the following general formulas (W2-1) to (W2-4). The metal-containing film-forming compound of [1] or [2] is characterized by this. [Chemical formula] (In the above general formulas (W2-1) to (W2-4), R W is a divalent organic group having 1 to 23 carbon atoms, and #1 and #2 each represent a bonding part with an ester and a carbon atom, respectively.) [4]: The metal-containing film-forming compound of [2] is characterized in that R W in the general formulas (W1-1) to (W1-4) is an unsaturated hydrocarbon group having 2 to 23 carbon atoms. [5]: The metal-containing film-forming compound of [4] is characterized in that R W is a group represented by the following general formula (1). [Chemical formula] (In the general formula (1), R a , R b and R c are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R a and R b may be bonded to form a cyclic substituent. *1 and *2 each represent a bonding portion with a carbonyl group, and *1 and *2 may be reversed.) [6]: The compound for forming a metal-containing film according to [3], wherein R W in the general formulas (W2-1) to (W2-4) is an unsaturated hydrocarbon group having 2 to 23 carbon atoms. [7]: The compound for forming a metal-containing film according to [6], wherein R W is a group represented by the following general formula (1). [Chemical formula] (In the general formula (1), R a , R b and R c are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R a and R b may be bonded to form a cyclic substituent. *1 and *2 each represent a bonding portion with a carbonyl group, and *1 and *2 may be reversed.) [8]: The compound for forming a metal-containing film according to any one of [1] to [7], wherein the terminal structure of the polymer having the repeating unit of the general formula (P-1) is the following general formula (T-1), or the terminal structure of the polymer having the repeating unit of the general formula (P-2) is the following general formula (T-2). [Chemical formula] (In the general formulas (T-1) to (T-2) above, R1, R2, R3, W1, W2, s1, s2 and s3 are the same as those in the general formulas (P-1) to (P-2).) [9]: The terminal structure of the polymer having the repeating unit of the general formula (P-1) or (P-2) is *-OC(=O)R (where R is a monovalent organic group, and * represents the bonding part with the Sn atom in the polymer), and it is a compound for forming a metal-containing film according to any one of [1] to [7].

[10] : In the terminal structure *-OC(=O)R, R is any one of the groups represented by the following general formulas (A-1) to (A-4), the following general formula (3), and the following general formula (4), and it is a compound for forming a metal-containing film according to [9].

Chemical formula

Chemical formula

Chemical formula

[11] : The metal-containing film-forming compound according to

[10] , wherein Y A1 in the general formulas (A-1) to (A-4), X in the general formula (3), or X in the general formula (4) is an unsaturated hydrocarbon group having 2 to 23 carbon atoms.

[12] : Y in the general formulas (A-1) to (A-4) A1 The metal-containing film-forming compound according to

[10] , wherein X in the general formula (3) or X in the general formula (4) is a group represented by the following general formula (1). [Chemical formula] (In the general formula (1), R a , R b and R c are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R a and R b may be bonded to form a cyclic substituent. *1 and *2 each represent a bonding portion with a carbonyl group, and *1 and *2 may be reversed.)

[13] : A metal-containing film-forming composition that functions as a resist underlayer film material used in semiconductor manufacturing, characterized by containing (a) a metal-containing film-forming compound according to any one of [1] to

[12] and (b) an organic solvent.

[14] : The metal-containing film-forming composition according to

[13] , wherein the composition is a metal-containing film-forming composition that can be used as a resist underlayer film in a multilayer resist method, and further contains one or more of (c) a crosslinking agent, (d) a surfactant, (e) a fluidity promoter, and (f) an acid generator.

[15] : The metal-containing film-forming composition according to

[13] or

[14] , wherein the (b) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180 °C and one or more organic solvents having a boiling point of 180 °C or higher.

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

[13] to

[15] on a substrate to be processed and then performing a heat treatment, (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 and then developing with a developer, (I-4) Using the resist upper layer film on which the pattern is formed as a mask, transferring the pattern to the metal-containing film by dry etching, and (I-5) Using the metal-containing film on which the pattern is formed as a mask to process the substrate to be processed and forming a pattern on the substrate to be processed A pattern forming method characterized by comprising the steps.

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

[13] to

[15] on the substrate to be processed and then performing heat treatment, (II-2) A step of forming a resist intermediate film on the metal-containing film, (II-3) A step of forming a resist upper layer film on the resist intermediate film using a photoresist material, (II-4) After pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film, (II-5) Using the resist upper layer film on which the pattern is formed as a mask, transferring the pattern to the resist intermediate film by dry etching, (II-6) Using the resist intermediate film to which the pattern is transferred as a mask, transferring the pattern to the metal-containing film by dry etching, and (II-7) Using the metal-containing film on which the pattern is formed as a mask to process the substrate to be processed and forming a pattern on the substrate to be processed A pattern forming method characterized by comprising the steps.

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

[13] to

[15] on the substrate to be processed and then performing heat treatment, (III-2) A step of forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist lower layer film, (III-3) A step of forming an organic thin film on the inorganic hard mask intermediate film, (III-4) A step of forming an upper resist film on the organic thin film using a photoresist material. (III-5) After pattern-exposing the upper resist film, developing it with a developer to form a pattern in the upper resist film. (III-6) Using the upper resist film with the pattern formed thereon as a mask, transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching. (III-7) Using the inorganic hard mask intermediate film with the pattern transferred thereon as a mask, transferring the pattern to the metal-containing film by dry etching, and (III-8) Using the metal-containing film with the pattern formed thereon as a mask to process the substrate to be processed and form a pattern on the substrate to be processed. A pattern formation method characterized by comprising the above steps.

[19] : A method of forming a pattern on a substrate to be processed, (IV-1) A step of forming a lower resist film on the substrate to be processed. (IV-2) After applying any one of the composition for forming a metal-containing film from

[13] to

[15] on the lower resist film, heat-treating to form a metal-containing film. (IV-3) A step of forming an upper resist film on the metal-containing film using a photoresist material, or a step of spin-coating an organic adhesion film on the metal-containing film and then forming an upper resist film on it using a photoresist material. (IV-4) After pattern-exposing the upper resist film, developing it with a developer to form a pattern in the upper resist film. (IV-5) Using the upper resist film with the pattern formed thereon as a mask, transferring the pattern to the metal-containing film, or the organic adhesion film and the metal-containing film by dry etching. (IV-6) Using the metal-containing film with the pattern transferred thereon as a mask, transferring the pattern to the lower resist film by dry etching, and (IV-7) A step of processing the substrate to be processed using the resist underlayer 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 above.

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

[13] to

[15] on the resist underlayer film on which the pattern is formed, and then performing heat treatment to coat the metal-containing film and fill 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 is formed by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern is formed; (V-9) A step of removing the resist intermediate film or the hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; Removing the resist underlayer film having the pattern with the (V-10) surface exposed by dry etching, and forming an inverted pattern of the original pattern on a metal-containing film; (V-11) A pattern forming method characterized by including a step of processing the substrate to be processed using the metal-containing film having the inverted pattern formed thereon as a mask to form an inverted pattern on the substrate to be processed.

[21] : The pattern forming method according to

[18] or

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

[0222] Note that the present invention is not limited to the above-described embodiments. The above-described embodiments are examples, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Explanation of Reference Numerals

[0223] 1... Substrate to be processed, 2... Layer to be processed, 2a... Pattern (pattern formed on the layer to be processed); 3... Metal-containing resist underlayer film, 3a... Pattern of the metal-containing resist underlayer film; 4... Silicon-containing resist intermediate film, 4a... Pattern of the silicon-containing resist intermediate film; 5... Resist upper layer film, 5a... Pattern of the resist upper layer film, 6... Exposed portion; 7... Resist underlayer film made of a coating-type organic underlayer film material, 7a... Pattern of the resist underlayer film made of a coating-type organic underlayer film material; 8... Metal-containing film, 8a... Pattern of the metal-containing film obtained by inverting the pattern of the resist underlayer film; 9... Substrate having dense lines & spaces, 10... Metal-containing resist underlayer film.

Claims

1. A compound for forming a metal-containing film, characterized in that the compound is a polymer containing any one or both of the repeating units represented by the following general formula (P-1) or (P-2). 【Chemical 1】 (In the general formulas (P-1) and (P-2), R １ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, 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. W １ is a substituted or unsubstituted linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 40 carbon atoms, and the hydrocarbon group contains an oxygen atom, a nitrogen atom, or a sulfur atom as a heteroatom, and may form an ether bond, a carbonyl group, an ester group, or an amide group, and may form a heterocyclic structure through the heteroatom. R ２ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a hydroxyl group, an amino group, or a halogen atom, s １ is an integer of 0 to 1, n １ is an integer of 0 to 1. Also, a plurality of these elements in the repeating unit may be different. W ２ is a substituted or unsubstituted linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 40 carbon atoms, and the hydrocarbon group contains an oxygen atom, a nitrogen atom, or a sulfur atom as a heteroatom, and may form an ether bond, a carbonyl group, an ester group, or an amide group, and may form a heterocyclic structure through the heteroatom. s ２ is an integer of 0 to 1. s ３ is 1 or 2, and when s ３ is 1, R ３ is a hydrogen atom or a hydrocarbon group having a hydroxyl group with 1 to 10 carbon atoms, and when s ３ is 2, R ３ is an oxygen atom and forms a carbonyl group together with the carbon atom to which it is bonded, and W ２ and R ３ may be bonded to each other to form a ring structure. Also, a plurality of these elements in the repeating unit may be different.)

2. The compound for forming a metal-containing film is a polymer containing a repeating unit represented by the general formula (P-1), and in the general formula (P-1), W １ is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms which may contain a hydroxyl group or an amino group (the hydrocarbon group contains an oxygen atom, a nitrogen atom, a sulfur atom and may form an ether bond, a carbonyl group, an ester group) or any of the groups represented by the following general formula (W １ -1) to (W １ -4). The compound for forming a metal-containing film according to claim 1, characterized in that it is any of them. 【Chemical Formula 2】 (In the above general formulas (W １ -1) to (W １ -4), R Ｗ is a divalent organic group having 1 to 23 carbon atoms, # １ is a bonding part with an ester, # ２ represents a bonding part with a benzene ring.)

3. The compound for forming a metal-containing film is a polymer containing a repeating unit represented by the general formula (P-2), and in the general formula (P-2), W ２ is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms which may contain a hydroxyl group or an amino group, or a cyclic hydrocarbon group bonded to R ３ (the hydrocarbon group contains an oxygen atom, a nitrogen atom, a sulfur atom and may form an ether bond, a carbonyl group, an ester group), or any of the groups represented by the following general formulas (W ２ -1) to (W ２ -4). The compound for forming a metal-containing film according to claim 1, characterized in that it is any of them. [Chemical Formula 3] (In the above general formulas (W ２ -1) to (W ２ -4), R Ｗ is a divalent organic group having 1 to 23 carbon atoms, # １ , # ２ each represents an ester and a bonding portion with a carbon atom.)

4. The above general formula (W １ -1) to (W １ -4), wherein R Ｗ is an unsaturated hydrocarbon group having 2 to 23 carbon atoms, the compound for forming a metal-containing film according to claim 2.

5. The above-mentioned R Ｗ The compound for forming a metal-containing film according to claim 4, wherein R is a group represented by the following general formula (1). [Chemical Formula 4] (In the general formula (1), R ａ , R ｂ and R ｃ are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R ａ and R ｂ may be bonded to form a cyclic substituent. *1 and *2 each represent a bonding portion with a carbonyl group, and *1 and *2 may be reversed.)

6. The above general formula (W ２ -1) to (W ２ -4), wherein R Ｗ is an unsaturated hydrocarbon group having 2 to 23 carbon atoms, and the compound for forming a metal-containing film according to claim 3.

7. Said R Ｗ The compound for forming a metal-containing film according to claim 6, wherein R is a group represented by the following general formula (1). 【Chemical Formula 5】 (In the general formula (1), R ａ , R ｂ and R ｃ are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R ａ and R ｂ may be bonded to form a cyclic substituent. *1 and *2 each represent a bonding portion with a carbonyl group, and *1 and *2 may be reversed.)

8. The metal-containing film-forming compound according to claim 1, wherein the terminal structure of the polymer having the repeating unit of the general formula (P-1) is represented by the following general formula (T-1), or the terminal structure of the polymer having the repeating unit of the general formula (P-2) is represented by the following general formula (T-2). 【Chemical Formula 6】 (In the above general formulas (T-1) to (T-2), R １ , R ２ , R ３ , W １ , W ２ , s １ , s ２ and s ３ are the same as in the above general formulas (P-1) to (P-2).)

9. The metal-containing film-forming compound according to claim 1, wherein the terminal structure of the polymer having the repeating unit of the general formula (P-1) or (P-2) is *-OC(=O)R (R is a monovalent organic group, and * represents the bonding part with the Sn atom in the polymer).

10. In the terminal structure *-OC(=O)R, the metal-containing film-forming compound according to claim 9, wherein R is any one of the groups represented by the following general formula (A-1) to (A-4), the following general formula (3), and the following general formula (4). [Chemical Formula 7] (In the general formulas (A-1) to (A-4), Y Ａ１ , Y Ａ２ may be the same as or different from each other, and is a substituted or unsubstituted divalent organic group having 1 to 23 carbon atoms and being saturated or having 2 to 23 carbon atoms and being unsaturated, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkylene group having 7 to 31 carbon atoms. R Ａ is a hydrogen atom, a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms and being saturated or having 2 to 20 carbon atoms and being unsaturated, 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 R Ａ１ is an organic group in which a protecting group is eliminated by the action of either or both of an acid and heat represented by the following general formula (2) to generate one or more hydroxyl groups or carboxyl groups, and * represents a bonding portion with a carbonyl group.) 【Chemical 8】 (In the general formula (2), R Ａ２ is an organic group in which the protecting group is removed by the action of either an acid, heat, or both, and * represents the bonding part with Y Ａ１ or Y Ａ２ .) 【Chemical Formula 9】 (In the general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, B is the following general formula (B), and * represents the bonding part with the carbonyl group.) 【Chemical Formula 10】 (In the general formula (B), Y Ｂ is a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms and being saturated or having 2 to 20 carbon atoms and being unsaturated, a substituted or unsubstituted divalent arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent arylalkylene group having 7 to 31 carbon atoms, and R Ｂ is a hydroxyl group or any of the structures represented by the following general formulas (B-1) to (B-3).) 【Chemical 11】 (In the general formulas (B-1) to (B-3), R Ｂ１ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents the bonding part with Y Ｂ .) 【Chemical Formula 12】 (In the general formula (4), X is a divalent organic group having 1 to 31 carbon atoms, C is any one of the groups represented by the following general formula (C-1) to (C-4), and * represents the bonding part with the carbonyl group.) 【Chemical 13】 (In the general formulas (C-1) and (C-3), R Ｃ１ is a hydrogen atom or a methyl group, and in the same formula, they may be the same as or different from each other. In (C-3) and (C-4), R Ｃ２ is a hydrogen atom or a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. * represents the bonding part with the carbonyl group.)

11. Y in the general formulas (A-1) to (A-4) Ａ１ , X in the general formula (3), or X in the general formula (4) is an unsaturated hydrocarbon group having 2 to 23 carbon atoms, and the compound for forming a metal-containing film according to claim 10.

12. Y in the general formulas (A-1) to (A-4) Ａ１ , the metal-containing film-forming compound according to claim 10, wherein X in the general formula (3) or X in the general formula (4) is a group represented by the following general formula (1). 【Chemical Formula 14】 (In the general formula (1), R ａ , R ｂ and R ｃ are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R ａ and R ｂ may be bonded to form a cyclic substituent. *1 and *2 each represent a bonding portion with a carbonyl group, and *1 and *2 may be reversed.)

13. A composition for forming a metal-containing film that functions as a resist underlayer film material used in semiconductor manufacturing, comprising (a) the metal-containing film-forming compound according to any one of claims 1 to 12 and (b) an organic solvent.

14. The composition for forming a metal-containing film according to claim 13, wherein the composition is a composition for forming a metal-containing film that can be used as a resist underlayer film in a multilayer resist method, and further contains one or more of (c) a crosslinking agent, (d) a surfactant, (e) a fluidity promoter, and (f) an acid generator.

15. The composition for forming a metal-containing film according to claim 13, wherein the (b) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

16. A method for forming a pattern on a substrate to be processed, comprising: (I-1) forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 13 on the substrate to be processed and then performing a heat treatment; (I-2) forming a resist upper layer film on the metal-containing film using a photoresist material; (I-3) after pattern-exposing the resist upper layer film, developing it with a developer to form a pattern in the resist upper layer film; (I-4) using the resist upper layer film having the pattern formed thereon as a mask, transferring the pattern to the metal-containing film by dry etching; and (I-5) processing the substrate to be processed using the metal-containing film having the pattern formed thereon as a mask to form a pattern on the substrate to be processed. A pattern forming method, characterized by comprising the above steps.

17. A method for forming a pattern on a substrate to be processed, comprising: (II-1) forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 13 on the substrate to be processed and then performing a heat treatment; (II-2) forming a resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material; (II-4) after pattern-exposing the resist upper layer film, developing it with a developer to form a pattern in the resist upper layer film; (II-5) using the resist upper layer film having the pattern formed thereon as a mask, transferring the pattern to the resist intermediate film by dry etching; (II-6) using the resist intermediate film having the pattern transferred thereto as a mask, transferring the pattern to the metal-containing film by dry etching; and (II-7) processing the substrate to be processed using the metal-containing film having the pattern formed thereon as a mask to form a pattern on the substrate to be processed. A pattern forming method, characterized by comprising the above steps.

18. A method for forming a pattern on a substrate to be processed, comprising: (III-1) forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 13 on the substrate to be processed and then performing a heat treatment; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist lower layer film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film. (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 pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern in the resist upper layer film; (III-6) A step of transferring a pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film with the pattern formed thereon as a mask; (III-7) A step of transferring a pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film with the pattern transferred thereon as a mask, and (III-8) A step of processing the substrate to be processed using the metal-containing film with the pattern formed thereon as a mask to form a pattern on the substrate to be processed A pattern forming method characterized by comprising the above steps.

19. A method for forming a pattern on a substrate to be processed, comprising: (IV-1) A step of forming a resist lower layer film on the substrate to be processed; (IV-2) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 13 on the resist lower layer film and then performing heat treatment; (IV-3) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, or a step of forming an organic adhesion film by spin coating on the metal-containing film and then forming a resist upper layer film using a photoresist material thereon; (IV-4) A step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern in the resist upper layer film; (IV-5) A step of transferring a pattern to the metal-containing film, or the organic adhesion film and the metal-containing film by dry etching using the resist upper layer film with the pattern formed thereon as a mask; (IV-6) A step of transferring a pattern to the resist lower layer film by dry etching using the metal-containing film with the pattern transferred thereon as a mask, and (IV-7) A step of processing the substrate to be processed using the resist lower layer film with the pattern formed thereon as a mask to form a pattern on the substrate to be processed A pattern forming method characterized by comprising the above steps.

20. A method for forming a pattern on a substrate to be processed, comprising: (V-1) A step of forming a resist lower layer film on the substrate to be processed; (V-2) A step of forming a combination of a resist intermediate film, or an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist lower layer film (V-3) Forming a resist upper layer film using a photoresist material on the resist intermediate film, or a combination of the inorganic hard mask intermediate film and the organic thin film; (V-4) After pattern-exposing the resist upper layer film, developing it with a developer to form a pattern in the resist upper layer film; (V-5) Using the resist upper layer film with the pattern formed thereon as a mask, transferring the pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching; (V-6) Using the resist intermediate film with the pattern transferred thereto, or the inorganic hard mask intermediate film as a mask, transferring the pattern to the resist lower layer film by dry etching; (V-7) Coating the composition for forming a metal-containing film according to claim 13 on the resist lower layer film with the pattern formed thereon, and then performing heat treatment to coat the metal-containing film and fill the spaces between the resist lower layer film patterns with the metal-containing film; (V-8) Etching back the metal-containing film covering the resist lower layer film with the pattern formed thereon by a chemical stripper or dry etching to expose the upper surface of the resist lower layer film with the pattern formed thereon; (V-9) Removing the resist intermediate film, or the hard mask intermediate film remaining on the upper surface of the resist lower layer film by dry etching; (V-10) Removing the resist lower layer film with the pattern formed thereon whose surface is exposed by dry etching to form an inverted pattern of the original pattern in the metal-containing film; (V-11) A pattern forming method comprising a step of processing the substrate to be processed using the metal-containing film with the inverted pattern formed thereon as a mask to form an inverted pattern on the substrate to be processed.

21. The pattern forming method according to claim 18, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

22. The pattern forming method according to claim 20, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

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