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 better dry etching resistance than conventional resist underlayer film materials and also having high filling and planarizing properties at the same time; a composition for forming a metal-containing film using the compound; and a patterning process using the composition.SOLUTION: A compound for forming a metal-containing film for use in a composition for forming a metal-containing film includes: at least one metal atom selected from the group consisting of Ti, Zr, and Hf; and a ligand coordinated to the metal atom, where the ligand includes a ligand derived from a compound represented by the general formula (1) in the figure.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a compound for forming a metal-containing film, a composition for forming a metal-containing film, and a patterning method using the composition.

Background Art

[0002] With the high integration and high speed of LSIs, the miniaturization of pattern dimensions has been rapidly progressing. Along with this miniaturization, lithography technology has achieved the formation of fine patterns by shortening the wavelength of the light source and appropriately selecting a resist composition for it. At the center of this has been the positive photoresist composition used as a single layer. This single-layer positive photoresist composition has a skeleton in the resist resin that has etching resistance against dry etching with chlorine-based or fluorine-based gas plasmas, and has a switching mechanism such that the exposed portion dissolves, thereby dissolving the exposed portion to form a pattern and dry-etching the substrate to be processed using the remaining resist pattern as an etching mask.

[0003] However, when the film thickness of the photoresist film used is directly miniaturized, that is, when the pattern width is made smaller, the resolution performance of the photoresist film deteriorates, and when trying to develop the photoresist film into a pattern with a developer, the so-called aspect ratio becomes too large, resulting in a problem that pattern collapse occurs. For this reason, the photoresist film has been thinned as the pattern is miniaturized.

[0004] On one hand, for processing a substrate to be processed, usually, a method of processing the substrate by dry etching using a photoresist film with a pattern formed thereon as an etching mask is used. However, in reality, there is no dry etching method that can achieve perfect etching selectivity between the photoresist film and the substrate to be processed. Therefore, during the processing of the substrate, the photoresist film is also damaged and collapses, resulting in the problem that the resist pattern cannot be accurately transferred to the substrate to be processed. Thus, with the miniaturization of patterns, higher dry etching resistance has been required for resist compositions. However, on the other hand, in order to improve the resolution, resins used in photoresist compositions have been required to have low light absorption at the exposure wavelength. Therefore, as the exposure light wavelength becomes shorter, such as i-line, KrF, and ArF, the resins have also changed from novolak resins, polyhydroxystyrene, to resins with an aliphatic polycyclic skeleton. However, in reality, the etching rate under the dry etching conditions during substrate processing has become faster, and recent photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] From this, it becomes necessary to dry-etch the substrate to be processed with a thinner and less etching-resistant photoresist film, and ensuring the materials and processes in this processing step has become an urgent task.

[0006] As one method to solve such problems, there is the multilayer resist method. This method involves interposing a resist lower layer film with different etching selectivity from the photoresist film (i.e., the resist upper layer film) between the resist upper layer film and the substrate to be processed. After obtaining a pattern on the resist upper layer film, the resist upper layer film pattern is used as a dry etching mask to transfer the pattern to the resist lower layer film by dry etching, and further, the resist lower layer film is used as a dry etching mask to transfer the pattern to the substrate to be processed by dry etching.

[0007] One of the multilayer resist methods is a three-layer resist method that can be performed using a general resist composition used in the single-layer resist method. In this three-layer resist method, for example, an organic film made of a novolak resin or the like is formed as a resist underlayer film on a substrate to be processed, a silicon-containing resist intermediate film is formed as a resist intermediate film thereon, and a normal organic photoresist film is formed as a resist upper layer film thereon. When performing dry etching with a fluorine-based gas plasma, the organic resist upper layer film has a good etching selectivity with respect to the silicon-containing resist intermediate film, so the resist upper layer film pattern can be transferred to the silicon-containing resist intermediate film by dry etching with a fluorine-based gas plasma. According to this method, even when using a resist composition that is difficult to form a pattern with a sufficient film thickness for directly processing the substrate to be processed or a resist composition that does not have sufficient dry etching resistance for substrate processing, a pattern can be transferred to the silicon-containing resist intermediate film (resist intermediate film), and then, if pattern transfer is performed by dry etching with an oxygen-based or hydrogen-based gas plasma, a pattern of an organic film (resist underlayer film) made of a novolak resin or the like that has sufficient dry etching resistance for substrate processing can be obtained. As the resist underlayer film as described above, many are already known, such as those described in Patent Document 1.

[0008] On the other hand, in recent years, the miniaturization of DRAM memories has been accelerating, and there is an increasing need for further improvement in dry etching resistance and a resist underlayer film having excellent embedding characteristics and planarization characteristics. As a coating-type resist underlayer film material having excellent embedding characteristics and planarization characteristics, for example, those described in Patent Document 2 have been reported, but when considering application in the advanced generations, there are concerns about dry etching resistance, and the application limit of the conventional coating-type resist underlayer film material is approaching.

[0009] In response to the above problems, the development of using a material containing a metal element for the resist underlayer film has been studied. Patent Document 3 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 one hand, when using a metal compound for a resist underlayer film, an issue is the embedding property. Although Patent Document 3 does not mention the embedding property, generally, metal compounds have a large thermal shrinkage during baking and induce a significant deterioration in the filling property of the pattern after high-temperature baking. Therefore, there is a concern that they are insufficient when used as a resist underlayer film material that requires high planarization characteristics, embedding characteristics, and heat resistance. Patent Documents 4 and 5 report that metal compounds modified with specific ligands have excellent embedding properties. However, the baking temperature for the embedding property evaluation performed is as low as 150°C, and there is a concern that they are insufficient when used as a resist underlayer film material that requires heat resistance (for example, characteristics against heat treatment that may be performed after forming the resist underlayer film).

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

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 an object thereof is to provide a compound for forming a metal-containing film having excellent dry etching resistance with respect to conventional resist underlayer film materials and having high embedding / planarization characteristics, a composition for forming a metal-containing film using the compound, and a pattern forming method using the composition.

Means for Solving the Problems

[0013] In order to solve the above-mentioned problems, the present invention provides a metal-containing film-forming compound used in a metal-containing film-forming composition, the metal-containing film-forming compound including at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and a ligand coordinated to the metal atom, the ligand including a ligand derived from a compound represented by the following general formula (1): [ka] (In general formula (1), R A1 is a monovalent organic group having 2 to 30 carbon atoms, X is a single bond or a linear or branched divalent organic group having 2 to 10 carbon atoms, and R A1 and X contains at least one structure represented by the following general formulas (a-1) to (a-3): [ka] (In general formulas (a-1) to (a-3), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and R b represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.

[0014] Such a metal-containing film-forming compound contains at least one of the crosslinking groups represented by the above general formulas (a-1) to (a-3). When used in a metal-containing film-forming composition, the compound exhibits small volume shrinkage during baking, and even after high-temperature baking, the composition exhibits excellent planarization properties / filling properties, and has sufficient dry etching resistance.

[0015] In the present invention, the R A1 Preferably, contains at least one of an aromatic ring, an alicyclic hydrocarbon, and a heterocycle.

[0016] For such a compound for forming a metal-containing film, since it contains a ligand having excellent heat resistance derived from the organic compound of the general formula (1) containing any one or more of the crosslinking groups represented by the general formulas (a-1) to (a-3), 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 composition for forming a metal-containing film excellent in planarization characteristics / embedding characteristics can be provided.

[0017] Further, in the present invention, it is preferable that the ligand contains a ligand derived from a compound represented by the following general formula (2).

Chemical formula

[0018] If the ligand is a ligand derived from a compound represented by the general formula (2), it becomes possible to highly balance the thermal fluidity and thermosetting properties of the compound for forming a metal-containing film, and when this is used in a composition for forming a metal-containing film, a composition for forming a metal-containing film showing more excellent planarization characteristics / embedding characteristics can be provided.

[0019] Further, in the present invention, it is preferable that W1 in the general formula (2) is any of the following structures.

Chemical formula

[0020] In the general formula (2), if W1 is any of the above structures, the heat resistance of the compound for forming a metal-containing film can be improved, and when this is used in a composition for forming a metal-containing film, a composition for forming a metal-containing film having more excellent planarization characteristics / embedding characteristics can be provided.

[0021] Further, in the present invention, the compound for forming a metal-containing film is preferably a reaction product of a metal-containing compound containing any one of the metal compounds represented by the following general formula (3), or a hydrolyzate, condensate, and hydrolytic condensate of the metal compound represented by the following general formula (3), and the compound represented by the general formula (1) or the general formula (2).

Chemical formula

[0022] For such a compound for forming a metal-containing film, since it is a compound for forming a metal-containing film derived from the metal compound represented by the general formula (3) or a metal-containing compound obtained by hydrolyzing, condensing, or hydrolytically condensing the metal compound represented by the general formula (3), when this is used in a composition for forming a metal-containing film, it is possible to form a dense metal-containing film, and a metal-containing film having extremely excellent dry etching resistance with respect to a substrate to be processed can be provided.

[0023] Further, in the present invention, the general formula (3) preferably has the structure of the following general formula (4).

Chemical formula

[0024] A metal compound having such a structure is preferable from the viewpoints of productivity and availability of raw materials.

[0025] Further, in the present invention, it is preferable that the compound for forming a metal-containing film further contains a ligand derived from a silicon compound represented by the following general formula (5). [Chemical formula] (In general formula (5), R 3A , R 3B and R 3C are each an organic group having 1 to 30 carbon atoms having any one of the crosslinking groups represented by the following general formulas (b-1) to (b-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, respectively.) [Chemical formula] (In general formulas (b-1) to (b-3), R3 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.)

[0026] By including such a ligand, the stability of the compound for forming a metal-containing film can be further improved.

[0027] The present invention also provides a composition for forming a metal-containing film used in semiconductor manufacturing, which contains the above-described (A) compound for forming a metal-containing film and (B) an organic solvent.

[0028] Such a composition for forming a metal-containing film contains a metal-containing compound having excellent heat resistance and thermal fluidity. Therefore, it has excellent dry etching resistance compared to conventional resist underlayer film materials and also has advanced embedding / planarization characteristics compared to conventional metal-containing film materials. A composition for forming a metal-containing film can be provided.

[0029] In the present invention, it is preferable that the composition further contains one or more of (E) a crosslinking agent, (G) a surfactant, and (H) an acid generator.

[0030] If it is a composition for forming a metal-containing film containing the above additives, it becomes a composition for forming a metal-containing film with more excellent coatability, dry etching resistance, and embedding / planarization characteristics.

[0031] In the present invention, it is preferable that the (B) organic solvent contains one or more organic solvents having a boiling point of 180 °C or higher as (B1) a high-boiling solvent.

[0032] By imparting thermal fluidity to the composition for forming a metal-containing film by adding a high-boiling solvent, the composition for forming a metal-containing film has advanced embedding / planarization characteristics.

[0033] In the present invention, it is preferable that the composition for forming a metal-containing film further contains a fluidity promoter (BP) having an organic group represented by the following general formula (3') and an aromatic ring.

Chemical formula

[0034] By imparting heat resistance and thermal fluidity to the composition for forming a metal-containing film by adding a fluidity promoter (BP), the composition for forming a metal-containing film further has advanced embedding / planarization characteristics.

[0035] At this time, it is preferable that the fluidity promoter (BP) has at least one structural unit represented by the following general formulas (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0036] If it is a composition for forming a metal-containing film to which a fluidity promoter (BP) having at least one structural unit represented by the general formulas (BP-1) to (BP-5) is added, it becomes a resist material having more excellent embedding / planarization characteristics.

[0037] 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 described above 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) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film having the pattern as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film having the pattern transferred thereto to form a pattern on the substrate to be processed A pattern forming method having the above steps is provided.

[0038] By the pattern forming method using the above two-layer resist process, a fine pattern can be formed on a workpiece (substrate to be processed).

[0039] 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 described above on a substrate to be processed and then performing a heat treatment; (II-2) A step of forming a silicon-containing resist intermediate film on the metal-containing film; (II-3) A step of forming a resist upper layer film on the silicon-containing 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 on which the pattern is formed as a mask, transferring the pattern to the silicon-containing resist intermediate film by dry etching; (II-6) Using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask, transferring the pattern to the metal-containing film by dry etching; and (II-7) Using the metal-containing film to which the pattern has been transferred as a mask to process the substrate to be processed and form a pattern on the substrate to be processed A pattern forming method having the above is provided.

[0040] By the pattern forming method using the above three-layer resist process, a fine pattern can be formed on the object to be processed with high precision.

[0041] Further, the present invention is a method for forming a pattern on a substrate to be processed, comprising: (III-1) After applying the composition for forming a metal-containing film described above on the substrate to be processed and performing heat treatment to form a metal-containing film; (III-2) Forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) Forming an organic thin film on the inorganic hard mask intermediate film; (III-4) Forming a resist 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 on which the pattern is formed 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 to which the pattern has been transferred as a mask, transferring the pattern to the metal-containing film by dry etching; and (III-8) Forming a pattern on the substrate to be processed by using the metal-containing film on which the pattern has been transferred as a mask to process the substrate to be processed provided is a pattern forming method having the above.

[0042] By the above pattern forming method using a four-layer resist process, a fine pattern can be formed on the object to be processed with high precision.

[0043] At this time, it is preferable that the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

[0044] When the inorganic hard mask intermediate film is formed by a CVD method or an ALD method, a fine pattern can be formed on the object to be processed with higher precision.

[0045] Further, the present invention is a method for forming a pattern on a substrate to be processed, comprising: (IV-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film described above on the substrate to be processed and then performing heat treatment; (IV-2) A step of forming a resist lower layer film on the metal-containing film; (IV-3) A step of forming a combination of a silicon-containing 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; (IV-4) A step of forming a resist upper layer film using a photoresist material on the silicon-containing resist intermediate film or the organic thin film; (IV-5) A step of forming a pattern on the resist upper layer film by performing pattern exposure on the resist upper layer film and then developing with a developer; (IV-6) A step of transferring the pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (IV-7) Using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film onto which the pattern has been transferred as a mask, transferring the pattern to the resist underlayer film by dry etching; (IV-8) Using the resist underlayer film onto which the pattern has been transferred as a mask, transferring the pattern to the metal-containing film by dry etching, and (IV-9) Using the metal-containing film onto which the pattern has been transferred as a mask, processing the substrate to be processed to form a pattern on the substrate to be processed A pattern forming method having the above steps is provided.

[0046] By the above pattern forming method using a multilayer resist process, a fine pattern can be formed on the object to be processed with high precision.

[0047] Further, the present invention is a method for forming a pattern on a substrate to be processed, comprising: (V-1) Forming a resist underlayer 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 resist underlayer film; (V-3) 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) After pattern exposure of the resist upper layer film, developing with a developer to form a pattern on the resist upper layer film; (V-5) Using the resist upper layer 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 onto which the pattern has been transferred as a mask, transferring the pattern to the resist underlayer film by dry etching; (V-7) On the resist underlayer film onto which the pattern has been transferred, after applying the composition for forming a metal-containing film described above and then performing heat treatment, a metal-containing film is coated to fill the spaces between the resist underlayer film patterns with the metal-containing film. (V-8) Etching back the metal-containing film covering the resist underlayer film onto which the pattern has been transferred by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern has been formed. (V-9) Removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching. (V-10) Removing the resist underlayer film onto which the pattern has been transferred with the surface exposed by dry etching to form an inverted pattern of the original pattern on the metal-containing film, and (V-11) Using the metal-containing film on which the inverted pattern has been formed as a mask to process the substrate to be processed and form an inverted pattern on the substrate to be processed. Provided is a tone inversion type pattern forming method having the above steps.

[0048] By the pattern forming method according to the above inversion process, a finer pattern can be formed on the object to be processed with higher precision.

Effect of the Invention

[0049] As described above, since the compound for forming a metal-containing film of the present invention contains at least one ligand having a crosslinking group represented by the above general formulas (a-1) to (a-3), 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 composition for forming a metal-containing film excellent in planarization characteristics / embedding characteristics can be provided. Further, the composition for forming a metal-containing film of the present invention can also be used as a resist underlayer film material for forming a resist underlayer film.

[0050] Particularly, in a fine patterning process using a multilayer resist method in the semiconductor device manufacturing process, even on a substrate to be processed having portions where embedding / planarization is difficult, such as a dense portion of a fine pattern structure with a high aspect ratio typified by a DRAM memory with increasing miniaturization, it is possible to embed without causing defects such as voids or peeling. Also, compared with conventional coating-type resist underlayer film materials, it has excellent dry etching resistance, so that a finer pattern can be formed on the object to be processed with even higher precision.

Brief Description of the Drawings

[0051]

Figure 1

Figure 2

Figure 3

Figure 4

Embodiments for Carrying Out the Invention

[0052] 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 excellent in embedding property and flatness, a metal-containing film-forming compound useful for the composition, and a pattern formation method using the composition, in order to form a resist underlayer film capable of transferring a resist pattern to a substrate to be processed with higher precision.

[0053] The inventors of the present invention have intensively studied, paying attention to a metal material that exhibits excellent etching resistance against conventional resist underlayer film materials. On the other hand, conventional metal compounds for forming resist underlayer films have poor heat resistance and cause rapid volume shrinkage during baking. Therefore, it is difficult to fill and planarize the steps of the substrate to be processed after high-temperature baking. The inventors of the present invention considered that if it has an organic group with excellent heat resistance characteristics, it can reduce the rapid volume shrinkage during baking and improve the thermal fluidity, so that it is possible to fill the steps of the substrate to be processed without generating voids even after high-temperature baking. Furthermore, if it has a structure containing a crosslinking group at the terminal, it is expected to be a compound for forming a metal-containing film with more excellent heat resistance characteristics because it has excellent thermosetting properties during baking.

[0054] The inventors of the present invention further intensively studied and found that a metal-containing film-forming compound containing at least one or more compounds represented by the following general formula (1) containing at least one organic crosslinking group represented by the following general formula (a-1) to (a-3) as a ligand has excellent thermosetting properties, so it can reduce the rapid volume shrinkage during baking and has good thermal fluidity, so that high-level embedding / planarization characteristics can be realized, and thus completed the present invention.

[0055] That is, the present invention is a metal-containing film-forming compound used in a metal-containing film-forming composition, wherein the metal-containing film-forming compound contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and a ligand coordinated to the metal atom, and the ligand contains a ligand derived from a compound represented by the following general formula (1).

Chemical formula

Chemical formula

[0056] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0057] <(Compound for forming a metal-containing film)> The present invention relates to a compound for forming a metal-containing film used in a composition for forming a metal-containing film, wherein the compound for forming a metal-containing film contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and a ligand coordinated to the metal atom, and the ligand contains a ligand derived from a compound represented by the following general formula (1). [Chemical formula] (In general formula (1), R A1 is a monovalent organic group having 2 to 30 carbon atoms, X is a single bond or a divalent organic group having 2 to 10 carbon atoms in a linear or branched form, and at least one of R A1 and X contains a structure represented by the following general formulas (a-1) to (a-3).) [Chemical formula] (In general formulas (a-1) to (a-3), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, R b is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding site.)

[0058] In the above general formula (1), R A1 is a monovalent organic group having 2 to 30 carbon atoms, X is a single bond or a divalent organic group having 2 to 10 carbon atoms in a linear or branched form, and R A1It contains at least one or more structures represented by the general formulas (a-1) to (a-3) in either or both of them and X.

[0059] In the general formulas (a-1) to (a-3), R a is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. From the viewpoint of raw material availability, a hydrogen atom, a methyl group, or a phenyl group is preferable, and from the viewpoint of thermosetting properties, a hydrogen atom is more preferable. R b is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. From the viewpoint of raw material availability, a hydrogen atom or a methyl group is preferable, and q is 0 or 1.

[0060] In the above general formula (1), the above R A1 is preferably one containing one or more of an aromatic ring, an alicyclic hydrocarbon, and a heterocyclic ring from the viewpoint of heat resistance.

[0061] Since the above ligand contains one or more of an aromatic ring, an alicyclic hydrocarbon, and a heterocyclic ring, the heat resistance of the metal-containing compound can be improved, and the reaction of the crosslinking group contained in the ligand can be promoted. As a result, the volume shrinkage during high-temperature baking is suppressed, and as a result, a metal-containing film excellent in embedding properties can be formed.

[0062] From the viewpoint of heat resistance, it is preferable that the above ligand contains a ligand derived from a compound represented by the following general formula (2).

Chemical formula

[0063] X in the general formula (2) above A is a single bond or a divalent organic group having 1 to 10 carbon atoms in a linear or branched form, and X A when containing a structure represented by the general formula (a-1) to (a-3), X A is preferably a divalent organic group having 3 to 10 carbon atoms in a linear or branched form, and more preferably a divalent organic group having 3 to 5 carbon atoms in a linear or branched form. On the other hand, X A when not containing a structure represented by the general formula (a-1) to (a-3), X A is preferably a single bond or a divalent organic group having 1 to 7 carbon atoms in a linear form, and more preferably a single bond or a divalent organic group having 1 to 2 carbon atoms in a linear form.

[0064] From the viewpoint of raw material availability, it is more preferable that W1 in the general formula (2) above is any of the following structures.

Chemical formula

[0065] The metal-containing film-forming compound is preferably a reaction product of a metal compound represented by the following general formula (3), or a metal-containing compound containing any of a hydrolyzate, a condensate, and a hydrolyzed condensate of the metal compound represented by the following general formula (3) (hereinafter, (a) metal-containing compound) and a compound represented by the general formula (1) or the general formula (2) above.

Chemical formula

[0066] For such a compound for forming a metal-containing film, when used in a composition for forming a metal-containing film, a metal-containing film excellent in dry etching resistance against oxygen gas can be formed.

[0067] [(a) Metal-containing compound] (Hydrolyzable group) The hydrolyzable group X in the general formula (3) above B includes a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, and -NR a’ R b’ is mentioned. R a’ and R b’ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0068] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0069] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, etc.

[0070] Examples of the carboxylate group include an acetate group, a propionate group, a butyrate group, an n-hexanecarboxylate group, an n-octanecarboxylate group, etc.

[0071] Examples of the acyloxy group include an acetoxy group, an ethylyloxy group, a propionyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amyloxy group, an n-hexanecarbonyloxy group, an n-octanecarbonyloxy group, etc.

[0072] The above -NR a’ R b’Examples thereof include an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, and the like.

[0073] The hydrolyzable group X B is preferably an alkoxy group, more preferably an i-propoxy group, an n-butoxy group, or a t-butoxy group.

[0074] L in the general formula (3) above is a monodentate ligand or a polydentate ligand having 0 to 30 carbon atoms.

[0075] (Monodentate ligand) Examples of the monodentate ligand include a hydroxo ligand, a carboxy ligand, an amide ligand, an amine ligand, an ammonia ligand (ammine), an olefin ligand, and the like.

[0076] Examples of the amide ligand include an unsubstituted amide ligand (NH2), a methylamide ligand (NHMe), a dimethylamide ligand (NMe2), a diethylamide ligand (NEt2), a dipropylamide ligand (NPr2), and the like.

[0077] Examples of the amine ligand include pyridine, a trimethylamine ligand, a piperidine ligand, and the like.

[0078] Examples of the olefin ligand include chain olefins such as ethylene and propylene, and cyclic olefins such as cyclopentene, cyclohexene, and norbornene.

[0079] (Polydentate ligand) Examples of the polydentate ligand include a ligand derived from a hydroxy acid ester, a ligand derived from a β-diketone, a ligand derived from a β-ketoester, a ligand derived from an α,α-dicarboxylic acid ester, a hydrocarbon having a π bond, a diphosphine, and the like.

[0080] Examples of the hydroxy acid ester include glycolic acid ester, lactic acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, salicylic acid ester, and the like.

[0081] Examples of the β-diketone include acetylacetone, 3-phenyl-2,4-pentanedione, 3-alkyl-2,4-pentanedione, 3,5-heptanedione, dipivaloylmethane, 1-phenyl-1,3-butanedione, 1,3-diphenyl-1,3-propanedione, and the like.

[0082] Examples of the β-keto ester include acetoacetic acid ester, α-alkyl-substituted acetoacetic acid ester, β-ketopentanoic acid ester, benzoylacetic acid ester, 1,3-acetonedicarboxylic acid ester, and the like.

[0083] Examples of the α,α-dicarboxylic acid ester include malonic acid diester, α-alkyl-substituted malonic acid diester, α-cycloalkyl-substituted malonic acid diester, α-aryl-substituted malonic acid diester, and the like.

[0084] Examples of the hydrocarbon having a π bond include chain dienes such as butadiene and isoprene, cyclic dienes such as cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, cyclohexadiene, and norbornadiene, and aromatic hydrocarbons such as benzene, toluene, xylene, hexamethylbenzene, naphthalene, and indene.

[0085] Examples of the diphosphine include 1,1-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 1,1'-bis(diphenylphosphino)ferrocene, and the like.

[0086] In the above general formula (3), a + b = 4, and a and b are integers from 0 to 4. As a, 0 to 3 is preferable, 0 to 2 is more preferable, 1 to 2 is further preferable, and 2 is particularly preferable. As b, 2 to 4 is preferable, 2 or 3 is more preferable, and 2 is further preferable. By setting a and b within the above ranges, the stability of the compound for forming a metal-containing film of the present invention can be enhanced.

[0087] Examples of the above-mentioned metal-containing compound (a) include, as a titanium-containing compound, titanium(IV) diisopropoxybis(2,4-pentanedionate), titanium(IV) tetra-n-butoxide, titanium(IV) tetra-n-propoxide, titanium(IV) tri-n-butoxymonostearate, titanium(IV) butoxide oligomer, aminopropyltrimethoxytitanium(IV), titanium(IV) triethoxymono(2,4-pentanedionate), titanium(IV) tri-n-propoxymono(2,4-pentanedionate), titanium(IV) triisopropoxymono(2,4-pentanedionate), titanium(IV) di-n-butoxybis(2,4-pentanedionate), etc.; as a zirconium-containing compound, zirconium(IV) dibutoxybis(ethylacetoacetate), zirconium(IV) di-n-butoxybis(2,4-pentanedionate), zirconium(IV) tetra-n-butoxide, zirconium(IV) tetra-n-propoxide, zirconium(IV) tetraisopropoxide, aminopropyltriethoxyzirconium(IV), 2-(3,4-epoxycyclohexyl)ethyltrimethoxyzirconium(IV), γ-glycidoxypropyltrimethoxyzirconium(IV), 3-isocyanatopropyltrimethoxyzirconium(IV), zirconium(IV) triethoxymono(2,4-pentanedionate), zirconium(IV) tri-n-propoxymono(2,4-pentanedionate), zirconium(IV) triisopropoxymono(2,4-pentanedionate), zirconium(IV) tri(3-methacryloxypropyl)methoxide, zirconium(IV) tri(3-acryloxypropyl)methoxide, etc.; and as a hafnium-containing compound, hafnium(IV) diisopropoxybis(2,4-pentanedionate), hafnium(IV) tetrabutoxide, hafnium(IV) tetraisopropoxide, hafnium(IV) tetraethoxide, hafnium(IV) dichlorobis(cyclopentadienyl), etc.

[0088] From the perspective of raw material availability, it is preferable that the general formula (3) has the structure of the following general formula (4). [Chemical formula] (In general formula (4), M is any one of Ti, Zr, and Hf, and R 1A is a monovalent organic group having 1 to 20 carbon atoms.)

[0089] In the general formula (4), R 1A is a monovalent organic group having 1 to 20 carbon atoms, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t-butyl group are preferable, and an i-propyl group, an n-butyl group, and a t-butyl group are more preferable.)

[0090] (A) During the synthesis reaction of the metal-containing film-forming compound, in addition to the metal-containing compound and the compound containing a group selected from the above general formulas (a-1) to (a-3), a compound that can become a monodentate ligand or a polydentate ligand in the metal-containing film-forming compound (hereinafter (b) ligand-forming compound) may be added.)

[0091] Examples of the above (b) ligand-forming compound include compounds derived from a hydroxy ligand, a carboxy ligand, an amide ligand, an amine ligand, an ammonia ligand, an olefin ligand, etc., which are listed as L in the above general formula (3), a ligand derived from a hydroxy acid ester, a ligand derived from β-diketone, a ligand derived from β-ketoester, a ligand derived from α,α-dicarboxylic acid ester, etc., and in addition, compounds having a plurality of hydroxy groups, etc.)

[0092] Furthermore, the (b) ligand-forming compound may be an organic compound having 1 to 40 carbon atoms containing at least one or more crosslinking groups represented by any of the following general formulas (c-1) to (c-4), (d-1) to (d-4), and (e-1) to (e-3).)

[0093]

Chemical formula

Chemical formula

[0094] Since the compound for forming a ligand in (b) contains at least one crosslinking group represented by any of the above (c-1) to (c-4), (d-1) to (d-4), and (e-1) to (e-3), the compound for forming a metal-containing film of the present invention synthesized using this can obtain sufficient thermal fluidity during film formation. Therefore, when used in a composition for forming a metal-containing film, a metal-containing film having excellent flatness can be formed.

[0095] (A) From the viewpoints of the productivity and stability of the compound for forming a metal-containing film, the above-mentioned ligand-forming compound (b) is more preferably a compound derived from a carboxy ligand, a compound derived from a ligand derived from β-diketone, or a compound having a plurality of hydroxy groups. These can be used alone or in combination of two or more.

[0096] Examples of the compound derived from the carboxy ligand include compounds represented by the following general formula (6’). [Chemical formula] (In the above general formula (6’), p1 is 0 or 1. When p1 is 1, X 1 is a divalent organic group having 2 to 20 carbon atoms, and W is an alkoxy group having 1 to 10 carbon atoms, the following general formula (6-A), or any one of the above general formulas (d-1) to (d-4). When p1 is 0, X 1 is a monovalent organic group having 8 to 30 carbon atoms containing a crosslinking group of any one of the structures represented by the above general formulas (c-2) to (c-4) and an aromatic ring.) [Chemical formula] (In the above general formula (6-A), Y A is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, R Aa is any one of the structures represented by the above general formulas (c-1) to (c-4), h represents 1 to 6, and * represents the bonding portion with the carbon atom of the carbonyl.)

[0097] For a compound derived from a carboxy ligand having such a structure, the thermosetting property of the metal-containing film-forming compound of the present invention synthesized using this compound is improved, and when used in a metal-containing film-forming composition, a metal-containing film excellent in mixing resistance with the resist upper layer film can be formed.

[0098] In the general formula (6’), it is preferable that p1 is 1 and W has a structure represented by the following general formula (6-B). [Chemical formula] (In the above general formula (6-B), R A4 has the structure represented by the above general formula (c-1), and R A5 has the structure represented by the above general formula (c-2) or (c-3), Z A is an oxygen atom or a secondary amine, L A is a divalent hydrocarbon group having 1 to 10 carbon atoms, R A6 is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, t1 is an integer from 1 to 6, s1 is an integer from 0 to 5, t1 + s1 is an integer from 1 or more to 6 or less, r is an integer from 1 to 10, u is 0 or 1, m is 0 or 1, and * represents the bonding portion with the carbon atom of the carbonyl.)

[0099] For a compound derived from a carboxy ligand having such a structure, since the heat resistance of the compound for forming a metal-containing film of the present invention synthesized using this is improved, when used in a composition for forming a metal-containing film, the formed metal-containing film exhibits excellent film-forming properties, and also suppresses the generation of sublimates during heat curing to prevent contamination of the apparatus.)

[0100] [[ID=2\0]]In the above general formula (6’), it is preferable that p1 is 1, W is an alkoxy group having 1 to 10 carbon atoms, and X 1 is any of the structures represented by the following formula (6-C). [Chemical formula]

[0101] For a compound derived from a carboxy ligand having such a structure, since the heat resistance of the compound for forming a metal-containing film of the present invention synthesized using this is improved, when used in a composition for forming a metal-containing film, the formed metal-containing film exhibits excellent film-forming properties, and also suppresses the generation of sublimates during heat curing to prevent contamination of the apparatus.)

[0102] Alternatively, in the above general formula (6’), it is preferable that p1 is 0 and X 1 is any of the structures represented by the following general formula (6-D). [Chemical formula] (In the above general formula (6-D), R c is the same as above, and * represents the bonding part with the carbon atom of the carbonyl group.)

[0103] Examples of the compound derived from the above carboxy ligand include the compound represented by the following general formula (7’). [Chemical formula] (In the above general formula (7’), X 2 is a divalent organic group having 1 to 31 carbon atoms, and R 7A is any one of the above general formulas (e-1) to (e-3).)

[0104] In the above general formula (7’), X 2 is a divalent organic group having 1 to 31 carbon atoms, and from the viewpoint of thermosetting properties, it is preferably a saturated divalent hydrocarbon group having 1 to 20 carbon atoms or an unsaturated divalent hydrocarbon group having 2 to 20 carbon atoms.

[0105] In the above general formula (e-2), R e2 is a hydrogen atom, a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms (saturated or 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 e2 is preferably a saturated monovalent hydrocarbon group having 1 to 20 carbon atoms or an unsaturated monovalent hydrocarbon group having 2 to 20 carbon atoms.

[0106] In the above general formulas (e-1) to (e-3), Y e is a divalent organic group having 1 to 20 carbon atoms, and is preferably a saturated divalent hydrocarbon group having 1 to 20 carbon atoms or an unsaturated divalent hydrocarbon group having 2 to 20 carbon atoms. If Y e is a saturated divalent hydrocarbon group having 1 to 20 carbon atoms or an unsaturated divalent hydrocarbon group having 2 to 20 carbon atoms, the thermosetting property of the compound for forming a metal-containing film of the present invention synthesized using this can be further improved. Also, it is preferable from the viewpoint of raw material availability.

[0107] Y e As an example, specifically, the following structures can be exemplified, but are not limited thereto.

Chemical formula

[0108] In the above general formula (e-4), R e3 is an organic group in which a protecting group is removed by the action of either an acid, heat, or both, and is 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. As the tertiary hydrocarbyl group, those having 4 to 20 carbon atoms are preferred, and among them, those having fewer carbon atoms are more preferred.

[0109] Examples of the compound derived from the ligand derived from β-diketone include, for example, a compound represented by the following general formula (8’).

Chemical formula

[0110] The compound of the above general formula (8’) preferably contains at least one or more crosslinking groups represented by any of the above general formulas (c-1) to (c-4) and (d-1) to (d-4). Such a compound is preferable because the thermosetting property of the compound for forming a metal-containing film of the present invention synthesized using this can be further improved.

[0111] Examples of the compound having a plurality of hydroxy groups include, for example, divalent alcohols represented by any of the following general formulas (8-A) to (8-C).

Chemical formula

[0112] The compounds of the above general formulas (8-A) to (8-C) preferably contain at least one crosslinking group represented by any of the above general formulas (c-1) to (c-4) and (d-1) to (d-4). Such compounds are preferable because the thermosetting property of the compound for forming a metal-containing film of the present invention synthesized using this can be further improved.

[0113] (A) In the compound for forming a metal-containing film, the content of the ligand containing a group selected from the above general formulas (a-1) to (a-3) is preferably 10 mol% to 90 mol% of the total ligands coordinated to the metal atom, more preferably 20 mol% to 80 mol%, and even more preferably 25 mol% to 75 mol%. (b) The content of the ligand derived from the ligand-forming compound is preferably 0 mol% to 50 mol% of the total ligands coordinated to the metal atom, and more preferably 0 mol% to 30 mol%. Ligands other than the ligand containing a group selected from the above general formulas (a-1) to (a-3) and the ligand derived from the (b) ligand-forming compound, for example, ligands derived from alkoxy groups having 1 to 10 carbon atoms, preferably have a content of 0 mol% to 90 mol% of the total ligands coordinated to the metal atom, and a content of 20 mol% to 80 mol% is more preferable.

[0114] Furthermore, in the synthesis reaction of the compound for forming a metal-containing film, (a) in addition to the metal-containing compound and the compound containing a group selected from the general formulas (a-1) to (a-3), (c) a silicon compound may be added.

[0115] (a) By substituting the hydrolyzable group of the metal-containing compound with a silicon-containing compound, the stability of the compound for forming a metal-containing film in the metal-containing film-forming composition can be improved.

[0116] That is, it is preferable that the compound for forming a metal-containing film further contains a ligand derived from a silicon compound represented by the following general formula (5). [Chemical formula] (In general formula (5), R 3A , R 3B and R 3C are each an organic group having 1 to 30 carbon atoms having a crosslinking group of any of the structures represented by the following general formulas (b-1) to (b-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, respectively.) [Chemical formula] (In general formulas (b-1) to (b-3), R3 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding site.)

[0117] (c) As the silicon compound, any of the following groups is more preferable, and trimethylsilanol is even more preferable from the viewpoint of productivity. [Chemical formula] (In the above formula, * represents a bonding site with a metal atom.)

[0118] (A) When the compound for forming a metal-containing film contains a ligand containing a group selected from the above general formulas (a-1) to (a-3) and (c) a ligand derived from a silicon compound, in the (A) compound for forming a metal-containing film, the content of the ligand containing a group selected from the above general formulas (a-1) to (a-3) is preferably 10 mol% to 90 mol% of the total ligands coordinated to the metal atom, more preferably 20 mol% to 80 mol%, and even more preferably 25 mol% to 75 mol%. The ligand derived from the (c) silicon compound preferably has a content of 10 mol% to 90 mol% of the total ligands coordinated to the metal atom, and more preferably 20 mol% to 80 mol%. Ligands other than the ligand containing a group selected from the above general formulas (a-1) to (a-3) and the ligand derived from the (c) silicon compound, for example, ligands derived from alkoxy groups having 1 to 10 carbon atoms, preferably have a content of 0 mol% to 90 mol% of the total ligands coordinated to the metal atom, and more preferably a content of 20 mol% to 80 mol%.

[0119] When synthesizing the compound (A) for forming a metal-containing film containing a ligand containing a group selected from the above general formulas (a-1) to (a-3), if the compound (A) for forming a metal-containing film contains a ligand containing a group selected from the above general formulas (a-1) to (a-3), the synthesis method is not particularly limited. For example, (a) a metal alkoxide or metal acetylacetonate (acac) can be used for the metal-containing compound, and it can be obtained by reacting the alkoxide or acac metal with a compound containing a group selected from the above general formulas (a-1) to (a-3). After hydrolytic condensation of the (a) metal-containing compound, it may be reacted with a compound containing a group selected from the above general formulas (a-1) to (a-3), or after reacting the (a) metal-containing compound with a compound containing a group selected from the above general formulas (a-1) to (a-3), it may be hydrolytically condensed. When it is difficult to control the hydrolytic condensation, it may be reacted with a compound containing a group selected from the above general formulas (a-1) to (a-3) in a non-aqueous environment. These are preferably adjusted appropriately according to the properties required for the (A) metal compound and the metal-containing film. (c) When a silicon compound and a compound containing a group selected from the above general formulas (a-1) to (a-3) are used as ligands, after reacting the (a) metal-containing compound with the (c) silicon compound, it is preferable to react it with a compound containing a group selected from the above general formulas (a-1) to (a-3).

[0120] Examples of the method for performing a hydrolytic condensation reaction using the (a) metal-containing compound include a method of subjecting the (a) metal-containing compound to a hydrolytic condensation reaction in a solvent containing water. In this case, other compounds having a hydrolyzable group may be added as necessary. Also, as a catalyst for the hydrolytic condensation reaction, an acid such as acetic acid may be added. The lower limit of the amount of water used in this hydrolytic condensation reaction is preferably 0.2 times the molar amount, more preferably 1 time the molar amount, and even more preferably 3 times the molar amount, relative to the hydrolyzable group contained in the (a) metal-containing compound or the like. The upper limit of the amount of water is preferably 20 times the molar amount, more preferably 15 times the molar amount, and even more preferably 10 times the molar amount.

[0121] (A) The solvent used in the synthesis reaction of the metal-containing film-forming compound is not particularly limited, and for example, the same solvents as those exemplified as the (B) organic solvent described below can be used. Typical solvents and solvent mixtures include those containing an ester, ether, or alcohol functional group. For example, a mixture of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) in a volume ratio of 70 / 30. Examples of other solvents that can be used include butanediol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, 1-butanol, 2-butanol, 2-methyl-1-propanol, 4-methyl-2-pentanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diamyl ether, isoamyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and the like.

[0122] <Metal-containing film-forming composition> Further, the present invention provides a metal-containing film-forming composition used in semiconductor manufacturing, which contains the (A) metal-containing film-forming compound described above and the (B) organic solvent.

[0123] For such a composition for forming a metal-containing film, since it contains a compound for forming a metal-containing film that highly combines thermal fluidity and thermosetting properties, it has excellent dry etching resistance compared to conventional resist underlayer film materials, and can provide a composition for forming a metal-containing film as a resist underlayer film material having advanced embedding / planarization characteristics.

[0124] Hereinafter, the 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.

[0125] <(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 (A) compound for forming a metal-containing film and, when contained, the following (E) crosslinking agent, (G) surfactant, (H) acid generator, and other additives.

[0126] Specifically, for example, the organic solvents described in paragraphs

[0091] to

[0092] of JP-A No. 2007-199653 can be added. More specifically, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and γ-butyrolactone, or a mixture containing one or more of these is preferably used.

[0127] The blending amount of the (B) organic solvent is preferably in the range of 200 to 10,000 parts by mass, more preferably 250 to 5,000 parts by mass, per 100 parts by mass of the (A) compound for forming a metal-containing film.

[0128] The metal-containing film-forming composition may contain one or more of the above (A) metal-containing film-forming compounds and (B) organic solvents, and may contain additives such as (E) crosslinking agent, (G) surfactant, and (H) acid generator as necessary. That is, it is preferable that the composition further contains one or more of (E) crosslinking agent, (G) surfactant, and (H) acid generator. Hereinafter, components contained in the metal-containing film-forming composition of the present invention other than the above (A) metal-containing film-forming compound and (B) organic solvent will be described.

[0129] <(B1) High-boiling solvent> In the metal-containing film-forming composition of the present invention, the (B) organic solvent may be used as a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents ((B1) high-boiling solvent) having a boiling point of 180°C or higher. That is, it is preferable that the (B) organic solvent contains one or more organic solvents having a boiling point of 180°C or higher as the (B1) high-boiling solvent.

[0130] (B1) 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.

[0131] (B1) The high - boiling solvent may be appropriately selected from, for example, the above - mentioned ones according to the temperature at which the composition for forming a metal - containing film of the present invention is heat - treated. 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, the volatilization during baking (heat treatment) does not become too fast, so that sufficient thermal fluidity can be obtained during film formation, and it is considered that a resist underlayer film excellent in embedding / planarization characteristics can be formed. Also, with such a boiling point, it volatilizes after baking and does not remain in the film, so it does not adversely affect the film physical properties such as etching resistance.

[0132] In addition, when using (B1) the high - boiling solvent, the blending amount is preferably 1 to 30 parts by mass with respect to 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.

[0133] [(E) Cross - linking agent] In addition, the composition for forming a metal-containing film of the present invention may further contain (E) a crosslinking agent in order to enhance the curability of the compound for forming a metal-containing film and further suppress intermixing with the resist upper layer film. The (E) crosslinking agent is not particularly limited, and various known types of crosslinking agents can be widely used. As an example, a melamine-based crosslinking agent, an acrylate-based crosslinking agent, a glycoluril-based crosslinking agent, a benzoguanamine-based crosslinking agent, a urea-based crosslinking agent, a β-hydroxyalkylamide-based crosslinking agent, an isocyanurate-based crosslinking agent, an aziridine-based crosslinking agent, an oxazoline-based crosslinking agent, an epoxy-based crosslinking agent, a phenol-based crosslinking agent (for example, a methylol or alkoxymethyl type crosslinking agent of polynuclear phenols) can be exemplified. The content of the (E) 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 compound (A) for forming a metal-containing film.

[0134] 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. Specific examples of the urea-based crosslinking agent include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy-substituted products, and their partial self-condensates. Specific examples of the β-hydroxyalkylamide-based crosslinking agent include N,N,N’,N’-tetrakis(2-hydroxyethyl)adipic acid amide. Specific examples of the isocyanurate-based crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate. Specific examples of the aziridine-based crosslinking agent include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Specific examples of the oxazoline-based crosslinking agent include 2,2'-isopropylidene bis(4-benzyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2,2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tert-butyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylene bis(2-oxazoline), 1,4-phenylene bis(2-oxazoline), and 2-isopropenyl oxazoline copolymer. Specific examples of the epoxy-based crosslinking agent include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0135] Specific examples of the polynuclear phenol-based crosslinking agent include compounds represented by the following general formula (XL-1).

Chemical formula

[0136] Q is a single bond or a q'-valent hydrocarbon group having 1 to 20 carbon atoms. q' is an integer of 1 to 5, and more preferably 2 or 3. Specific examples of Q include groups obtained by removing q' hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R'3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of 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.

[0137] As examples of the compound represented by the general formula (XL-1), specifically, the following compounds can be exemplified. Among them, from the viewpoints of improving the curability and film thickness uniformity of the metal-containing film, hexamethoxymethylated products of triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred. R'3 is the same as described above.

[0138]

Chemical formula

[0139]

Chemical formula

[0140] <(G) Surfactant> In the composition for forming a metal-containing film of the present invention, (G) a surfactant can be added to improve the coatability in spin coating. The (G) surfactant can be used alone or in combination of two or more. As the (G) surfactant, for example, those described in paragraphs

[0142] to

[0147] of JP-A-2009-269953 can be used. When the (G) surfactant is added, the addition amount is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the above (A) compound for forming a metal-containing film. Within such a range, the coatability is surely improved, and a thin and uniform metal-containing film can be formed.

[0141] <(H) Acid generator> In the composition for forming a metal-containing film of the present invention, (H) an acid generator can be added to further accelerate the curing reaction of the above (A) compound for forming a metal-containing film. The (H) acid generator includes those that generate an acid by thermal decomposition and those that generate an acid by light irradiation, and any of them can be added. Specifically, those described in paragraphs

[0061] to

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

[0142] The above (H) acid generator can be used alone or in combination of two or more. When the (H) acid generator is added, the addition amount is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the above (A) compound for forming a metal-containing film.

[0143] <Other additives> In addition, as an additive for imparting embedding / planarization characteristics, the composition for forming a metal-containing film of the present invention preferably uses, for example, polyethylene glycol, a liquid additive having a polypropylene glycol structure, or a thermally decomposable polymer having a weight loss rate of 40% by mass or more between 30°C and 250°C and a weight average molecular weight of 300 to 200,000. This thermally decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formulas (DP1) and (DP1a).

[0144] [Chemical formula] (In general formula (DP1), R6 is a hydrogen atom or a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms which may be substituted, and Y' is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.)

[0145] [Chemical formula] (In general formula (DP1a), R 6a is an alkyl group having 1 to 4 carbon atoms, Y a is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms, which may have an ether bond, and n represents the average number of repeating units and is 3 to 500.)

[0146] [Flowability promoter (BP)] In addition, a flowability promoter (BP) can be added as an additive for imparting embedding / planarization characteristics to the composition for forming a metal-containing film of the present invention. The flowability promoter (BP) preferably has any of the organic groups represented by the following general formula (3') and an aromatic ring. That is, it is preferable that the composition for forming a metal-containing film further contains a flowability promoter (BP) having any of the organic groups represented by the following general formula (3') and an aromatic ring. [Chemical formula] (In general formula (3'), * represents a bonding site to an oxygen atom, and R Bis a divalent organic group having 1 to 10 carbon atoms, R A is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.)

[0147] Since the fluidity promoter (BP) has an organic group of the above general formula (3'), the composition for forming a metal-containing film can be imparted with thermal fluidity and thermosetting properties. Further, since the fluidity promoter (BP) has an aromatic ring, deterioration of the dry etching resistance of the composition for forming a metal-containing film can be alleviated.)

[0148] The fluidity promoter (BP) preferably has at least one structural unit represented by the following general formulas (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5). (Structural units: BP-1, BP-2, and BP-3)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0149] For a resin having structural units represented by the above general formulas (BP-1), (BP-2), and (BP-3), since a highly carbon-dense condensed carbon ring containing a cald structure is introduced, it has excellent heat resistance. Due to having the above characteristics, even when subjected to a high-temperature baking treatment, a metal-containing film capable of filling a stepped substrate without generating voids can be formed. Further, since it also has excellent dry etching resistance, even when added to the composition for forming a metal-containing film of the present invention, heat resistance and thermal fluidity can be imparted without significantly deteriorating the excellent dry etching resistance of the composition for forming a metal-containing film.)

[0150] The resin having structural units represented by the above general formulas (BP-1), (BP-2), and (BP-3) can be a compound represented by the following general formulas (bp-1), (bp-2), and / or (bp-3).

Chemical formula

[0151] In W 1a , W2, R a , Y, n1, and n2 in the above general formulas (bp-1) and (bp-2) are as described for the above general formulas (BP-1) and (BP-2).

[0152]

Chemical formula

[0153] In the above general formula (bp-3), Z1 and R a , n4, and n5 are as explained above in relation to general formula (BP-3).

[0154] Specific examples of resins having structural units represented by the above general formulae (BP-1), (BP-2), and (BP-3) include, but are not limited to, the following compounds. [ka]

[0155] The compounds represented by the above general formulae (bp-1), (bp-2), and (bp-3) preferably have a ratio Mw / Mn (i.e., dispersity) of the weight average molecular weight Mw to the number average molecular weight Mn in terms of polystyrene, as determined by gel permeation chromatography, within the range of 1.00≦Mw / Mn≦1.25, and more preferably 1.00≦Mw / Mn≦1.10.

[0156] A compound having a dispersity within such a range can provide a metal-containing film-forming composition with better thermal fluidity, and when incorporated into the composition, can provide a metal-containing film-forming composition with better embedding / planarization properties.

[0157] The resins having structural units represented by the above general formulae (BP-1), (BP-2), and (BP-3) can be polymers having repeating units represented by the following general formulae (bp-4), (bp-5), and / or (bp-6). [ka] (In general formulas (bp-4) and (bp-5), W 1a , W2, R a , Y, n1, and n2 are the same as above, and L a is a divalent organic group having 1 to 40 carbon atoms.

[0158] In the above general formulas (bp-4) and (bp-5), W 1a , W2, R a , Y, n1, and n2 are as described for the above general formulas (BP-1) and (BP-2).

[0159] [Chemical formula] (In general formula (bp-6), Z1, R a , n4, and n5 are the same as above, and L a is a divalent organic group having 1 to 40 carbon atoms.)

[0160] In the above general formula (bp-6), Z1, R a , n4, and n5 are as described for the above general formula (BP-3).

[0161] These are polymers obtained using the compounds represented by the above general formulas (bp-1), (bp-2), and (bp-3). Because the above compounds are used, they are excellent in dry etching resistance and heat resistance. Further, because they are polymers having repeating units instead of monomers, the outgas components are few. Also, because they are polymers having a molecular weight distribution, the crystallinity is relaxed and an improvement in film formability can be expected.

[0162] L, which is a linking group constituting the repeating units of the above general formulas (bp-4), (bp-5), and (bp-6) a is a divalent organic group having 1 to 40 carbon atoms, and specific examples thereof include the following.

[0163] [Chemical formula]

[0164] Furthermore, it is preferable that the linking group L a of the above polymer is a group represented by the following general formula (10). [Chemical formula] (In the general formula (10) above, R1 is a hydrogen atom or an organic group containing an aromatic ring having 6 to 20 carbon atoms, and the dashed line represents a bond.)

[0165] Specific examples of the general formula (10) include the following. Among these, from the viewpoint of easy availability of raw materials, a methylene group, that is, R1 is preferably a hydrogen atom.

Chemical formula

[0166] Furthermore, the weight average molecular weight (Mw) in terms of polystyrene of the polymer having repeating units represented by the general formulas (bp-4), (bp-5), and (bp-6) by gel permeation chromatography is preferably from 1,000 to 12,000, and more preferably Mw is from 2,000 to 10,000.

[0167] Within such a molecular weight range, solubility in an organic solvent can be ensured, and sublimates generated during baking can be suppressed. In addition, since the thermal fluidity of the composition for forming a metal-containing film becomes good, when blended into the composition, a composition for forming a metal-containing film with more excellent embedding / flattening characteristics can be provided.

[0168] (Constituent unit: BP-4)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0169] In the above General Formula (BP-4), m3 and m4 each independently represent 1 or 2, and Z is either a single bond or any of the structures represented by the above General Formula (7). R x each independently represents any of the structures represented by the above General Formula (8).

[0170] From the viewpoints of dry etching resistance and heat resistance, in the above General Formula (BP-4), it is preferable that Z is either a single bond or any of the structures represented by the following Formula (4A).

Chemical formula

[0171] In the above general formula (8), * represents a bonding site to the aromatic ring, and Q1 represents a linear saturated hydrocarbon group having 1 to 30 carbon atoms or a structure represented by the above general formula (9). When Q1 represents a linear hydrocarbon group having 1 to 30 carbon atoms, the methylene group constituting Q1 may be substituted with an oxygen atom or a carbonyl group. From the viewpoints of dry etching resistance and heat resistance, Q1 preferably has a structure represented by the above general formula (9).

[0172] In the above general formula (9), * represents a bonding site to the carbonyl group, and R i is a group represented by the above formula (4’). R j represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n6 and n7 represent the number of substituents on the aromatic ring and each represents an integer of 0 to 7. However, n6 + n7 is an integer of 0 or more and 7 or less. n8 represents an integer of 0 to 2.

[0173] Since the compound containing the structural unit represented by the above general formula (BP-4) has a high carbon density because it has a structure in which the aromatic rings are connected by a single bond or the general formula (7), the composition for forming a metal-containing film containing these compounds is excellent in heat resistance. Further, as shown in the above formula (7), the linking group Z can be appropriately selected from various linking groups according to the desired performance. In particular, by introducing the structure represented by the above formula (4A) as Z, heat resistance / etching resistance can be imparted without impairing the film-forming property. Further, since it has a highly flexible terminal R x it is possible to form a thick film of the composition for forming a metal-containing film without generating defects such as cracks in spite of containing a rigid aromatic ring structure. Furthermore, the terminal R xIt contains a terminal group Q1 that imparts thermal fluidity. As the terminal group Q1, a flexible hydrocarbon structure that contributes to the improvement of thermal fluidity and a rigid aromatic ring structure that contributes to etching resistance and heat resistance can be introduced in any proportion according to the required performance. As described above, the composition for forming a metal-containing film to which these compounds are added can achieve both high-dimensional embedability / planarization characteristics and heat resistance, and a thick film can be formed according to the required characteristics.

[0174] (Constituent unit: BP-5) [Chemical formula] (In the general formula (BP-5), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X C is a divalent organic group having 1 to 30 carbon atoms, R a is the group represented by the above formula (4’). p is an integer from 0 to 5, q1 is an integer from 1 to 6, p + q1 is an integer from 1 or more to 6 or less, and q2 is 0 or 1.)

[0175] In the above general formula (BP-5), as the divalent organic group having 1 to 30 carbon atoms represented by X C , for example, alkane diyl groups such as methylene group, ethanediyl group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, octanediyl group, decanediyl group, monocyclic cycloalkane diyl groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclooctanediyl group, cyclodecanediyl group, methylcyclohexanediyl group, ethylcyclohexanediyl group, bicyclo[2.2.1]heptane diyl group, bicyclo[2.2.2]octane diyl group, tricyclo[5.2.1.0 2,6 decane diyl group (dicyclopentylene group), tricyclo[3.3.1.1 3,7 decane diyl group, tetracyclo[6.2.1.1 3,6 .0 2,7Examples thereof include polycyclic cycloalkanediyl groups such as dodecandiyl group and adamantandiyl group, arenediyl groups such as phenylene group and naphthylene group, and the like.

[0176] The above X C Examples of the alkanediyl-oxy group represented by include groups formed by combining the above alkanediyl group and an oxygen atom. Further, the above X C Examples of the cycloalkanediyl-oxy group represented by include groups formed by combining the above cycloalkanediyl group and an oxygen atom.

[0177] Some or all of the hydrogen atoms of the above alkanediyl group, cycloalkanediyl group, alkanediyl-oxy group, cycloalkanediyl-oxy group, arenediyl group and the like may be substituted, and examples of the substituent include groups similar to the examples of the substituent that the organic group represented by the above R a may have.

[0178] The above X C Examples of the organic group represented by include groups represented by the following formula.

Chemical formula

[0179] The above X C From the viewpoint of raw material availability, preferably, a methylene group can be mentioned.

[0180] Specific examples of the resin having the structural unit represented by the above general formula (BP-5) include the following.

[0181]

Chemical formula

[0182]

Chemical formula

[0183] The polymer containing the structural unit represented by the general formula (BP-5) has a structure in which aromatic rings are linked by an organic group (X C ), so it has a high carbon density. Therefore, the composition for forming a metal-containing film containing these polymers exhibits high dry etching resistance and excellent heat resistance. Furthermore, since the organic group having the structure represented by the above formula (4’) that contributes to the improvement of thermal fluidity is directly bonded to the aromatic ring which is the mother nucleus structure of the resin via an oxygen atom, the composition for forming a metal-containing film to which these polymers are added can achieve both high-dimensional embedding / flattening characteristics and heat resistance / etching resistance. Also, since the aromatic ring structure of the mother nucleus is not too rigid and forms a repeating structure via the organic group (X C ) which is a linking group, it is possible to form a metal-containing film without generating defects such as cracks.

[0184] In the composition for forming a metal-containing film of the present invention, the fluidity promoter (BP) preferably has a content of 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less with respect to 100 parts by mass of the compound for forming a metal-containing film.

[0185] The addition amount of the fluidity promoter can be adjusted to an arbitrary ratio according to the required characteristics of the process using the composition for forming a metal-containing film of the present invention. When it is desired to minimize the deterioration of dry etching resistance, the ratio of the fluidity promoter can be decreased. When a certain degree of deterioration of dry etching resistance is acceptable and it is desired to further improve the embedding / flattening characteristics, the ratio of the fluidity promoter can be increased.

[0186] <Resist underlayer film, and method for forming a filling 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 planarization film for semiconductor manufacturing using the above-described composition for forming a metal-containing film.

[0187] In the method for forming a resist underlayer film using the composition for forming a metal-containing film of the present invention, the above 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 or 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.

[0188] Also, 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 fired 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 as a resist underlayer film.

[0189] 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 1,000 ppm or less, more preferably 100 ppm or less (volume basis). Preventing oxidation of the metal-containing film during baking is preferable because the absorption does not increase and the etching resistance does not decrease.

[0190] The method for forming a filling film can be the same as the method for forming a resist underlayer film described above.

[0191] <Pattern formation method using a composition for forming a metal-containing film> In addition, in the present invention, as a pattern formation method by a two-layer resist process using the above-described composition for forming a metal-containing film, a method for forming a pattern on a substrate to be processed, (I-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film described above 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 subjecting the resist upper layer film to pattern exposure and then developing it 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 having the pattern as a mask, and (I-5) A step of processing the substrate to be processed using the metal-containing film having the pattern transferred thereto as a mask to form a pattern on the substrate to be processed A pattern formation method having the above steps is provided.

[0192] Since the resist upper layer film of the two-layer resist process exhibits etching resistance to chlorine-based gases, in the above two-layer resist process, it is preferable to perform dry etching of the metal-containing film using an etching gas mainly composed of chlorine-based gas with the resist upper layer film as a mask.

[0193] In addition, 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 method for forming a pattern on a substrate to be processed, (II-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film described above on a substrate to be processed and then performing heat treatment, (II-2) A step of forming a silicon-containing resist intermediate film on the metal-containing film, (II-3) A step of forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist material, (II-4) A step of forming a pattern on the resist upper layer film by subjecting the resist upper layer film to pattern exposure and then developing it with a developer, (II-5) A step of transferring a pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern is formed as a mask. (II-6) A step of transferring a pattern to the metal-containing film by dry etching using the silicon-containing resist intermediate film on which the pattern is transferred as a mask, and (II-7) A step of processing the substrate to be processed using the metal-containing film on which the pattern is transferred as a mask to form a pattern on the substrate to be processed. provided is a pattern forming method having the above steps.

[0194] A pattern forming method by a three-layer resist process will be described with reference to FIG. 1. In the present invention, as a pattern forming method by a three-layer resist process using such a composition for forming a metal-containing film, as shown in FIG. 1(A), a metal-containing film 3 is formed on a processed layer 2 on a substrate to be processed 1 using the composition for forming a metal-containing film, a silicon-containing resist intermediate film 4 is formed on the metal-containing film using a silicon-containing resist intermediate film material, and a resist upper layer film 5 is formed on the silicon-containing resist intermediate film using a photoresist material. Subsequently, as shown in FIG. 1(B), after pattern exposure of the exposed portion 6 of the resist upper layer film, as shown in FIG. 1(C), development is performed with a developer to form a resist upper layer film pattern 5a on the resist upper layer film. As shown in FIG. 1(D), a silicon-containing resist intermediate film pattern 4a is transferred to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern is formed as a mask. As shown in FIG. 1(E), a metal-containing film pattern 3a is transferred to the metal-containing film by dry etching using the silicon-containing resist intermediate film on which the pattern is transferred as a mask. As shown in FIG. 1(F), provided is a pattern forming method of processing the processed layer 2 on the substrate to be processed using the metal-containing film on which the pattern is formed as a mask to form a pattern 2a on the substrate to be processed 1.

[0195] Since the silicon-containing resist intermediate film in the above three-layer resist process exhibits etching resistance to chlorine-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 with an etching gas mainly composed of chlorine-based gas.

[0196] As the silicon-containing resist intermediate film in the above three-layer resist process, a polysiloxane-based resist intermediate film is also preferably used. By imparting an antireflection effect to the silicon-containing resist intermediate film, reflection can be suppressed. Particularly for 193 nm exposure, when a material with a high etching selectivity with respect to the substrate and containing many aromatic groups as an organic film is used, the k value becomes high and substrate reflection increases. However, by imparting absorption such that an appropriate k value is obtained as the silicon-containing resist intermediate film, it becomes possible to suppress reflection and reduce substrate reflection to 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 absorbing group having a silicon-silicon bond pendant and crosslinkable by an acid or heat for 193 nm exposure is preferably used.

[0197] 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 described above, a silicon-containing resist intermediate film is formed on the metal-containing film using a silicon-containing resist intermediate film material, an organic antireflection 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 or the adhesion 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 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 onto which the pattern has been transferred as a mask, a pattern is transferred to the metal-containing film by dry etching, A pattern forming method is provided, which includes a step of processing the substrate to be processed using the metal-containing film onto which the pattern has been transferred as a mask to form a pattern on the substrate to be processed.

[0198] Alternatively, an inorganic hard mask intermediate film may be formed instead of the silicon-containing resist intermediate film. In this case, at least, A metal-containing film is formed on the substrate to be processed using the composition for forming a metal-containing film of the present invention, An inorganic hard mask intermediate film 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 intermediate film using a photoresist composition, and a circuit pattern is formed on the resist upper layer film, Using the resist upper layer film on which the pattern has been formed as a mask, the pattern is transferred to the inorganic hard mask intermediate film, Using the inorganic hard mask intermediate film onto which the pattern has been transferred as a mask, the pattern is transferred to the metal-containing film, Furthermore, by processing the substrate to be processed using the metal-containing film onto which the pattern has been transferred as a mask to form a pattern on the substrate to be processed, a semiconductor device circuit pattern can be formed on the substrate.

[0199] In the present invention, as a method for forming a pattern by a four-layer resist process using such a composition for forming a metal-containing film, a method for forming a pattern on a substrate to be processed, (III-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film described above on the substrate to be processed and then performing a 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 metal-containing 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 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 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 transferred as a mask to process the substrate to be processed and form a pattern on the substrate to be processed. provided is a patterning method having the above steps.

[0200] As described above, when forming an inorganic hard mask intermediate film 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. That is, it is preferable that the inorganic hard mask intermediate film is formed by a CVD method or an ALD method. For example, as a method for forming a silicon nitride film, it is described in Japanese Patent Application Laid-Open No. 2002-334869 and International Publication No. 2004 / 066377. The film thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, more preferably 10 to 100 nm. Also, as the inorganic hard mask intermediate film, 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 the 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 intermediate film formed by a CVD method or an ALD method and a metal-containing film formed by a spin coating method is possible.

[0201] As described above, a photoresist film may be formed as a resist upper layer film on the inorganic hard mask intermediate film. However, an organic anti-reflection film (BARC) or an adhesion film may be spin-coated on the inorganic hard mask intermediate film, and a photoresist film may be formed thereon. In particular, when a SiON film is used as the inorganic hard mask intermediate film, reflection can be suppressed even in high-NA immersion lithography exceeding 1.0 by the two-layer anti-reflection film of the SiON film and the BARC. Another merit of forming the BARC is that it has the effect of reducing the pull-off of the photoresist pattern directly above the SiON film.

[0202] In the above pattern formation method, the resist upper layer film may be either positive or negative, and the same photoresist composition as that usually used can be used. Further, the photoresist composition may contain metal atoms such as Sn, In, Ga, Ge, Al, Ce, La, Cs, Zr, Hf, Ti, Bi, Sb, and Zn. When the resist upper layer film is formed from the above photoresist composition, it may be formed by a spin coating method or a vapor deposition process such as CVD or ALD.

[0203] When the resist upper layer film is formed by the spin coating method, pre-baking is performed after coating the photoresist composition, and the range of 60 to 180 °C for 10 to 300 seconds is preferable. Thereafter, exposure is performed according to a conventional method, post-exposure bake (PEB) and development are performed to obtain a resist pattern. The thickness of the resist upper layer film is not particularly limited, but 10 to 500 nm, particularly 20 to 400 nm is preferable.

[0204] When forming a resist upper layer film by a vapor deposition process using CVD or ALD, the photoresist composition is an EUV-sensitive metal oxide-containing film, and the metal is selected from Sn, Zr, Hf, Ti, Bi, Sb, etc., and among them, Sn, which is excellent in EUV sensitivity, is preferable. The metal oxide-containing film may be a photosensitive organometallic oxide film such as an organic tin oxide (for example, haloalkyl Sn, alkoxyalkyl Sn, or amidoalkyl Sn). Some specific examples of suitable precursors include trimethyltin chloride, dimethyltin dichloride, methyltin trichloride, tris(dimethylamino)methyltin(IV), and (dimethylamino)trimethyltin(IV).

[0205] The metal oxide-containing film may be deposited by PECVD or PEALD using, for example, a Lam Vector (registered trademark) tool. In the ALD example, the Sn oxide precursor is separated from the O precursor / plasma. The deposition temperature is preferably in the range of 50°C to 600°C. The deposition pressure is preferably between 100 and 6,000 mTorr. The flow rate of the precursor liquid of the metal oxide-containing film (for example, the organotin oxide precursor) may be 0.01 to 10 cmm, and the gas flow rate (CO2, CO, Ar, N2) may be 100 to 10,000 sccm. The plasma power may be 200 to 1,000 W per 300 mm wafer station using high-frequency plasma (for example, 13.56 MHz, 27.1 MHz, or a higher frequency). The deposition thickness is preferably 100 to 2,000 Å.

[0206] Examples of the exposure light include high-energy rays with a wavelength of 300 nm or less, specifically, excimer lasers of 248 nm, 193 nm, 157 nm, soft X-rays of 3 to 20 nm, electron beams, and X-rays.

[0207] As a method for forming a pattern of 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.

[0208] In addition, it is preferable that the development method in the pattern formation method be development with an alkali or an organic solvent.

[0209] Next, etching is performed using the obtained resist pattern as a mask. For etching the silicon-containing resist intermediate film and the inorganic hard mask intermediate film in the three-layer resist process, a fluorocarbon-based gas is used with the resist upper layer film pattern as a mask. Thereby, a silicon-containing resist intermediate film pattern and an inorganic hard mask intermediate film pattern are formed.

[0210] Next, using the obtained silicon-containing resist intermediate film pattern and inorganic hard mask intermediate film 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.

[0211] Etching of the next substrate to be processed can also be performed by a conventional method. For example, if the substrate to be processed is SiO2, SiN, or a silica-based low dielectric constant insulating film, etching mainly using a fluorocarbon-based gas is performed. When the substrate processing 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.

[0212] 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 etching of these substrates to be processed.

[0213] Note that the object to be processed (substrate to be processed) is not particularly limited, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, 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 and their stopper films are used, and they can usually be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming the processed layer, substrates and processed layers made of different materials are used.

[0214] The pattern formation method using the composition for forming a metal-containing film of the present invention preferably uses a substrate to be processed 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 substrate to be processed 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 substrate to be processed is preferably 30 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. In the method of processing a stepped substrate having a pattern of the above height, by forming the composition for forming a metal-containing film of the present invention and performing 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.

[0215] Furthermore, 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 above composition for forming a metal-containing film, a resist lower layer film is formed on the metal-containing film using an organic resist lower layer film material, a silicon-containing resist intermediate film is formed on the resist lower layer film using a silicon-containing resist intermediate film material, optionally, 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 silicon-containing film, on the BARC, or on the adhesion 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 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 resist lower layer film by dry etching, Using the resist underlayer film onto which the pattern has been transferred as a mask, transfer the pattern onto the metal-containing film. Provided is a patterning method including a step of processing a substrate to be processed using the metal-containing film onto which the pattern has been transferred as a mask to form a pattern on the substrate to be processed.

[0216] Examples of the organic resist underlayer film material that can be used for the resist underlayer film include those known as resist underlayer films for the three-layer resist method or the two-layer resist method using a silicon resist composition. In addition to the 4,4'-(9-fluorenylidene)bisphenol novolak resin (molecular weight 11,000) described in JP-A-2005-128509, a number of resins such as novolak resins, which are known as resist underlayer film materials for the two-layer resist method and the three-layer resist method, can be used. When it is desired to increase the heat resistance compared to ordinary novolak, a polycyclic skeleton such as 6,6'-(9-fluorenylidene)-di(2-naphthol) novolak resin can be incorporated, and a polyimide-based resin can also be selected (for example, JP-A-2004-153125).

[0217] The resist underlayer film can be formed on the substrate to be processed by a spin coating method or the like using a composition solution, similar to a photoresist composition. After forming the organic underlayer film by a spin coating method or the like, it is desirable to perform baking to evaporate the organic solvent. The baking temperature is preferably in the range of 80 to 400°C, and the baking time is preferably in the range of 10 to 300 seconds.

[0218] Instead of the resist underlayer film, an organic hard mask formed by a CVD method or an ALD method can also be applied.

[0219] Since the resist underlayer film of the multilayer resist process exhibits etching resistance to chlorine-based gases, in the multilayer resist process, it is preferable to perform dry etching of the metal-containing film using the resist underlayer film as a mask using an etching gas mainly composed of a chlorine-based gas.

[0220] 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 method for forming a pattern on a substrate to be processed, (IV-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film described above on a substrate to be processed and then performing heat treatment, (IV-2) A step of forming a resist lower layer film on the metal-containing film, (IV-3) A step of forming a combination of a silicon-containing 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, (IV-4) A step of forming a resist upper layer film using a photoresist material on the silicon-containing resist intermediate film or the organic thin film, (IV-5) A step of forming a pattern on the resist upper layer film by pattern exposure and then developing with a developer, (IV-6) A step of transferring the pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film having the pattern as a mask, (IV-7) A step of transferring the pattern to the resist lower layer film by dry etching using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film having the pattern as a mask, (IV-8) A step of transferring the pattern to the metal-containing film by dry etching using the resist lower layer film having the pattern as a mask, and (IV-9) A step of processing the substrate to be processed using the metal-containing film having the pattern transferred thereto to form a pattern on the substrate to be processed A pattern formation method having the above steps is provided.

[0221] <Tone inversion type pattern formation method using a composition for forming a metal-containing film> In addition, in the present invention, as a tone inversion type pattern formation method using such a composition for forming a metal-containing film, a method for forming a pattern on a substrate to be processed, (V-1) Step of forming a resist underlayer film on a substrate to be processed; (V-2) 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) 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) Step of performing pattern exposure on the resist upper layer film and then developing with a developer to form a pattern in the resist upper layer film; (V-5) 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 with the pattern as a mask; (V-6) 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 with the pattern as a mask; (V-7) Step of coating the composition for forming a metal-containing film on the resist underlayer film with the transferred pattern, 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) Step of etching back the metal-containing film covering the resist underlayer film with the transferred pattern by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film with the pattern formed; (V-9) Step of removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) Step of removing the resist underlayer film with the transferred pattern having the exposed surface by dry etching to form an inverted pattern of the original pattern on the metal-containing film, and (V-11) Step of processing the substrate to be processed using the metal-containing film with the inverted pattern as a mask to form an inverted pattern on the substrate to be processed. Provided is a tone inversion type pattern forming method having the above steps.

[0222] A tone inversion type pattern forming method using a composition for forming a metal-containing film will be described with reference to FIG. 2. In the present invention, as a tone inversion type pattern forming method using such a composition for forming a metal-containing film, as shown in FIG. 2(G), a resist underlayer film 7 is formed on a processing layer 2 on a substrate 1 to be processed, and a resist intermediate film 4, or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film is formed on the resist underlayer film 7, and a resist upper layer film 5 is formed using a photoresist material on the resist intermediate film 4, or the combination of the inorganic hard mask intermediate film and the organic thin film.Subsequently, as shown in FIG. 2(H), after the exposed portion 6 of the resist upper layer film is pattern-exposed, as shown in FIG. 2(I), it is developed with a developer to form a resist upper layer film pattern 5a on the resist upper layer film. As shown in FIG. 2(J), using the resist upper layer film on which the pattern is formed as a mask, a resist intermediate film pattern 4a or an inorganic hard mask intermediate film pattern is transferred to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching. As shown in FIG. 2(K), using the resist intermediate film or the inorganic hard mask intermediate film on which the pattern is transferred as a mask, a resist lower layer film pattern 7a is transferred to the resist lower layer film by dry etching. As shown in FIG. 2(L), a metal-containing film 8 is coated on the resist lower layer film on which the pattern is formed using the above metal-containing film-forming composition, and the space between the resist lower layer film patterns 7a is filled with the metal-containing film 8. As shown in FIG. 2(M), the metal-containing film covering the resist lower layer film on which the pattern is formed is etched back by a chemical stripper or dry etching to form an inverted metal-containing film pattern 8a, exposing the upper surface of the resist lower layer film on which the pattern is formed. As shown in FIG. 2(N), the resist intermediate film or the hard mask intermediate film remaining on the upper surface of the resist lower layer film pattern 7a is removed by dry etching. As shown in FIG. 2(O), the resist lower layer film on which the pattern is formed and whose surface is exposed is removed by dry etching to form an inverted pattern of the original pattern in the metal-containing film. As shown in FIG. 2(P), a tone inversion type pattern forming method is provided, which includes a step of processing the layer to be processed 2 using the metal-containing film on which the inverted pattern is formed as a mask to form an inverted pattern 2b in the layer to be processed 2.

[0223] 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 resist underlayer film material, a CVD method, an ALD method, or the like. Examples of the coating-type resist 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 / 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.

[0224] In the above tone inversion pattern forming method, after coating the obtained resist underlayer film pattern with a composition for forming a metal-containing film, 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 inorganic hard mask intermediate film remaining on the resist underlayer film is removed by dry etching with a fluorocarbon-based gas, and the exposed resist underlayer film pattern on the surface is removed by dry etching with an oxygen-based gas to form a metal-containing film inversion pattern.

[0225] In the above-described tone inversion type pattern forming method, it is preferable that the resist underlayer film pattern 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 / planarization characteristics, 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 even 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 fluorocarbon gas with respect to the resist underlayer film using a conventional coating type resist 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

[0226] 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.

[0227] [Synthesis Example] In the following synthesis examples and comparative synthesis examples, the following organic group raw material group G: (G1) to (G24) and silicon-containing organic group raw material group H: (H1) to (H2) were used.

[0228] The organic group raw material group G: (G1) to (G24) is shown below.

Chemical formula

[0229] The silicon-containing organic group raw material group H: (H1) to (H2) is shown below.

Chemical formula

[0230] For the metal source M, the following metal compounds were used. (M1): Zr(OBu)4: zirconium(IV) tetrabutoxide (80 mass% 1-butanol solution) (Tokyo Chemical Industry Co., Ltd., Z0016) (M2): Hf(OBu)4: hafnium(IV) n-butoxide (Sigma-Aldrich Corp, 667943) (M3): Ti(OBu)4: tetrabutyl orthotitanate (Tokyo Chemical Industry Co., Ltd., B0742)

[0231] [Synthesis Example 1] Synthesis of Compound (A-1) for Forming Metal-Containing Film Under a nitrogen atmosphere, 10.0 g of 1-butanol and 5.6 g of organic group raw material G1 were added to 12.0 g of zirconium(IV) tetrabutoxide (80 mass% 1-butanol solution) M1, and the mixture was stirred at room temperature for 30 minutes. This solution was concentrated at 30 °C under reduced pressure, then further heated to 60 °C, and heating was continued under reduced pressure until no more effluent was produced. When no more distillate was visible, 14.8 g of a 120.0 g PGMEA / PGME (mass ratio 70 / 30) solution and 4.5 g of silicon-containing organic group raw material H1 were added, and stirring was continued for 1 hour at a reaction temperature of 60 °C. After cooling to room temperature, the resulting reaction solution was filtered through a 0.45 μm PTFE filter to obtain a PGMEA / PGME solution of the compound (A-1) for forming a metal-containing film. The concentration of the components other than the solvent in the solution was 22.0 mass%.

[0232] [Synthesis Examples 2 to 19, Comparative Synthesis Examples 1 to 5] Synthesis of Compounds (A-2) to (A-19) for Forming Metal-Containing Films and Comparative Compounds (R-1) to (R-5) Compounds (A-2) to (A-19) and comparative compounds (R-1) to (R-5) shown in Tables 1 and 2 were obtained under the same reaction conditions as in Synthesis Example 1, except that the metal source M, the organic group raw material group G, and the silicon-containing organic group raw material group H were used in the amounts shown in Tables 1 and 2.

[0233] [Table 1]

[0234] [Table 2]

[0235] [Synthesis Example 20] Synthesis of Compound (A-20) for Forming Metal-Containing Film Under a nitrogen atmosphere, while stirring 20.5 g of a solution of 24.0 g of zirconium(IV) tetrabutoxide (M1) in n-butanol, a solution of 0.68 g of deionized water in 27.5 g of n-butanol was added dropwise at room temperature over 2 hours. 9.6 g of the organic group raw material group (G5) 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 was produced. When no distillate was observed, 45.0 g of a PGMEA / PGME (mass ratio 70 / 30) solution was added, and the mixture was heated at 40 °C under reduced pressure to obtain a PGMEA / PGME solution of the compound (A-20) for forming a metal-containing film. The concentration of the components other than the solvent in the solution was 19% by mass.

[0236] [Synthesis Examples 21 to 22] Synthesis of Compounds (A-21) to (A-22) for Forming Metal-Containing Film Compounds (A-21) to (A-22) for forming a metal-containing film shown in Table 3 were obtained under the same reaction conditions as in Synthesis Example 20, except that the above metal source M and the above organic group raw material group G were used in the charged amounts shown in Table 3.

[0237] [Table 3]

[0238] [Comparative Synthesis Example 6] Synthesis of Compound (R-6) for Comparative Example The 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, 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 was produced. When no distillate was observed, 1,200 g of PGMEA was added, and the mixture was heated at 40 °C under reduced pressure until no more IPA distilled off, to obtain 1,000 g of a PGMEA solution of a titanium-containing compound (R-6) (compound concentration: 20% by mass).

[0239] [Comparative Synthesis Example 7] Synthesis of Compound (R-7) for Comparative Example Under a nitrogen atmosphere, 160.2 g of 1,5-dihydroxynaphthalene, 56.8 g of formaldehyde, and 300 g of PGME (propylene glycol monomethyl ether) were added and homogenized at an internal temperature of 100 °C. Then, a mixture of 8.0 g of p-toluenesulfonic acid monohydrate and 8.0 g of PGME, which had been 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 completion of the reaction, the mixture 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. 300 g of THF was added to the residue to form a homogeneous solution, and then 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). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent, and the following results were obtained. (R-7): Mw = 3,300, Mw / Mn = 2.54 [Chemical formula]

[0240] [Synthesis of Fluidity Promoter] For the synthesis of the fluidity promoter, the following organic group raw material groups G: (G25) to (G27) and modifiers K: (K1) to (K2) were used.

[0241] The organic group raw material groups G: (G25) to (G27) are shown below.

Chemical formula

[0242] The modifiers K: (K1) to (K2) are shown below.

Chemical formula

[0243] [Synthesis of fluidity promoter (BPA-1)] Under a nitrogen atmosphere, 45.5 g of the compound (G25) of the organic group raw material group G, 9.8 g of potassium carbonate, and 150 g of DMF were added, and a homogeneous dispersion was obtained at an internal temperature of 50°C. 17.6 g of the modifier (K1) was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and then the separated 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 the fluidity promoter (BPA-1). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (BPA-1): Mw = 965, Mw / Mn = 1.08

Chemical formula

[0244] [Synthesis of fluidity promoter (BPA-2)] 80.0 g of the compound (G26) in the organic group raw material group G, 51.0 g of the modifier (K2), and 600 g of 2-methoxy-1-propanol were made into a homogeneous solution at an internal temperature of 100 °C under a nitrogen atmosphere. Then, 5.7 g of benzyltriethylammonium chloride was added, and the mixture was stirred at an internal temperature of 120 °C for 12 hours. After cooling to room temperature, 1,500 g of methyl isobutyl ketone was added, and the organic layer was washed 5 times with 300 g of pure water. The organic layer was dried to dryness under reduced pressure to obtain the fluidity promoter (BPA-2). When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (BPA-2): Mw = 900, Mw / Mn = 1.04

Chemical formula

[0245] [Synthesis of fluidity promoter (BPA-3)] Under a nitrogen atmosphere, 20.0 g of the resin (G27) in the organic group raw material group G, 34.5 g of potassium carbonate, and 100 g of DMF were added to form a homogeneous dispersion at an internal temperature of 50 °C. 23.8 g of the modifier (K1) was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and then the separated 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 to dryness under reduced pressure to obtain the fluidity promoter (BPA-3). When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (BPA-3): Mw = 9,400, Mw / Mn = 3.59

Chemical formula

[0246] [Preparation of the composition for forming a metal-containing film (UDL-1)] The compound (A-1) for forming a metal-containing film was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) containing 0.5% by mass of surfactant FC-4430 (manufactured by Sumitomo 3M Limited) at the ratios shown in Table 4, and filtered through a 0.02 μm membrane filter to prepare a composition (UDL-1) for forming a metal-containing film.

[0247] [Preparation of Compositions (UDL-2 to 29) for Forming Metal-Containing Films and Comparative Compositions (Comparative UDL-1 to 7) for Forming Metal-Containing Films] Except that the types and contents of the respective components were as shown in Tables 4 and 5, the same operations as for UDL-1 were carried out to prepare each chemical solution. In Tables 4 and 5, "-" indicates that the corresponding component was not used. As the crosslinking agent, the following formula (C-1) was used; as the acid generator (TAG), the following formula (F-1) was used; as the high-boiling solvent (B1), ethylene glycol dibenzyl ether: boiling point 364 °C was used; as the metal nanoparticles (G-1), ZrO2 nanoparticles (5 nm core, 915505 Sigma-Aldrich Corp) were used.

[0248] [Crosslinking Agent, Acid Generator] The crosslinking agent (C-1) and the acid generator (F-1) used in the composition for forming a metal-containing film are shown below. [Chemical Formula]

[0249] [Table 4]

[0250] [Table 5]

[0251] [Evaluation of Embedding Characteristics (Examples 1-1 to 1-29, Comparative Examples 1-1 to 1-7)] The compositions prepared above (UDL-1 to 29, and Comparative Example UDL-1 to 7) were each applied onto a SiO2 wafer substrate having a dense line & space pattern (line width 60 nm, line depth 100 nm, distance between the centers of two adjacent lines 120 nm), and heated at 350 °C for 60 seconds using a hot plate to form a metal-containing film with a film thickness of 80 nm. The substrate used was a base substrate 9 (SiO2 wafer substrate) having a dense line & space pattern as shown in FIGS. 3(Q) (top view) and (R) (cross-sectional view). The cross-sectional shapes of each wafer substrate obtained in the embedding evaluations A and B were observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and it was confirmed whether there were voids (gaps) inside the metal-containing film filling the space between the lines. The results are shown in Tables 6 and 7. When a composition for forming a metal-containing film with poor embedding characteristics was used, voids were generated inside the metal-containing film filling the space between the lines in this evaluation. When a composition for forming a metal-containing film with good embedding characteristics was used, in this evaluation, as shown in FIG. 3(S), the metal-containing film 10 without voids filled the space between the lines of the base substrate 9 having a dense line & space pattern.

[0252]

Table 6

[0253]

Table 7

[0254] As shown in Table 6, in Examples 1-1 to 1-29 using the metal-containing film-forming compositions (UDL-1 to 29) of the present invention, it was possible to fill the dense line & space pattern without generating voids even after baking at 350 °C, and it was confirmed that good embedding characteristics were obtained even under high-temperature baking conditions. On the other hand, as shown in Table 7, unlike the metal-containing film-forming compounds of the present invention, Comparative Examples 1-1 to 1-3, 1-5 to 1-6 using metal compounds (Comparative Examples UDL-1 to 3, 5 to 6) that do not contain any of the crosslinking groups represented by General Formulas (a-1) to (a-3) showed voids observed at the bottom of the pattern after baking at 350 °C. These are presumably due to the low durability of the organic ligand coordinated to the metal, resulting in a large volume shrinkage due to high-temperature baking and the generation of voids.

[0255] [Planarization Characteristic Evaluation (Examples 2-1 to 2-29, Comparative Examples 2-1 to 2-2)] For the underlying substrate 11 (SiO2 wafer substrate) having a dense line & space pattern as shown in Fig. 4(T), the cross-sectional shape of each wafer substrate in which no voids were observed in the above embedding evaluation after baking at 350 °C as shown in Fig. 4(U) was observed using a scanning electron microscope (SEM), and the step (Delta 12 in Fig. 4(U)) of the filling film 12 in the line pattern dense portion and the non-line pattern forming portion was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Tables 8 and 9. In this evaluation, it can be said that the smaller the step, the better the planarization characteristics.

[0256]

Table 8

[0257]

Table 9

[0258] As shown in Tables 8 and 9, in Examples 2-1 to 2-29 using the metal-containing film-forming composition (UDL-1 to 29) of the present invention, the film step difference between the pattern portion and the non-pattern portion was small, and it was found to have flattening performance comparable to that of Comparative Example 2-1 using a carboxylic acid as a ligand and Comparative Example 2-2 using an organic resist underlayer film material. Comparing UDL-7 to 9 in which the number of crosslinking groups contained in the organic ligand was changed, the result was obtained that the more the number of crosslinking groups contained in the organic ligand, the more excellent the flattening characteristics were shown. In addition, UDL-4 to 18 and 20 to 29 having an aromatic ring-containing ligand were found to exhibit good flatness, presumably because of their excellent heat resistance. Further, UDL-26 to which a high-boiling solvent (B1) was added and UDL-27 to 29 to which a fluidity promoter (BPA-1 to 3) was added showed more excellent flattening characteristics. It is presumed that the addition of the additive further improved the thermal fluidity of the metal-containing film-forming composition.

[0259] [Etching Resistance Evaluation (Examples 3-1 to 3-29, Comparative Examples 3-1 to 3-7)] The metal-containing film-forming composition (UDL-1 to 29 and Comparative Example UDL-1 to 7) was applied onto a silicon substrate, heated at 350 °C for 60 seconds using a hot plate to form a metal-containing film with a film thickness of 80 nm, and the film thickness a was measured. Next, each etching was performed under the following conditions using an etching apparatus TE8500 manufactured by Tokyo Electron, and the film thickness b was measured. The film thickness etched per minute was calculated as the etching rate (nm / min) from the film thickness etched during the specified time (film thickness a - film thickness b). When the etching rate was 50 nm / min or less, it was rated as A (extremely good), when it was greater than 50 nm / min and 70 nm / min or less, it was rated as B (good), and when it was greater than 70 nm / min, it was rated as C (poor). The results are shown in Tables 10 and 11.

[0260] Dry Etching Conditions with CF4 Gas Pressure: 1 Pa Antenna RF Power: 100 W Bias RF Power: 15 W CF4 Gas Flow Rate: 15 sccm Time: 30 sec

[0261] [Table 10]

[0262] [Table 11]

[0263] As shown in Tables 10 and 11, Examples 3-1 to 3-29 using the metal-containing film-forming composition (UDL-1 to 29) of the present invention were found to exhibit extremely excellent etching resistance to CF4 gas as compared with Comparative Example 3-7 using an organic resist underlayer film material (Comparative Example UDL-7). Also, in Comparative Example 3-4 using a carboxylic acid as a ligand, deterioration of the etching resistance to CF4 gas was confirmed, which is presumably because the coordination ability of the carboxylic acid to the metal atom is large and more organic components remain in the metal-containing film after baking.

[0264] [Pattern formation method (Examples 4-1 to 4-29, Comparative Examples 4-1 to 4-7)] The above metal-containing film-forming compositions (UDL-1 to 29, Comparative Examples UDL-1 to 7) were each applied onto a SiO2 wafer substrate having a trench pattern (trench width: 10 μm, trench depth: 0.10 μm), baked in the air at 350°C for 60 seconds to form a metal-containing film with a film thickness of 70 nm. A silicon atom-containing resist intermediate film material (SOG-1) was applied thereon and baked at 220°C for 60 seconds to form a resist intermediate film with a film thickness of 50 nm. A single-layer resist for ArF of a resist upper layer film material was applied thereon and baked at 105°C for 60 seconds to form a photoresist film with a film thickness of 100 nm. A liquid immersion protective film material (TC-1) was applied onto the photoresist film and baked at 90°C for 60 seconds to form a protective film with a film thickness of 50 nm.

[0265] As the silicon atom-containing resist intermediate film material (SOG-1), a polymer represented by an ArF silicon-containing intermediate film polymer (SiP1) and a thermal crosslinking catalyst (CAT1) were dissolved in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Limited) at the ratios shown in Table 12, and filtered through a fluororesin filter with a pore size of 0.1 μm to prepare the silicon atom-containing resist intermediate film material (SOG-1).

[0266]

Table 12

[0267] The structural formulas of the used ArF silicon-containing intermediate film polymer (SiP1) and thermal crosslinking catalyst (CAT1) are shown below.

Chemical formula

[0268] As the resist upper layer film material (single-layer resist for ArF), a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) were dissolved in a solvent containing 0.1% by mass of a surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) at the ratios shown in Table 13, and filtered through a 0.1-μm fluororesin filter for preparation.

[0269]

Table 13

[0270] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) used for the resist upper layer film material (single-layer resist for ArF) are shown below.

Chemical formula

[0271] The immersion protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent at the ratio shown in Table 14 and filtering it through a 0.1-μm fluororesin filter.

[0272]

Table 14

[0273] The protective film polymer (PP1) used for the immersion protective film material (TC-1) is shown below.

Chemical formula

[0274] Subsequently, exposure was performed using an ArF immersion lithography apparatus (manufactured by Nikon Corporation; NSR-S610C, NA1.30, σ0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase shift mask), followed by baking (PEB) at 100°C for 60 seconds and development for 30 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) to obtain a 55-nm 1:1 positive line-and-space pattern (resist upper layer film pattern).

[0275] Subsequently, the resist intermediate film was etched using the resist upper layer film pattern as a mask by dry etching to form a hard mask pattern, the metal-containing film was etched using the obtained hard mask pattern as a mask to form a metal-containing film pattern, and the SiO2 film was etched using the obtained metal-containing film pattern as a mask. The etching conditions are as shown below.

[0276] Transfer conditions of the resist upper layer film pattern to the resist intermediate film. Dry etching conditions with CF4 gas Pressure: 1 Pa Antenna RF power: 100 W Bias RF power: 15 W CF4 gas flow rate: 15 sccm Time: 60 sec

[0277] Transfer conditions of the hard mask pattern onto the metal-containing film. Dry etching conditions with Cl2 gas Pressure: 1 Pa Antenna RF power: 320 W Bias RF power: 30 W Cl2 gas flow rate: 25 sccm Time: 45 sec

[0278] Transfer conditions of the metal-containing film pattern onto the SiO2 film. Dry etching conditions with CF4 gas Pressure: 1 Pa Antenna RF power: 100 W Bias RF power: 15 W CF4 gas flow rate: 15 sccm Time: 60 sec

[0279] The results of observing the pattern cross-section with an electron microscope (S-4700) manufactured by Hitachi, Ltd. are shown in Tables 15 and 16.

[0280]

Table 15

[0281]

Table 16

[0282] As shown in Table 15, in Examples 4-1 to 4-29 using the metal-containing film-forming composition (UDL-1 to 29) of the present invention, in all cases, the resist upper layer film pattern was finally successfully transferred onto the substrate, and it was confirmed that the metal-containing film-forming composition of the present invention is suitably used for fine processing by the multilayer resist method. On the other hand, as shown in Table 16, in Comparative Examples 4-1 to 4-6 using Comparative Examples UDL-1 to 6 in which insufficient performance was confirmed in the embedding property evaluation and the etching resistance evaluation, pattern collapse occurred during pattern processing, and finally a good pattern could not be obtained. Further, in Comparative Example 4-7 using Comparative Example UDL-7 in which insufficient performance was confirmed in the etching resistance evaluation, pattern distortion of the pattern shape occurred during pattern processing, and finally a good pattern could not be obtained.

[0283] [SOC Pattern Inversion Method (Examples 5-1 to 5-29, Comparative Examples 5-1 to 5-8)] A coating-type resist lower layer film material (SOC-1) was applied as a resist lower layer film on a silicon wafer substrate on which a 300 nm SiO2 film was formed, baked at 350 °C for 60 seconds to form a resist lower layer film with a film thickness of 80 nm. Then, a silicon atom-containing resist intermediate film material (SOG-1) was applied thereon and baked at 220 °C for 60 seconds to form a resist intermediate film with a film thickness of 40 nm. Then, a single-layer resist for ArF of a resist upper layer film material was applied thereon and baked at 105 °C for 60 seconds to form a photoresist film with a film thickness of 100 nm. A liquid immersion protective film material (TC-1) was applied on the photoresist film and baked at 90 °C for 60 seconds to form a protective film with a film thickness of 50 nm.

[0284] As the silicon atom-containing resist intermediate film material (SOG-1), the resist upper layer film material (single-layer resist for ArF), and the liquid immersion protective film material (TC-1) on the photoresist film, the same materials as those in the above pattern formation method (Example 4) were used.

[0285] As the coating-type resist underlayer film material (SOC-1), a polymer represented by the resist underlayer film polymer (SOP1) and 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Limited) were dissolved in an organic solvent at the ratios shown in Table 17, and filtered through a fluororesin filter with a pore size of 0.2 μm to prepare the coating-type resist underlayer film material (SOC-1).

[0286]

Table 17

[0287] The structural formula of the used resist underlayer film polymer (SOP1) is shown in Table 18.

Table 18

[0288] Next, it was exposed using an ArF immersion exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA1.30, σ0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase shift mask), baked at 100°C for 60 seconds (PEB), developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds, and a 55 nm 1:1 positive line and space pattern (resist upper layer film pattern) was obtained.

[0289] Next, using the etching apparatus Telius manufactured by Tokyo Electron, the resist intermediate film was etched by dry etching using the resist upper layer film pattern as a mask to form a hard mask pattern, and the obtained hard mask pattern was used as a mask to etch the resist underlayer film (SOC-1) to form a SOC-1 film pattern. The etching conditions are as shown below.

[0290] Transfer conditions of the resist upper layer film pattern to the resist intermediate film. Chamber pressure: 50 mT RF power (upper part): 500 W RF power (lower part): 300 W CF4 gas flow rate: 150 sccm CHF3 gas flow rate: 50 sccm Time: 20 sec

[0291] Transfer conditions of the hard mask pattern to the underlying resist film. Chamber pressure: 10 mT RF power (upper): 1,000 W RF power (lower): 300 W CO2 gas flow rate: 150 sccm CO gas flow rate: 50 sccm N2 gas flow rate: 50 sccm H2 gas flow rate: 150 sccm Time: 60 sec

[0292] Next, the above metal-containing film-forming composition (UDL-1 to 29, Comparative Example UDL-1 to 7) was applied onto the obtained SOC-1 film pattern, and baked at 350 °C for 60 seconds in the air to form a metal-containing film with a film thickness of 80 nm. Then, the metal-containing film covering the SOC-1 film pattern was etched to expose the upper surface of the SOC-1 film pattern. The resist intermediate film remaining on the surface of the SOC-1 film pattern with the upper surface exposed was removed by etching, and then the exposed SOC-1 film pattern was removed by etching, reversing the above pattern on the metal-containing film. Using the obtained metal-containing film pattern as a mask, the SiO2 film was etched. As a comparative example, the SiO2 film was also etched using the SOC-1 film pattern as a mask without using the metal-containing film-forming composition (Comparative Examples 5-8). The etching conditions are as shown below.

[0293] [[ID=3२]]Etching back conditions of the metal-containing film (exposure of the SOC-1 film pattern). Pressure: 1 Pa Antenna RF power: 320 W Bias RF power: 30 W Cl2 gas flow rate: 25 sccm Time: 15 sec

[0294] Removal of the resist intermediate film remaining on the SOC-1 film pattern. Dry etching conditions with CF4 gas Pressure: 1 Pa Antenna RF power: 100 W Bias RF power: 15 W CF4 gas flow rate: 15 sccm Time: 45 sec

[0295] Removal of the SOC-1 film pattern. Dry etching conditions with O2 gas Pressure: 1 Pa Antenna RF power: 300 W Bias RF power: 0 W O2 gas flow rate: 25 sccm Time: 30 sec

[0296] Transfer conditions of the metal-containing film pattern to the SiO2 film. Dry etching conditions with CF4 gas Pressure: 1 Pa Antenna RF power: 100 W Bias RF power: 15 W CF4 gas flow rate: 15 sccm Time: 60 sec

[0297] Comparative Examples 5-8: Transfer conditions of the SOC-1 film pattern to the SiO2 film. Dry etching conditions with CF4 gas Pressure: 1 Pa Antenna RF power: 100 W Bias RF power: 15 W CF4 gas flow rate: 15 sccm Time: 60 sec

[0298] The results of observing the pattern cross-section with an electron microscope (S-4700) manufactured by Hitachi, Ltd. are shown in Tables 19 and 20.

[0299]

Table 19

[0300]

Table 20

[0301] As shown in Table 19, in Examples 5-1 to 5-29 using the metal-containing film-forming composition (UDL-1 to 29) of the present invention, in all cases, the SOC-1 film pattern was accurately inverted, and the inverted pattern was finally well transferred to the substrate without pattern collapse. From this, it was confirmed that the metal-containing film-forming composition of the present invention is suitably used for microfabrication using a tone inversion etching method in a multilayer resist process. On the other hand, as shown in Table 20, in Comparative Example 5-8 in which the SOC-1 film pattern was directly transferred to the SiO2 film, pattern distortion of the SOC-1 film was confirmed because the etching resistance of the SOC-1 film was insufficient. In Comparative Examples 5-1 to 5-6 using Comparative Examples UDL-1 to 6 in which performance deficiencies were confirmed in the embedding property evaluation and the etching resistance evaluation, pattern collapse occurred during pattern processing, and finally a good inverted pattern could not be obtained. On the other hand, in Comparative Example 5-7 using Comparative Example UDL-7 in which performance deficiencies were confirmed in the etching resistance evaluation, pattern distortion of the pattern shape occurred during pattern inversion processing, and finally a good inverted pattern could not be obtained.

[0302] [Storage Stability Evaluation (Examples 6-1 to 6-29, Comparative Examples 6-1 to 6-7)] The metal-containing film-forming compositions (UDL-1 to 29 and Comparative Examples UDL-1 to 7) were applied onto a silicon substrate and heated at 350 °C for 60 seconds using a hot plate to form a metal-containing film with a film thickness of 80 nm. Then, after storing these metal-containing film-forming compositions at 23 °C for 30 days, metal-containing films were formed on the silicon substrate under the same conditions as above, and their film thicknesses were measured. The results of the storage stability test are shown in Tables 21 and 22.

[0303]

Table 21

[0304]

Table 22

[0305] As shown in Table 21, even when the metal-containing film-forming compositions (UDL-1 to 29) of the present invention were left at 23°C for 30 days, there was almost no change in the film thickness of the metal-containing films formed from these metal-containing film-forming compositions, indicating excellent storage stability (Examples 6-1 to 6-29). Further, in Examples 6-1 to 6-10, 6-12 to 14, and 6-17 to 6-19 containing a silicon-containing ligand, compared with Examples 6-11, 6-15 to 6-16 not containing a silicon-containing ligand, the change in the film thickness of the metal-containing film formed on a silicon substrate after leaving the metal-containing film-forming composition at 23°C for 30 days was smaller, suggesting that the presence of the silicon-containing ligand contributes to the improvement of the storage stability of the metal-containing film-forming composition of the present invention. On the other hand, as shown in Table 22, in Comparative Example 6-5 using a ligand other than alcohol, a large increase in film thickness was confirmed when left at 23°C for 30 days.

[0306] From the above, a metal-containing film-forming composition containing the metal-containing film-forming compound of the present invention has both high embedding / planarization characteristics and dry etching resistance, and is thus extremely useful as a resist underlayer film material used in the multilayer resist method and a reverser used in the tone inversion etching method. Also, in the pattern formation method of the present invention using this composition, it has been clarified that even when the workpiece is a substrate having a step, a fine pattern can be formed with high precision.

[0307] This specification includes the following aspects. [1]: A metal-containing film-forming compound used in a metal-containing film-forming composition, wherein the metal-containing film-forming compound contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and a ligand coordinating to the metal atom, and the ligand contains a ligand derived from a compound represented by the following general formula (1).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[10] : The composition for forming a metal-containing film according to the above [8] or the above [9], characterized in that the (B) organic solvent contains one or more organic solvents having a boiling point of 180 ° C or higher as a high-boiling solvent.

[11] : The composition for forming a metal-containing film according to any one of the above [8] to the above

[10] , characterized in that the composition for forming a metal-containing film further contains a fluidity promoter (BP) having an organic group represented by the following general formula (3') and an aromatic ring. [Chemical formula] (In the general formula (3'), * represents a bonding site to an oxygen atom, and R B is a divalent organic group having 1 to 10 carbon atoms, and R A is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.)

[12] : The composition for forming a metal-containing film according to the above

[11] , characterized in that the fluidity promoter (BP) has at least one structural unit represented by the following general formulas (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5). [Chemical formula] (In general formulas (BP-1) and (BP-2), W 1a and W2 are each independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. R a is each independently a group represented by the following formula (4’). Y is a group represented by the following formula (5’). n1 is each independently 0 or 1, n2 is each independently 1 or 2, and V is each independently a hydrogen atom or a linking moiety.) [Chemical formula] (In general formula (BP-3), Z1 is a group represented by the following general formula (6), and R a is each independently a group represented by the following formula (4’). n4 is each independently 0 or 1, n5 is each independently 1 or 2, and V is each independently a hydrogen atom or a linking moiety.) [Chemical formula] (In formula (4’), * represents the bonding portion with the oxygen atom.) [Chemical formula] (In formula (5’), * represents a bond.) [Chemical formula] (In general formula (6), W 1a , W2, Y, and n1 are the same as described above, and * represents a bond.) [Chemical formula] (In general formula (BP-4), m3 and m4 each independently represent 1 or 2, and Z is either a single bond or a structure represented by the following general formula (7). R x is either a structure represented by the following general formula (8).) [Chemical formula] (In general formula (7), * represents a bond, l represents an integer from 0 to 3, and R a1 ~R f1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, a phenyl group, or a phenylethyl group, and R a1 and R b1 may combine to form a cyclic compound.) [Chemical formula] (In general formula (8), * represents a bonding site to an aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9).) [Chemical formula] <4001995> (In general formula (9), * represents a bonding site to a carbonyl group, and R i is the group represented by the above formula (4’). R j represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n6 and n7 represent the number of substituents on the aromatic ring, and each represents an integer from 0 to 7. However, n6 + n7 is an integer from 0 or more to 7 or less. n8 represents an integer from 0 to 2.) [Chemical formula] (In general formula (BP-5), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X C is a divalent organic group having 1 to 30 carbon atoms, and R a is the group represented by the above formula (4’). p is an integer from 0 to 5, q1 is an integer from 1 to 6, p + q1 is an integer from 1 or more to 6 or less, and q2 is 0 or 1.)

[13] : 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 metal-containing film-forming composition according to any one of [8] to

[12] above on the 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) 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) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film with the pattern formed thereon as a mask, and (I-5) A step of processing the substrate to be processed using the metal-containing film with the pattern transferred thereon as a mask to form a pattern on the substrate to be processed A pattern forming method characterized by comprising the above steps.

[14] : A method of 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 composition for forming a metal-containing film of [8] to

[12] on the substrate to be processed and then performing heat treatment, (II-2) A step of forming a silicon-containing resist intermediate film on the metal-containing film, (II-3) A step of forming a resist upper layer film on the silicon-containing 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) A step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film with the pattern formed thereon as a mask, (II-6) A step of transferring the pattern to the metal-containing film by dry etching using the silicon-containing resist intermediate film with the pattern transferred thereon as a mask, and (II-7) A step of processing the substrate to be processed using the metal-containing film with the pattern transferred thereon as a mask to form a pattern on the substrate to be processed A pattern forming method characterized by comprising the above steps.

[15] : A method of 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 from [8] to

[12] 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 metal-containing film. (III-3) A step of forming an organic thin film on the inorganic hard mask intermediate film. (III-4) A step of forming a resist upper layer film using a photoresist material on the organic thin film. (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 the 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 as a mask. (III-7) A step of transferring the pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film with the pattern transferred as a mask, and (III-8) A step of processing the substrate to be processed using the metal-containing film with the pattern transferred as a mask to form a pattern on the substrate to be processed A pattern formation method characterized by comprising the above steps.

[16] : The pattern formation method according to

[15] , wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

[17] : A method of forming a pattern on a substrate to be processed, comprising: (IV-1) A step of forming a metal-containing film by applying any one of the metal-containing film-forming compositions from [8] to

[12] on a substrate to be processed and then performing heat treatment. (IV-2) A step of forming a resist lower layer film on the metal-containing film. (IV-3) A step of forming a combination of a silicon-containing 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. (IV-4) Forming a resist upper layer film on the silicon-containing resist intermediate film or the organic thin film using a photoresist material; (IV-5) After pattern-exposing the resist upper layer film, developing it with a developer to form a pattern in the resist upper layer film; (IV-6) Using the resist upper layer film with the pattern formed thereon as a mask, transferring the pattern to the silicon-containing resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film by dry etching; (IV-7) Using the silicon-containing resist intermediate film or the inorganic hard mask intermediate film with the pattern transferred thereto as a mask, transferring the pattern to the resist lower layer film by dry etching; (IV-8) Using the resist lower layer film with the pattern transferred thereto as a mask, transferring the pattern to the metal-containing film by dry etching, and (IV-9) Using the metal-containing film with the pattern transferred thereto as a mask to process the substrate to be processed and 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: (V-1) Forming a resist lower layer 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 resist lower layer film; (V-3) Forming a resist upper layer film on the resist intermediate film, or the combination of the inorganic hard mask intermediate film and the organic thin film using a photoresist material; (V-4) 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 or the inorganic hard mask intermediate film onto which the pattern has been transferred as a mask, transferring the pattern to the resist underlayer film by dry etching; (V-7) Coating any one of the composition for forming a metal-containing film from [8] to

[12] onto the resist underlayer film onto which the pattern has been transferred, and then performing heat treatment to coat the metal-containing film and filling the spaces between the resist underlayer film patterns with the metal-containing film; (V-8) Etching back the metal-containing film covering the resist underlayer film onto which the pattern has been transferred by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern has been formed; (V-9) Removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) Removing the resist underlayer film onto which the pattern has been transferred and whose surface is exposed by dry etching to form an inverted pattern of the original pattern on the metal-containing film; and (V-11) Using the metal-containing film on which the inverted pattern has been formed as a mask to process the substrate to be processed and form an inverted pattern on the substrate to be processed. A tone inversion type pattern forming method characterized by comprising the above steps.

[0308] Note that the present invention is not limited to the above embodiments. The above embodiments are illustrative, 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

[0309] 1... Substrate to be processed, 2... Layer to be processed, 2a... Pattern (pattern on the layer to be processed), 2b... Inverted pattern (inverted pattern on the layer to be processed), 3... Metal-containing film, 3a... Metal-containing film pattern, 4... Silicon-containing resist intermediate film (resist intermediate film), 4a... Silicon-containing resist intermediate film pattern (resist intermediate film pattern), 5... Resist upper layer film, 5a... Resist upper layer film pattern, 6... Exposed portion, 7... Resist lower layer film, 7a... Resist lower layer film pattern, 8... Metal-containing film, 8a... Inverted metal-containing film pattern, 9... Lower substrate, 10... Metal-containing film, 11... Lower substrate, 12... Filling film, Delta 12... Step of the filling film.

Claims

1. A compound for forming a metal-containing film, which is used in a composition for forming a metal-containing film. The compound for forming a metal-containing film contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and a ligand coordinated to the metal atom. The ligand contains a ligand derived from a compound represented by the following general formula (1). A compound for forming a metal-containing film, characterized by the above. 【Chemical 1】 (In general formula (1), R Ａ１ is a monovalent organic group having 2 to 30 carbon atoms, X is a single bond or a divalent organic group having 2 to 10 carbon atoms in a straight chain or branched form, and R Ａ１ and X each contain at least one structure represented by the following general formulas (a-1) to (a-3).) [Chemical Formula 2] (In general formulas (a-1) to (a-3), R ａ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, R ｂ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding site.)

2. The R in the general formula (1) Ａ１ The metal-containing film-forming compound according to claim 1, wherein the R contains any one or more of an aromatic ring, an alicyclic hydrocarbon, and a heterocyclic ring.

3. The compound for forming a metal-containing film according to claim 1, characterized in that the ligand contains a ligand derived from a compound represented by the following general formula (2). 【Chemical 3】 (In general formula (2), W １ is a divalent or trivalent organic group having 3 to 20 carbon atoms containing any one or more of an aromatic ring, an alicyclic hydrocarbon, and a heterocyclic ring, R Ａ２ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 10 carbon atoms, R Ａ３ is a monovalent organic group having 1 to 10 carbon atoms, X Ａ is a single bond or a divalent organic group having 1 to 10 carbon atoms in a linear or branched form, R Ａ２ and X Ａ contains at least one or more of the structures represented by the general formulas (a-1) to (a-3), s is an integer of 1 to 6, t is an integer of 0 to 5, and t + s is an integer of 1 or more and 6 or less. )

4. The W in the general formula (2) １ The compound for forming a metal-containing film according to claim 3, wherein the compound is any of the following structures. 【Chemical Formula 4】

5. The compound for forming a metal-containing film according to claim 3, characterized in that the compound for forming a metal-containing film is a reaction product of a metal compound represented by the following general formula (3), or a metal-containing compound containing any one of a hydrolyzate, a condensate, and a hydrolyzate-condensate of the metal compound represented by the following general formula (3), and the compound represented by the general formula (1) or the general formula (2). 【Chemical Formula 5】 (In general formula (3), M is any one of Ti, Zr, and Hf. L is a monodentate ligand or a multidentate ligand having 0 to 30 carbon atoms, and X Ｂ is a hydrolyzable group selected from a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, and -NR ａ’ R ｂ’ R. R ａ’ and R ｂ’ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a + b = 4, and a and b are integers from 0 to 4.)

6. The compound for forming a metal-containing film according to claim 5, characterized in that the general formula (3) has the structure of the following general formula (4). 【Chemical Formula 6】 (In the general formula (4), M is any one of Ti, Zr, and Hf, and R １Ａ is a monovalent organic group having 1 to 20 carbon atoms.)

7. The compound for forming a metal-containing film according to claim 1, characterized in that the compound for forming a metal-containing film further contains a ligand derived from a silicon compound represented by the following general formula (5). 【Chemical Formula 7】 (In general formula (5), R ３Ａ , R ３Ｂ and R ３Ｃ is any organic group having 1 to 30 carbon atoms and having a crosslinking group of any of the structures represented by the following general formulas (b-1) to (b-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Any of the selected organic groups.) 【Chemical 8】 (In general formulas (b-1) to (b-3), R ３ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding site.)

8. A composition for forming a metal-containing film used in semiconductor manufacturing, characterized by containing (A) the compound for forming a metal-containing film according to any one of claims 1 to 7, and (B) an organic solvent.

9. The composition for forming a metal-containing film according to claim 8, characterized in that the composition further contains one or more of (E) a crosslinking agent, (G) a surfactant, and (H) an acid generator.

10. The composition for forming a metal-containing film according to claim 8, characterized in that the (B) organic solvent contains one or more organic solvents having a boiling point of 180 °C or higher as (B1) a high-boiling solvent.

11. The composition for forming a metal-containing film according to claim 8, characterized in that the composition for forming a metal-containing film further contains a fluidity promoter (BP) having any one of the organic groups represented by the following general formula (3') and an aromatic ring. 【Chemical Formula 9】 (In the general formula (3'), * represents a bonding site to an oxygen atom, and R Ｂ is a divalent organic group having 1 to 10 carbon atoms, and R Ａ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.)

12. The composition for forming a metal-containing film according to claim 11, wherein the fluidity promoter (BP) has at least one structural unit represented by the following general formulas (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5). 【Chemical 10】 (In general formulas (BP-1) and (BP-2), W １ａ and W ２ are each independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. R ａ are each independently a group represented by the following formula (4'). Y is a group represented by the following formula (5'). n1 is each independently 0 or 1, n2 is each independently 1 or 2, and V is each independently a hydrogen atom or a linking portion.) 【Chemical 11】 (In the general formula (BP-3), Z １ has a group represented by the following general formula (6), and R ａ are each independently a group represented by the following formula (4'). n4 are each independently 0 or 1, n5 are each independently 1 or 2, and V are each independently a hydrogen atom or a linking moiety.) 【Chemical Formula 12】 (In formula (4'), * represents a bonding portion with an oxygen atom.) 【Chemical 13】 (In formula (5'), * represents a bond.) 【Chemical 14】 (In general formula (6), W １ａ , W ２ , Y, and n1 are the same as described above, and * represents a bond.) 【Chemical Formula 15】 (In general formula (BP-4), m3 and m4 each independently represent 1 or 2, and Z is either a single bond or a structure represented by the following general formula (7). R ｘ is any of the structures represented by the following general formula (8).) 【Chemical 16】 (In general formula (7), * represents a bond, l represents an integer of 0 to 3, and R ａ１ ~R ｆ１ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, a phenyl group, or a phenylethyl group, and R ａ１ and R ｂ１ may combine to form a cyclic compound.) 【Chemical 17】 (In general formula (8), * represents the bonding site to the aromatic ring, and Q １ is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or has a structure represented by the following general formula (9).) 【Chemical Formula 18】 (In general formula (9), * represents the bonding site to the carbonyl group, and R ｉ is the group represented by the said formula (4'). R ｊ represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n6 and n7 represent the number of substituents on the aromatic ring, and each represents an integer of 0 to 7. However, n6 + n7 is an integer of 0 or more and 7 or less. n8 represents an integer of 0 to 2.) 【Chemical Formula 19】 (In the general formula (BP-5), R １ is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X Ｃ is a divalent organic group having 1 to 30 carbon atoms, and R ａ is a group represented by the formula (4'). p is an integer of 0 to 5, q1 is an integer of 1 to 6, p + q1 is an integer of 1 or more and 6 or less, and q2 is 0 or 1.)

13. 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 according to claim 8 on the 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) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film having the pattern as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film having the pattern transferred thereto as a mask to form a pattern on the substrate to be processed A pattern forming method characterized by comprising the above steps.

14. 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 according to claim 8 on the substrate to be processed and then performing a heat treatment; (II-2) A step of forming a silicon-containing resist intermediate film on the metal-containing film; (II-3) A step of forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist material; (II-4) A step of forming a pattern on the resist upper layer film by pattern exposure and then developing with a developer; (II-5) A step of transferring the pattern to the silicon-containing 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 silicon-containing 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 transferred thereto as a mask to form a pattern on the substrate to be processed A pattern forming method characterized by comprising the above steps.

15. A method for forming a pattern on a substrate to be processed, comprising: Step (III-1) of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 8 onto a substrate to be processed and then performing a heat treatment; Step (III-2) 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 metal-containing film; Step (III-3) of forming an organic thin film on the inorganic hard mask intermediate film; Step (III-4) of forming an upper resist film using a photoresist material on the organic thin film; Step (III-5) of performing pattern exposure on the upper resist film and then developing with a developer to form a pattern in the upper resist film; Step (III-6) of using the upper resist film on which the pattern is formed as a mask and transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching; Step (III-7) of using the inorganic hard mask intermediate film on which the pattern is transferred as a mask and transferring the pattern to the metal-containing film by dry etching; and Step (III-8) of using the metal-containing film on which the pattern is transferred as a mask to process the substrate to be processed and form a pattern in the substrate to be processed A pattern forming method characterized by comprising the above steps.

16. The pattern forming method according to claim 15, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

17. A method of forming a pattern in a substrate to be processed, comprising: Step (IV-1) of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 8 onto a substrate to be processed and then performing a heat treatment; Step (IV-2) of forming a lower resist film on the metal-containing film; Step (IV-3) of forming a combination of a silicon-containing 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; Step (IV-4) of forming an upper resist film using a photoresist material on the silicon-containing resist intermediate film or the organic thin film; Step (IV-5) of performing pattern exposure on the upper resist film and then developing with a developer to form a pattern in the upper resist film; Step (IV-6) of using the upper resist film on which the pattern is formed as a mask and transferring the pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching; Step (IV-7) of transferring a pattern onto the resist underlayer film by dry etching using, as a mask, a silicon-containing resist intermediate film or an inorganic hard mask intermediate film onto which the pattern has been transferred. Step (IV-8) of transferring a pattern onto the metal-containing film by dry etching using, as a mask, the resist underlayer film onto which the pattern has been transferred; and Step (IV-9) of processing the substrate to be processed using, as a mask, the metal-containing film onto which the pattern has been transferred to form a pattern on the substrate to be processed. A pattern forming method, characterized by comprising these steps.

18. A method of forming a pattern on a substrate to be processed, comprising: Step (V-1) of forming a resist underlayer film on the substrate to be processed; Step (V-2) of forming, on the resist underlayer film, 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; Step (V-3) 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; Step (V-4) of forming a pattern on the resist upper layer film by exposing the resist upper layer film to pattern exposure and then developing it with a developer; Step (V-5) of transferring a pattern onto the resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching using, as a mask, the resist upper layer film on which the pattern has been formed; Step (V-6) of transferring a pattern onto the resist underlayer film by dry etching using, as a mask, the resist intermediate film or the inorganic hard mask intermediate film onto which the pattern has been transferred; Step (V-7) of coating the metal-containing film forming composition according to claim 8 on the resist underlayer film onto which the pattern has been transferred 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; Step (V-8) of etching back the metal-containing film covering the resist underlayer film onto which the pattern has been transferred by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern has been formed; Step (V-9) of removing, by dry etching, the resist intermediate film or the inorganic hard mask intermediate film remaining on the upper surface of the resist underlayer film. The step of removing the resist underlayer film on which the pattern with the exposed (V-10) surface is transferred by dry etching to form an inverted pattern of the original pattern on the metal-containing film, and the 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 A tone inversion type pattern forming method characterized by comprising these steps.

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