Materials for forming organic films, substrates for manufacturing semiconductor devices, methods for forming organic films, and methods for forming patterns.

Abstract

To provide: a compound that can be cured under film-forming conditions in inert gas so as to form an organic film which is excellent in heat resistance and in filling and planarization characteristics of a pattern formed on a substrate, and also has good adhesiveness to the substrate; and a material for forming an organic film containing the compound.SOLUTION: A material for forming an organic film contains: (A) a compound for forming an organic film represented by a general formula (1A) in the figure; and (B) an organic solvent. (Y represents an n1-valent organic group, a trivalent nitrogen atom, or a tetravalent carbon atom; n1 represents an integer of 3 to 8; and X is a partial structure represented by a general formula (1B) in the figure.)SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a material for forming an organic film, a substrate for manufacturing a semiconductor device using the material, a method for forming an organic film, a method for forming a pattern by a multilayer resist method, and a compound that can be suitably used for the material.

Background Art

[0002] Conventionally, the high integration and high speed of semiconductor devices have been achieved by miniaturization of pattern dimensions due to shortening of the wavelength of the light source in lithography technology (optical lithography) using optical exposure as a general-purpose technology. In order to form such a fine circuit pattern on a substrate for manufacturing a semiconductor device (a substrate to be processed), a method is usually used in which a photoresist film on which a pattern is formed is used as an etching mask, and the substrate to be processed is processed by dry etching. However, in reality, there is no dry etching method that can achieve complete etching selectivity between the photoresist film and the substrate to be processed. Therefore, in recent years, substrate processing by the multilayer resist method has become common. This method involves interposing an intermediate film having different etching selectivity from a photoresist film (hereinafter also referred to as an upper resist film) between the upper resist film and the substrate to be processed. After obtaining a pattern on the upper resist film, the upper resist film pattern is used as a dry etching mask, and the pattern is transferred to the intermediate film by dry etching. Further, the intermediate film is used as a dry etching mask, and the pattern is transferred to the substrate to be processed by dry etching.

[0003] One multilayer resist method is the three-layer resist method, which can be performed using the same resist compositions as those used in the single-layer resist method. In this method, an organic underlayer film (hereinafter also called an organic film) is formed on a substrate by coating and firing an organic underlayer film material (hereinafter also called an organic film-forming material) made from an organic resin-containing composition. A silicon-containing film (hereinafter also called a silicon-containing resist interlayer) is then formed on top of this by coating and firing a resist interlayer material (hereinafter also called a silicon-containing resist interlayer material) made from a silicon-containing resin-containing composition. Finally, a general organic photoresist film (resist upper layer) is formed on top of this. After patterning the resist upper layer, dry etching is performed using a fluorine-based gas plasma. Since the organic resist upper layer can achieve a good etching selectivity ratio with respect to the silicon-containing resist interlayer, the resist upper layer pattern can be transferred to the silicon-containing resist interlayer. According to this method, even if a resist top layer film does not have sufficient thickness to directly process the substrate, or a resist top layer film does not have sufficient dry etching resistance for processing the substrate, the silicon-containing resist interlayer film usually has a thickness equal to or less than that of the resist top layer film, so the pattern can be easily transferred to the silicon-containing resist interlayer film. Subsequently, by using the pattern-transferred silicon-containing resist interlayer film as a dry etching mask and dry etching the pattern onto an organic film with an oxygen-based or hydrogen-based gas plasma, the pattern can be transferred onto an organic film with sufficient dry etching resistance for processing the substrate. This pattern-transferred organic film pattern can then be transferred to the substrate by dry etching using a fluorine-based gas or a chlorine-based gas.

[0004] On the other hand, miniaturization in the manufacturing process of semiconductor devices is approaching an inherent limit derived from the wavelength of the light source used for photolithography. Therefore, in recent years, the integration of semiconductor devices without relying on miniaturization has been investigated, and one method for this is semiconductor devices with complex structures such as multi-gate structures, some of which have already been put into practical use. When forming such structures using the multilayer resist method, it is possible to apply organic film-forming materials that can fill minute patterns such as holes, trenches, and fins formed on the substrate without gaps with a film, or fill steps, densely patterned areas, and areas without patterns with a film to perform planarization. By forming a flat organic film surface on a stepped substrate using such organic film-forming materials, variations in the film thickness of the silicon-containing resist interlayer and resist upper layer formed on it can be suppressed, thereby reducing the focus margin in photolithography and the margin reduction in subsequent processing steps of the substrate. This makes it possible to manufacture semiconductor devices with a high yield. On the other hand, in the single-layer resist method, the thickness of the upper resist film becomes thicker in order to fill in the steps and patterns on the substrate to be processed. This narrows the margin for pattern formation during exposure, making it difficult to manufacture semiconductor devices with a high yield, as it can lead to pattern collapse after exposure and development, as well as degradation of the pattern shape due to reflection from the substrate during exposure.

[0005] Furthermore, as a method for increasing the speed of next-generation semiconductor devices, the application of new materials with high electron mobility, such as strained silicon and gallium arsenide, and precision materials such as ultrathin polysilicon films controlled in angstroms, is beginning to be considered. However, in substrates to which such new precision materials are applied, under the conditions for planarization film formation using the above-mentioned organic film-forming materials, for example, under film formation conditions of 300°C or higher in air, the material may be corroded by oxygen in the air, preventing the semiconductor device from achieving the performance intended by the material design, and potentially failing to achieve a yield that is viable for industrial production. Therefore, in order to avoid the decrease in yield caused by substrate corrosion due to air under such high-temperature conditions, organic film-forming materials that can be formed in an inert gas are highly anticipated.

[0006] Conventionally, condensation resins using carbonyl compounds such as ketones and aldehydes, or aromatic alcohols, as condensing agents for phenolic and naphthol compounds have been known as organic film-forming materials for multilayer resist methods. Examples include the fluorenebisphenol novolac resin described in Patent Document 1, the bisphenol compound and its novolac resin described in Patent Document 2, the adamantanephenol compound novolac resin described in Patent Document 3, and the bisnaphthol compound and its novolac resin described in Patent Document 4. Such materials are formed as films with solvent resistance to coating film materials used in subsequent processes by crosslinking with methylol compounds as crosslinking agents, or by a curing reaction through oxidation at the α-position of the aromatic ring by the action of oxygen in the air and subsequent condensation. However, since the driving force for exhibiting this solvent resistance is oxidation, it is not possible to satisfy various properties such as sufficient heat resistance and flatness in an inert gas environment. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2005-128509 [Patent Document 2] Japanese Patent Publication No. 2006-293298 [Patent Document 3] Japanese Patent Publication No. 2006-285095 [Patent Document 4] Japanese Patent Publication No. 2010-122656 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] The present invention has been made in view of the above circumstances, and aims to provide a compound that can form an organic film that hardens not only in air but also under film formation conditions in an inert gas, and that has excellent heat resistance, embedding and planarization characteristics of patterns formed on a substrate, as well as good adhesion to the substrate, and an organic film forming material containing the compound. Furthermore, the present invention aims to provide a substrate for semiconductor device manufacturing using the material, a method for forming an organic film, and a method for forming a pattern. [Means for solving the problem]

[0009] To solve the above problems, the present invention provides an organic film forming material, The present invention provides an organic film-forming material characterized by containing (A) an organic film-forming compound represented by the following general formula (1A), and (B) an organic solvent. [ka] (In the formula, Y is an n1-valent organic group, a trivalent nitrogen atom, or a tetravalent carbon atom, n1 is an integer from 3 to 8, and X is a substructure represented by the following general formula (1B).) [ka] (In the formula, dashed lines represent bonds. R1 and R2 represent halogen atoms, C1-C4 alkyl groups, C1-C4 alkyloxy groups, C2-C4 alkynyl groups, or C2-C4 alkenyl groups, and the hydrogen atoms on the carbon atoms constituting the alkyl groups, alkyloxy groups, alkynyl groups, or alkenyl groups may be substituted with fluorine atoms. Furthermore, aromatic rings that can be substituted by R1 may form a bridging structure via single bonds or via a divalent group obtained by removing one hydrogen atom from R1. n4 and n5 represent integers from 0 to 2. Ar1 and Ar2 represent a benzene ring or a naphthalene ring, respectively. n2 represents 0 or 1, n3 represents 1 or 2, and R3 represents a hydrogen atom or a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group.)

[0010] Such organicfilm As a forming material, it can be used as a material for forming an organic film that can be cured not only in air but also under film-forming conditions in an inert gas, and has high heat resistance, good adhesion to a substrate, and excellent embedding / planarization characteristics.

[0011] In this case, it is preferable that R3 in the general formula (1B) is any one of those represented by the following formula (1C).

Chemical formula

[0012] Introducing the above terminal structure into the organic film-forming compound as the component (A) is preferable from the viewpoints of imparting excellent curability, flatness, embedding characteristics, and adhesion to the substrate.

[0013] Moreover, it is preferable that n1 in the general formula (1A) is 3 or 4.

[0014] Adjusting the number of substituents in the organic film-forming compound as the component (A) to an appropriate range is preferable from the viewpoint of preventing the loss of thermal fluidity due to rapid curing.

[0015] Also, it is preferable that n2 in the general formula (1B) is 1.

[0016] By introducing the above structure into the organic film-forming compound as the component (A), the carbon density can be increased, so etching resistance can be imparted, and further shrinkage of the film due to heat is suppressed, so it becomes possible to form a film with good heat resistance and flatness.

[0017] Moreover, it is preferable that Y in the general formula (1A) is any one of the partial structures shown in the following formula (1D).

Chemical formula

[0018] (A) It is preferable that the organic film-forming compound, which is component (A), has the structure described above, from the viewpoint of improving various physical properties such as heat resistance, solvent solubility, and flatness.

[0019] It is preferable that the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of component (A) as determined by gel permeation chromatography is 1.00 ≤ Mw / Mn ≤ 1.10.

[0020] (A) By controlling the Mw / Mn ratio of the organic film-forming compound, which is component (A), within this range, it is possible to form an organic film with excellent embedding properties and flatness.

[0021] The (B) organic solvent is preferably a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

[0022] An organic film-forming material in which the organic solvent is a mixture as described above can provide an organic film with more advanced embedding / planarization properties by imparting thermal fluidity through the addition of a high-boiling-point solvent. In this invention, the boiling point is the value at 1 atmosphere (1013 hPa).

[0023] Furthermore, the organic film-forming material of the present invention may further contain one or more of (C) an acid generator, (D) a surfactant, (E) a crosslinking agent, and (F) a plasticizer.

[0024] The organic film-forming material of the present invention may contain one or more of the above components (C) to (F), depending on its purpose.

[0025] Furthermore, the present invention provides a substrate for manufacturing semiconductor devices, characterized in that an organic film formed on the substrate is obtained by curing the organic film-forming material of the present invention.

[0026] Such substrates contain an organic film that possesses high heat resistance, good adhesion to the substrate, and advanced embedding / planarization characteristics, resulting in a good yield of semiconductor devices when used in the manufacturing process.

[0027] Furthermore, the present invention provides a method for forming an organic film applicable in the manufacturing process of a semiconductor device, characterized by rotating the application of the organic film forming material of the present invention onto a workpiece substrate, and then heat-treating the workpiece substrate coated with the organic film forming material in an inert gas atmosphere at a temperature of 50°C to 600°C for a range of 5 to 7200 seconds to obtain a cured film.

[0028] The organic film formed by the method of the present invention and applied in the semiconductor device manufacturing process hardens even when formed in an inert gas, possesses high heat resistance and advanced embedding / planarization characteristics, and when used in the semiconductor device manufacturing process, it results in a good yield of semiconductor devices.

[0029] Furthermore, the present invention provides a method for forming an organic film applicable in the manufacturing process of a semiconductor device, characterized by: rotating the application of the organic film-forming material of the present invention onto a workpiece substrate; heat-treating the workpiece substrate coated with the organic film-forming material in air at a temperature of 50°C to 300°C for 5 to 600 seconds to form a coated film; and subsequently applying heat treatment in an inert gas atmosphere at a temperature of 200°C to 600°C for 10 to 7200 seconds to obtain a cured film.

[0030] The organic film formed by the method of the present invention and applied in the manufacturing process of semiconductor devices hardens even when partially deposited in an inert gas, and possesses high heat resistance and advanced embedding / planarization characteristics, resulting in a good yield of semiconductor devices when used in the manufacturing process.

[0031] Furthermore, in the method for forming an organic film according to the present invention, it is preferable that the oxygen concentration in the inert gas be 1% by volume or less.

[0032] The organic film-forming material of the present invention can be heated in such an inert gas atmosphere, yet it will harden sufficiently without generating sublimation, and it can form an organic film with excellent adhesion to the substrate. Furthermore, heating in such an inert gas atmosphere can prevent corrosion of the substrate being processed. In this invention, the oxygen concentration is expressed on a volume basis.

[0033] Furthermore, in the present invention, a substrate having a structure or step with a height of 30 nm or more can be used as the substrate to be processed.

[0034] The method for forming an organic film according to the present invention is particularly useful when forming a flat organic film on such a workpiece substrate.

[0035] Furthermore, the present invention provides a pattern formation method characterized by forming an organic film on a workpiece using the organic film forming material of the present invention, forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material, forming a resist upper layer on the silicon-containing resist interlayer using a photoresist composition, forming a circuit pattern on the resist upper layer, transferring the pattern to the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0036] Furthermore, the present invention provides a pattern formation method characterized by forming an organic film on a workpiece using the organic film forming material of the present invention, forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material, forming an organic anti-reflective film on the silicon-containing resist interlayer, forming a resist upper layer on the organic anti-reflective film using a photoresist composition to form a four-layer film structure, forming a circuit pattern on the resist upper layer, transferring the pattern to the organic anti-reflective film and the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0037] Furthermore, the present invention provides a pattern formation method characterized by forming an organic film on a workpiece using the organic film forming material of the present invention, forming an inorganic hard mask selected from silicon oxide film, silicon nitride film, silicon oxynitride film, titanium oxide film, and titanium nitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0038] Furthermore, the present invention provides a pattern formation method characterized by forming an organic film on a workpiece using the organic film forming material of the present invention, forming an inorganic hard mask selected from silicon oxide film, silicon nitride film, silicon oxynitride film, titanium oxide film, and titanium nitride film on the organic film, forming an organic anti-reflective film on the inorganic hard mask, forming a resist upper layer film on the organic anti-reflective film using a photoresist composition to form a four-layer film structure, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic anti-reflective film and the inorganic hard mask by etching using the resist upper layer film on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0039] The organic film forming material of the present invention can be suitably used in various pattern formation methods, such as a three-layer resist process using a silicon-containing resist interlayer or an inorganic hard mask, or a four-layer resist process using an organic anti-reflective film in addition to these. In the manufacturing process of semiconductor devices, if circuit patterns are formed using the pattern formation method of the present invention, semiconductor devices can be manufactured with a high yield.

[0040] When using the inorganic hard mask, it is preferable to form it by CVD or ALD.

[0041] In the pattern formation method of the present invention, an inorganic hard mask can be formed by, for example, the method described above.

[0042] Furthermore, in the present invention, it is preferable to form the circuit pattern using lithography with light having a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0043] In forming the circuit pattern, it is preferable to develop the circuit pattern using alkaline development or an organic solvent.

[0044] In the pattern formation method of the present invention, such circuit pattern formation means and developing means can be suitably used.

[0045] Furthermore, it is preferable to use a semiconductor device substrate, or a semiconductor device substrate on which any of the following films—metal film, metal carbide film, metal oxide film, metal nitride film, metal oxide carbide film, or metal oxide nitride film—is formed.

[0046] It is preferable to use a workpiece containing silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof.

[0047] With the pattern forming method of the present invention, patterns can be formed by processing the workpiece as described above.

[0048] Furthermore, the present invention provides a compound represented by the following general formula (1A). [ka] (In the formula, Y is an n1-valent organic group, a trivalent nitrogen atom, or a tetravalent carbon atom, n1 is an integer from 3 to 8, and X is a substructure represented by the following general formula (1B).) [ka] (In the formula, dashed lines represent bonds. R1 and R2 represent halogen atoms, C1-C4 alkyl groups, C1-C4 alkyloxy groups, C2-C4 alkynyl groups, or C2-C4 alkenyl groups, and the hydrogen atoms on the carbon atoms constituting the alkyl groups, alkyloxy groups, alkynyl groups, or alkenyl groups may be substituted with fluorine atoms. Furthermore, aromatic rings that can be substituted by R1 may form a bridging structure via single bonds or via a divalent group obtained by removing one hydrogen atom from R1. n4 and n5 represent integers from 0 to 2. Ar1 and Ar2 represent a benzene ring or a naphthalene ring, respectively. n2 represents 0 or 1, n3 represents 1 or 2, and R3 represents a hydrogen atom or a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group.)

[0049] Compounds containing three or more such cardi structures in a single molecule can harden not only in air but also under inert gas deposition conditions due to substituents introduced at the terminal structures, forming organic films that possess high heat resistance, good adhesion to substrates, and advanced embedding / planarization properties. Furthermore, the introduction of multiple cardi structures into the molecule reduces the crystallinity of the compound, improving solubility in solvents without compromising heat resistance, and enabling a balance between the conflicting properties of thermal fluidity and heat resistance.

[0050] In this case, it is preferable that R3 in the general formula (1B) is one of those shown in the following formula (1C). [ka] (The dashed lines in the above equation represent connections.)

[0051] By introducing such terminal structures, properties such as crosslinking, good adhesion to the substrate, and advanced embedding / planarization characteristics can be achieved.

[0052] The compounds of the present invention are preferably such that n1 in the general formula (1A) is 3 or 4.

[0053] Adjusting the number of substituents in the compound to an appropriate range is preferable from the viewpoint of preventing loss of thermal fluidity due to rapid curing.

[0054] Furthermore, it is preferable that n2 in the general formula (1B) is 1.

[0055] By introducing the above-described structure into the compound, the carbon density can be increased, thereby providing etching resistance. Furthermore, thermal shrinkage of the film is suppressed, making it possible to form a film with good heat resistance and flatness.

[0056] Furthermore, it is preferable that Y in the general formula (1A) is one of the substructures shown in the following formula (1D). [ka] (In the above formula, the dashed lines represent bonding bonds, and R4 represents a hydrogen atom or a methyl group.)

[0057] The compound of the present invention is preferable to have the structure described above from the viewpoint of improving various physical properties such as heat resistance, solvent solubility, and flatness. [Effects of the Invention]

[0058] As described above, the compound of the present invention hardens without generating by-products even when deposited in an inert gas that prevents substrate corrosion, and is a useful compound for forming organic films that combine high heat resistance, good adhesion to the substrate, and advanced embedding and planarization properties. Furthermore, the organic film forming material containing this compound (organic film forming compound) is a material that forms organic films that have excellent embedding / planarization properties as well as various properties such as heat resistance and etching resistance. Therefore, an organic film obtained using the organic film forming material of the present invention will have advanced embedding / planarization properties, resulting in an organic film without micro-pores due to poor embedding or surface irregularities due to insufficient flatness. For this reason, the organic film forming material of the present invention is extremely useful as an organic film forming material in multilayer resist methods such as the two-layer resist method, the three-layer resist method using a silicon-containing interlayer, and the four-layer resist method using a silicon-containing interlayer and an organic anti-reflective film, or as a planarization material for semiconductor device manufacturing. Furthermore, the organic film formed from the organic film-forming material of the present invention has excellent heat resistance, so even when a CVD hard mask is formed on the organic film, there is no change in film thickness due to thermal decomposition, making it suitable for pattern formation. Moreover, semiconductor device substrates planarized with the organic film of the present invention have a wider process tolerance during patterning, making it possible to manufacture semiconductor devices with a high yield. And, in the semiconductor device manufacturing process, if circuit patterns are formed using the pattern formation method of the present invention, semiconductor devices can be manufactured with a high yield. [Brief explanation of the drawing]

[0059] [Figure 1] This is an explanatory diagram of the planarization characteristics in the present invention. [Figure 2] This is an explanatory diagram of an example of a pattern formation method using the three-layer resist method of the present invention. [Figure 3] This is an explanatory diagram of the embedding characteristics evaluation method in the example. [Figure 4] This is an explanatory diagram of the method for evaluating planarization characteristics in the embodiment. [Figure 5] This is an explanatory diagram of the adhesion measurement method in the example. [Modes for carrying out the invention]

[0060] As described above, in order to prevent substrate corrosion, there has been a need to develop organic film-forming compounds that can form organic films without generating by-products even under inert gas deposition conditions, such as above 300°C, and that not only have excellent embedding and planarization characteristics for patterns formed on the substrate, but also have good dry etching resistance during substrate processing. Furthermore, even when forming a CVD hard mask on the organic film, there has been a need to develop organic film-forming materials that do not cause changes in the thickness of the organic film due to thermal decomposition, and organic film-forming compounds that are useful for pattern formation methods using such materials.

[0061] Normally, when forming an organic film, an organic film-forming compound is dissolved in an organic solvent to form a composition, which is then applied to a substrate on which the structure and wiring of a semiconductor device are formed, and the organic film is formed by firing. Immediately after application of the composition, a coating film is formed that conforms to the shape of the stepped structure on the substrate. However, when the coating film is fired, most of the organic solvent evaporates before it hardens, and the organic film is formed by the organic film-forming compound remaining on the substrate. The inventors of the present invention realized that if the organic film-forming compound remaining on the substrate at this time has sufficient thermal fluidity, it is possible to flatten the stepped shape immediately after application by thermal fluidity and form a flat film.

[0062] The inventors have conducted further intensive studies and have found that an organic film-forming compound having a fluorene-type substituent represented by the following general formula (1A) exhibits thermosetting properties equivalent to conventional organic film-forming materials not only in air but also in inert gases due to the action of substituents introduced at the terminals, and exhibits excellent thermal fluidity, resulting in superior embedding / planarization characteristics. Because it proceeds via a curing mechanism independent of oxidation, there is no deterioration of etching resistance due to oxidation of the organic film-forming compound, and it has good dry etching resistance. Furthermore, because it has multiple rigid fluorene structures, it provides an organic film-forming material that also possesses heat resistance without changes in coating film thickness due to thermal decomposition, even when forming a CVD hard mask, thus completing the present invention.

[0063] In other words, the present invention is an organic film-forming material characterized by containing (A) an organic film-forming compound represented by the following general formula (1A), and (B) an organic solvent. [ka] (In the formula, Y is an n1-valent organic group, a trivalent nitrogen atom, or a tetravalent carbon atom, n1 is an integer from 3 to 8, and X is a substructure represented by the following general formula (1B).) [ka] (In the formula, dashed lines represent bonds. R1 and R2 represent halogen atoms, C1-C4 alkyl groups, C1-C4 alkyloxy groups, C2-C4 alkynyl groups, or C2-C4 alkenyl groups, and the hydrogen atoms on the carbon atoms constituting the alkyl groups, alkyloxy groups, alkynyl groups, or alkenyl groups may be substituted with fluorine atoms. Furthermore, aromatic rings that can be substituted by R1 may form a bridging structure via single bonds or via a divalent group obtained by removing one hydrogen atom from R1. n4 and n5 represent integers from 0 to 2. Ar1 and Ar2 represent a benzene ring or a naphthalene ring, respectively. n2 represents 0 or 1, n3 represents 1 or 2, and R3 represents a hydrogen atom or a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group.)

[0064] Furthermore, the present invention relates to a compound represented by the above general formula (1A) that can be used as a material for forming organic films.

[0065] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0066] The organic film-forming material of the present invention is characterized by containing an organic film-forming compound (component A) represented by the above general formula (1A) and an organic solvent (component B). The organic film-forming material only needs to contain the compound (organic film-forming compound) represented by the above general formula (1A) and an organic solvent, and may contain other components as needed. The components will be described below.

[0067] <Compounds for organic film formation> The organic film-forming compound of the present invention is represented by the following general formula (1A) and is an organic film-forming compound. [ka] (In the formula, Y is an n1-valent organic group, a trivalent nitrogen atom, or a tetravalent carbon atom, n1 is an integer from 3 to 8, and X is a substructure represented by the following general formula (1B).) [ka] (In the formula, dashed lines represent bonds. R1 and R2 represent halogen atoms, C1-C4 alkyl groups, C1-C4 alkyloxy groups, C2-C4 alkynyl groups, or C2-C4 alkenyl groups, and the hydrogen atoms on the carbon atoms constituting the alkyl groups, alkyloxy groups, alkynyl groups, or alkenyl groups may be substituted with fluorine atoms. Furthermore, aromatic rings that can be substituted by R1 may form a bridging structure via single bonds or via a divalent group obtained by removing one hydrogen atom from R1. n4 and n5 represent integers from 0 to 2. Ar1 and Ar2 represent a benzene ring or a naphthalene ring, respectively. n2 represents 0 or 1, n3 represents 1 or 2, and R3 represents a hydrogen atom or a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group.)

[0068] As shown in the general formula (1B) above, the introduction of three or more cardi structures into the molecule reduces the crystallinity of the compound, improving solubility in solvents without compromising heat resistance, thus enabling a balance between thermal fluidity and heat resistance, which are typically trade-off properties. Furthermore, OR3 can be cured in air and under inert gas conditions by selecting substituents, and the chain length can be adjusted as appropriate from the viewpoint of flatness and curability. In addition, high adhesion to the substrate can be imparted by mixing it with compounds that partially contain ether groups or hydroxyl groups. Moreover, various physical properties such as etching resistance and optical properties can be adjusted by appropriately selecting the structure that forms the main skeleton represented by Y. These compounds prevent film delamination when forming inorganic hard masks directly on organic films using CVD or ALD methods, enabling the formation of organic films with excellent process tolerance.

[0069] Examples of n1-valent organic groups in the above general formula (1A) include the following, and if these aromatic rings are present, substituents may be present, such as C1-C10 alkyl groups, C3-C10 alkynyl and alkenyl groups, C6-C10 aryl groups, nitro groups, and halogens. atom Examples include nitrile groups, alkoxycarbonyl groups with 1 to 10 carbon atoms, and alkanoyloxy groups with 1 to 10 carbon atoms.

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] Among the compounds represented by the above general formula (1A), the substituent R1 on the aromatic ring of general formula (1B) is a hydrogen atom in the other aromatic ring. Instead The following is an example of how a cross-linking structure is formed (where R1 groups of different aromatic rings bond to each other to form a cross-linking structure). Ar1, Ar2, n1, n2, n3, n5, R1, R2, R3 are the same as above. [ka]

[0075] Among the above, from the viewpoint of adjusting the number of substituents in the compound to an appropriate range to prevent loss of thermal fluidity due to rapid hardening, and from the viewpoint of the fact that the molecular weight of the compound increases as the substituent represented by X increases, thereby impairing thermal fluidity, it is preferable that n1 = 3 or 4 is satisfied, that is, when Y is a trivalent or tetravalent organic group, and n1 = 3 is more preferable due to the ease of obtaining the raw materials.

[0076] Furthermore, from the viewpoint of ease of raw material availability, heat resistance, and thermal fluidity, Y is more preferably one of the substructures shown by the following formula (1D). [ka] (In the above formula, the dashed lines represent bonding bonds, and R4 represents a hydrogen atom or a methyl group.)

[0077] In the above general formula (1A), X is given by the following general formula (1B). [ka] (In the formula, dashed lines represent bonds. R1 and R2 represent halogen atoms, C1-C4 alkyl groups, C1-C4 alkyloxy groups, C2-C4 alkynyl groups, or C2-C4 alkenyl groups, and the hydrogen atoms on the carbon atoms constituting the alkyl groups, alkyloxy groups, alkynyl groups, or alkenyl groups may be substituted with fluorine atoms. Furthermore, aromatic rings that can be substituted by R1 may form a bridging structure via single bonds or via a divalent group obtained by removing one hydrogen atom from R1. n4 and n5 represent integers from 0 to 2. Ar1 and Ar2 represent a benzene ring or a naphthalene ring, respectively. n2 represents 0 or 1, n3 represents 1 or 2, and R3 represents a hydrogen atom or a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group.)

[0078] Examples of substructures represented by the above general formula (1B) include the following. R1, R2, R3, n3, n4, and n5 are the same as above. [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] In the general formula (1B) above, it is preferable that the substructures represented by Ar1 and Ar2 are either benzene rings or a combination of a benzene ring and a naphthalene ring. When Ar1 and Ar2 are benzene rings, improved heat resistance can be expected from the viewpoint of symmetry, and when Ar1 and Ar2 are a combination of a benzene ring and a naphthalene ring, an asymmetric structure is formed, further improving the solubility of the compound in solvents. Among these, it is more preferable that Ar1 and Ar2 are benzene rings due to the ease of obtaining raw materials.

[0084] The substituents R1 and R2 on the aromatic in the above general formula (1B) are, respectively, halogen atoms such as fluorine, chlorine, bromine, and iodine; C1-C4 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, and t-butyl groups; C1-C4 alkoxy groups such as methoxy, ethoxy, propyloxy, n-butoxy, s-butoxy, and t-butoxy groups; and C2-C4 alkyl groups such as vinyl, allyl, and butenyl groups. Ke Al groups with 2 to 4 carbon atoms, such as nyl groups, ethynyl groups, propargyl groups, and butynyl groups. tree Examples include nyl groups, and some or all of the hydrogen atoms on the carbon atoms of alkyloxy groups, alkyl groups, alkenyl groups, and alkynyl groups may be substituted with fluorine substituents such as fluorine atoms. For example, a methyl group may be a trifluoromethyl group, difluoromethyl group, or monofluoromethyl group. Among these, n4 and n5=0 are preferred from the viewpoint of heat resistance and etching resistance, and R1 is preferably a trifluoromethyl group from the viewpoint of flatness and solubility.

[0085] In the above general formula (1B), R3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, or an alkenyl group. Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, and t-butyl groups, while examples of alkenyl groups having 2 to 4 carbon atoms include vinyl, allyl, butenyl, and alkynyl groups having 2 to 4 carbon atoms. treeExamples of nyl groups include ethynyl, propargyl, and butynyl groups. Among these, the structure shown in (1C) below is preferred, and the propargyl group is more preferred from the viewpoint of thermosetting properties. [ka]

[0086] In the general formula (1B) above, n2 is an integer of 0 or 1. From the viewpoint of heat resistance and etching resistance, it is preferable that n2 = 1, i.e., a naphthalene ring.

[0087] In the above general formula (1B), n3 is an integer of 1 or 2. From the viewpoint of curability, n3=2 is preferred, and in particular, when substituents similar to catechol, represented by -OR3, are adjacent, as in the substructure below, it is especially preferred from the viewpoint of adhesion and heat resistance. [ka]

[0088] Furthermore, in the above general formula (1B), it is preferable that n2=1 and n3 is an integer of 1 or 2, and more preferably that n3=2 from the viewpoint of curability, and particularly preferable from the viewpoint of adhesion and heat resistance when substituents represented by -OR3 similar to catechol are adjacent, as in the substructure shown below. [ka]

[0089] Furthermore, in the case of a substructure having a substituent represented by OR3, if a propargyloxy group is located at the β-position on the naphthalene ring as shown below, it is thought that the propargyloxy group forms a cyclized product by baking and then polymerizes, thereby exhibiting thermosetting properties. In this case, the propargyloxy group not only provides fluidity before cyclization and acts as a curable group after cyclization, but also contributes to improved heat resistance through the formation of a ring structure. In this curing reaction, since no degradable additives such as thermal acid generators that become outgassing components or by-products such as condensation reactions are generated, sublimation components during baking can be suppressed, and film shrinkage can also be suppressed. These effects make it possible to achieve both heat resistance and embedding / planarization properties, which are conflicting properties, making this even more preferable.

[0090] [ka]

[0091] Furthermore, when the proportion of hydrogen atoms in the structure constituting R3 is a, and the proportion of C1-C4 alkyl groups, C2-C4 alkynyl groups, and alkenyl groups is b, the proportions of hydrogen atoms, which are expected to have an effect on adhesion to the substrate and film formation properties, and C1-C4 alkyl groups, C2-C4 alkynyl groups, and alkenyl groups, which are expected to have an effect on heat resistance and thermal fluidity, can be adjusted to any desired ratio to match the desired performance. When adjusting to any desired ratio, it is also possible to adjust the substituent introduction rate by reaction, and separately, compounds in which R3 is substituted with hydrogen atoms and compounds in which C1-C4 alkyl groups, C2-C4 alkynyl groups, and alkenyl groups can be prepared separately and mixed to adjust to the desired ratio.

[0092] In addition, it is preferable that the ratio Mw / Mn, which is the ratio of the weight-average molecular weight Mw to the number-average molecular weight Mn in polystyrene terms, measured by gel permeation chromatography (GPC) of the compound represented by general formula (1A), is 1.00 ≤ Mw / Mn ≤ 1.10. By definition, if it is a monomolecule compound, Mw / Mn will be 1.00, but due to the separation capabilities of gel permeation chromatography, the measured value may exceed 1.00. Generally, polymers with repeating units are extremely difficult to approach Mw / Mn = 1.00 unless a special polymerization method is used, and they have a distribution of Mw, resulting in an Mw / Mn value greater than 1. In this invention, in order to distinguish between monomolecule compounds and polymers, 1.00 ≤ Mw / Mn ≤ 1.10 is defined as an indicator of monomolecule nature. In this invention, the average molecular weight and dispersion are the weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersion (Mw / Mn) in polystyrene terms, measured by GPC using tetrahydrofuran as the eluent.

[0093] By controlling the Mw / Mn ratio of the compound for the organic film-forming composition within this range, it is possible to form an organic film with excellent embedding properties and flatness.

[0094] [Method for producing compounds for forming organic films] An example of a method for producing the compound represented by the general formula (1A) of the present invention is a method in which an intermediate fluorenol is obtained by an addition reaction of ketones having Ar1 and Ar2 with an organometallic reagent having metal M (STEP 1), followed by a dehydration condensation reaction using an acid catalyst with benzene or naphthalene having OR3 as a substituent as a raw material (STEP 2) to obtain the target product. The reactions used in STEP 1 and STEP 2 can use one or more raw materials, and these can be appropriately combined depending on the required properties.

[0095] [ka] (In the above formula, Y, Ar1, Ar2, n1, n2, n3, n4, n5, R1, R2, R3 are the same as above, M represents a metal such as Li or MgX1, and X1 represents a halogen atom.)

[0096] Examples of organometallic reagents used in Step 1 include Grignard reagents, organolithium reagents, organozinc reagents, and organotitanium reagents, with Grignard reagents and organolithium reagents being particularly preferred. Grignard reagents and organolithium reagents may be prepared by direct metallation of their respective halides with metallic magnesium or metallic lithium, or by a metal-halogen exchange reaction with aliphatic organometallic compounds such as isopropylmagnesium halide, methyllithium, or butyllithium.

[0097] Furthermore, organozinc reagents and organotitanium reagents can be prepared by reacting the corresponding Grignard reagent or organolithium reagent with zinc halide, titanium(IV) halide, alkoxytitanium(IV), etc. Metal salt compounds may be present during the preparation of the above organometallic reagents, or during the reaction of the above organometallic reagents with smanene oxide. In this case, the reaction proceeds with the use of transition metal catalysts such as palladium or nickel.

[0098] Examples of the above-mentioned metal salt compounds include cyanides, halides, and perhalates. Lithium salts such as lithium chloride, lithium bromide, lithium iodide, and lithium perchlorate, and copper salts such as copper(I) cyanide, copper(II) cyanide, copper(I) chloride, copper(II) chloride, and dilithium tetrachloroquette can be cited as preferred metal salt compounds.

[0099] The above metal salt compounds are 0.01 to 5.0 in proportion to organometallic reagents. Current Quantity, preferably 0.2 to 2.0 Current By adding a certain amount, the solubility of organometallic reagents can be increased, facilitating their preparation, and the nucleophilicity and Lewis acidity of the reagents can be adjusted.

[0100] For the preparation of the above organometallic reagents and their reaction with sumanene oxide, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, and cyclopentyl methyl ether, hydrocarbons such as benzene, toluene, xylene, mesitylene, hexane, heptane, octane, and isooctane, and aprotic polar solvents such as N,N,N',N'-tetramethylethylenediamine, hexamethylphosphoric triamide, and N,N-dimethylformamide can be used individually or in combination.

[0101] The reaction temperature depends on the type of ketones containing Ar1 and Ar2, the type of organometallic reagent, and the reaction conditions, but is preferably -70 to 150°C. For example, if the organometallic reagent is an organozinc reagent or a Grignard reagent, the temperature can be selected in various ways depending on the reaction, such as at room temperature or under reflux at the boiling point of the solvent. The reaction time is usually preferably 30 minutes to 48 hours.

[0102] The reaction method involves pre-prepared organometallic reagents and ketones containing Ar1 and Ar2. of Methods include charging the reagents all at once into the solvent, dispersing or dissolving either the organometallic reagent or the ketone containing Ar1 or Ar2 in the solvent, and then adding the other reagent dropwise. The resulting fluorenol intermediates can be quenched with water or other solvents. rear The reaction can proceed directly to the dehydration condensation reaction in STEP 2, but it is also possible to remove unreacted raw materials, catalysts, etc., present in the system as reaction intermediates by diluting the mixture with an organic solvent, followed by liquid-liquid washing or crystallization with a poor solvent to recover the mixture as a powder.

[0103] As the acid catalyst used in the dehydration condensation reaction shown in STEP 2, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide, and titanium(IV) oxide can be used. The amount of these catalysts used can be in the range of 0.1 to 20 moles, preferably 0.2 to 10 moles, relative to the number of moles of the intermediate fluorenols.

[0104] There are no particular restrictions on the solvents used, but examples include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide. These can be used individually or in combination of two or more types. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably from -50°C to around the boiling point of the solvent, and more preferably from room temperature to 150°C. The reaction time can be appropriately selected from 0.1 to 100 hours.

[0105] The reaction methods include charging fluorenols, benzene or naphthalenes and an acid catalyst all at once; dispersing or dissolving the fluorenols, benzene or naphthalenes and then adding the catalyst all at once or in portions, or diluting with a solvent and adding it dropwise; or dispersing or dissolving the catalyst and then adding the fluorenols, benzene or naphthalenes individually all at once or in portions, or diluting with a solvent and adding them dropwise. In this case, depending on the reactivity of the benzene or naphthalene, it is preferable to use 2 moles or more of benzene or naphthalene when the amount of fluorenol is 1 mole. After the reaction is complete, the target product can be recovered by diluting with an organic solvent and then performing liquid-liquid washing to remove the catalyst used in the reaction.

[0106] The organic solvent used at this time is not particularly limited as long as it can dissolve the target substance and separates into two layers when mixed with water, but examples include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, and ethylcyclopentyl methyl ether; chlorine-based solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The washing water used at this time can usually be what is called deionized water or ultrapure water. One or more washes are sufficient, but washing more than 10 times does not necessarily mean that the washing effect will be obtained, so it is preferable to wash about 1 to 5 times.

[0107] To remove acidic components from the system during liquid-liquid washing, washing with a basic aqueous solution may be performed. Examples of basics include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium compounds.

[0108] Furthermore, in order to remove metal impurities or basic components from the system during liquid-liquid washing, washing with an acidic aqueous solution may be performed. Examples of suitable acids include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids, and organic acids such as oxalic acid, fumaric acid, maleic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0109] The above-mentioned separation and washing with basic aqueous solutions and acidic aqueous solutions may be performed individually or in combination. From the viewpoint of removing metal impurities, it is preferable to perform the separation and washing in the order of basic aqueous solution followed by acidic aqueous solution.

[0110] After the liquid-liquid washing with the above-mentioned basic and acidic aqueous solutions, further washing with neutral water may be performed. One or more washes are sufficient, but preferably 1 to 5 washes. As neutral water, deionized water or ultrapure water as described above can be used. One or more washes are sufficient, but if the number of washes is insufficient, basic and acidic components may not be removed. Washing more than 10 times does not necessarily guarantee the desired effect, so preferably 1 to 5 washes are sufficient.

[0111] Furthermore, the reaction product after the liquid-liquid separation can be recovered as a powder by concentrating the solvent to dryness or crystallizing it under reduced pressure or atmospheric pressure. However, to improve the handling of the material for forming the organic film, it is also possible to keep it in a solution of an appropriate concentration. The concentration at this time is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass. At such a concentration, the viscosity does not tend to become high, thus preventing impairment of handling, and it is also economical because the amount of solvent does not become excessive.

[0112] The solvent used in this case is not particularly limited as long as it can dissolve the compound, but specific examples include ketones such as cyclohexanone and methyl-2-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate. These can be used individually or in combination of two or more types.

[0113] [Alternative method for producing compounds] Furthermore, when R3 of the compound represented by the above general formula (1A) used in the organic film-forming material of the present invention is other than a hydrogen atom, an alternative manufacturing method is to obtain an intermediate by a dehydration condensation reaction using an acid catalyst with fluorenols and benzene or naphthalenes having a hydroxyl group, so-called phenols or naphthols, as shown below (STEP 1-1). The monomolecule compound can be obtained by a substitution reaction using a base catalyst (STEP 2-1) with a raw material represented by R3-X2 having a leaving group X2 that converts the hydroxyl group to OR3. In this case, it is possible to use one or two or more R3-X2s, and furthermore, the ratio of hydroxyl group to OR3 can be controlled by controlling the reaction rate. By partially introducing a polar structure such as a hydroxyl group, the film-forming properties and the base of the film can be improved. board It also becomes possible to control the degree of adhesion.

[0114] [ka] (In the above formula, Y, Ar1, Ar2, n1, n2, n3, n4, n5, R1, R2, R3 are the same as above, and X2 represents a halogen atom, tosylate, or mesylate.)

[0115] The dehydration condensation reaction in (STEP 1-1) can be carried out by the method described above for producing the compound of general formula (1A). anti The application method and the method for recovering the compound can be carried out by the method for producing the compound shown in the general formula (1A) above.

[0116] Examples of base catalysts used in the substitution reaction of (STEP2-1) include inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate, as well as organic amine compounds such as triethylamine, pyridine, and N-methylmorpholine. These may be used individually or in combination of two or more.

[0117] The solvent used in this process is not particularly limited as long as it is inert to the above reaction. For example, ether-based solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water can be used individually or in combination.

[0118] Reaction method and compound things The recovery method can be carried out by the method described in the manufacturing method for the compound shown in the general formula (1A) above.

[0119] The compounds used in the organic film-forming material obtained by this method thingsFor preparation, various halides, tosylates, and mesylates can be used individually or in combination to suit the required performance. For example, those with side chain structures that contribute to improved planarization properties, and rigid aromatic ring structures that contribute to etching resistance and heat resistance can be combined in any proportion. compound Materials for forming organic films using this technology can achieve a high level of both embedding / planarization properties and etching resistance.

[0120] As described above, the organic film-forming compound of the present invention provides an organic film-forming material that hardens without generating by-products even when film is formed in an inert gas that prevents corrosion of the substrate, has good adhesion to the substrate, and can form an organic film that also has heat resistance of, for example, 400°C or higher and advanced embedding / planarization characteristics.

[0121] In this invention, planarization characteristics refer to the ability to planarize the surface of a substrate. With a material (composition) containing the organic film-forming compound of the present invention, for example, as shown in Figure 1, by applying the organic film-forming material 3' to a substrate 1 and heating it to form an organic film 3, it is possible to reduce a 100 nm step on the substrate 1 to 30 nm or less. The step shape shown in Figure 1 is a typical example of a step shape in a substrate for semiconductor device manufacturing, and the step shape of a substrate that can be planarized with a material containing the organic film-forming compound of the present invention is, of course, not limited to this.

[0122] <Materials for organic film formation> Furthermore, the present invention provides an organic film-forming material comprising (A) the organic film-forming compound of the present invention described above and (B) an organic solvent. In the organic film-forming material of the present invention, the organic film-forming compound of the present invention described above can be used individually or in combination of two or more. The organic film-forming material of the present invention can also be referred to as an organic film-forming composition.

[0123] Furthermore, in the present invention, as described above, substitutions represented by two or more R3 types are used. It's the base. Methods of using them in combination, or intentionally substituting the proportion of substituent R3 to achieve the desired performance. base introduction The ratio can be controlled. Specifically, when the proportion of hydrogen atoms in the structure constituting R3 in a compound is a, and the proportion of C1-C4 alkyl groups, C2-C4 alkynyl groups, and alkenyl groups is b, the proportion of hydrogen atoms, which are expected to have an effect on adhesion to the substrate and film formation properties, and the proportion of C1-C4 alkyl groups, C2-C4 alkynyl groups, and alkenyl groups, which are expected to have an effect on heat resistance and thermal fluidity can be adjusted to any ratio, and the proportion of b can be set to a+b=100 to match the desired performance. (%) Replace so that base One method is to adjust the introduction rate. When controlling the substituent introduction rate, the desired compound can be obtained by carrying out the reaction using a compound having one or more leaving groups X2, as described in the above-mentioned [Alternative Method for Producing Compounds].

[0124] <Organic solvents> The organic solvents that can be used in the organic film-forming material of the present invention are not particularly limited as long as they dissolve the organic film-forming compound of the present invention, as well as optional components such as acid generators, crosslinking agents, and other additives. Specifically, solvents with a boiling point of less than 180°C, such as those described in paragraphs (0091) to (0092) of Japanese Patent Application Publication No. 2007-199653, can be used. Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and mixtures of two or more of these are preferably used.

[0125] Such a material can be applied by rotary coating, and because it contains the organic film-forming compound of the present invention as described above, it becomes an organic film-forming material that combines heat resistance of 400°C or higher with advanced embedding / planarization characteristics.

[0126] Furthermore, the organic film-forming material of the present invention may also contain a high-boiling-point solvent with a boiling point of 180°C or higher added to the above-mentioned solvent with a boiling point of less than 180°C (a mixture of a solvent with a boiling point of less than 180°C and a solvent with a boiling point of 180°C or higher). As for the high-boiling-point organic solvent, there are no particular restrictions on the type of solvent, such as hydrocarbons, alcohols, ketones, esters, ethers, or chlorinated solvents, as long as it can dissolve the organic film-forming compound. 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, ethylene glycol 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, triethylene Glycol diacetate, 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 monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate, which may be used individually or in combination.

[0127] The boiling point of the high-boiling point solvent mentioned above can be appropriately selected according to the temperature at which the organic film-forming material is heat-treated. Preferably, the boiling point of the added high-boiling point solvent is 180°C to 300°C, and more preferably 200°C to 300°C. With such a boiling point, there is no risk of excessive volatilization during baking (heat treatment) due to a boiling point that is too low, thus sufficient thermal fluidity can be obtained. Furthermore, with such a high boiling point, there is no risk of residual solvent remaining in the film after baking without volatilizing, thus avoiding adverse effects on film properties such as etching resistance.

[0128] Furthermore, when using the high-boiling point solvent described above, it is preferable that the amount of high-boiling point solvent added is 1 to 30 parts by mass per 100 parts by mass of solvent with a boiling point of less than 180°C. With such an amount, there is no risk of the amount being too small to provide sufficient thermal fluidity during baking, or of the amount being too large remaining in the film and leading to deterioration of film properties such as etching resistance. The amount of organic solvent added is preferably 200 to 10,000 parts, more preferably 300 to 5,000 parts, per 100 parts (parts by mass; the same applies hereinafter unless otherwise specified) of the above compound (A).

[0129] With such organic film-forming materials, the addition of a high-boiling-point solvent to the above-mentioned organic film-forming compound imparts thermal fluidity, resulting in an organic film-forming material that also possesses advanced embedding / planarization properties.

[0130] <Other ingredients> The organic film-forming material of the present invention may further contain one or more of (C) an acid generator, (D) a surfactant, (E) a crosslinking agent, and (F) a plasticizer, depending on its purpose.

[0131] ((C) Acid Generator) In the organic film-forming material of the present invention, an acid generator can be added as component (C) to further promote the curing reaction. Acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation, and either type can be added. Specifically, the materials described in paragraphs (0061) to (0085) of Japanese Patent Application Publication No. 2007-199653 can be added, but are not limited to these.

[0132] The above acid generating agents can be used individually or in combination of two or more. When adding an acid generating agent, the amount to be added is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, per 100 parts of the compound.

[0133] ((D) Surfactants) The organic film-forming material of the present invention may contain a surfactant as component (D) to improve its applicability in spin coating. As the surfactant, for example, those described in (0142) to (0147) of Japanese Patent Application Publication No. 2009-269953 can be used.

[0134] The above-mentioned surfactants can be used individually or in combination of two or more. When adding surfactants, the amount added is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, per 100 parts of the compound.

[0135] ((E) Crosslinking agent) The organic film-forming material of the present invention may also contain a crosslinking agent as component (E) to enhance curability and further suppress intermixing with the upper film. The crosslinking agent is not particularly limited, and various known crosslinking agents of different types can be widely used. Examples include melamine-based crosslinking agents, glycoluryl-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, and epoxy-based crosslinking agents.

[0136] Examples of melamine-based crosslinking agents include hexamethoxymethylated melamine, hexasubtoxicmethylated melamine, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of glycoluryl-based crosslinking agents include tetramethoxymethylated glycoluryl, tetrabutoxymethylated glycoluryl, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensates. Examples of β-hydroxyalkylamide-based crosslinking agents include N,N,N',N'-tetra(2-hydroxyethyl)adipamide. Examples of isocyanurate-based crosslinking agents include triglycidyl isocyanurate and triallyl isocyanurate. Examples of aziridine-based crosslinking agents include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Examples of oxazoline-based crosslinking agents include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tertbutyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymers.Examples of epoxy crosslinking agents include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0137] Examples of polynuclear phenolic crosslinking agents include compounds represented by the following general formula (1E). [ka] (In the formula, Q is a single bond or an s-valent hydrocarbon group having 1 to 20 carbon atoms. 10 (where is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; s is an integer from 1 to 5.)

[0138] Q is a single bond or an s-valent hydrocarbon group having 1 to 20 carbon atoms. s is an integer from 1 to 5, more preferably 2 or 3. Examples of Q include groups obtained by removing s hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. 10 The C1-C20 alkyl group is either a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosanyl groups, with hydrogen atoms or methyl groups being preferred.

[0139] Examples of compounds represented by the above general formula (1E) include the following compounds. Among these, triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and hexamethoxymethylated tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the viewpoint of improving the curability and uniformity of the organic film. 10 This is the same as above.

[0140] [ka]

[0141] [ka]

[0142] above record shelf The crosslinking agent can be used individually or in combination of two or more types. The amount of crosslinking agent added is preferably 1 to 100 parts, more preferably 5 to 50 parts, per 100 parts of the compound.

[0143] ((F) Plasticizer) Furthermore, to further improve the planarization / embedding properties, a plasticizer may be added as component (F) to the organic film-forming material of the present invention. The plasticizer is not particularly limited, and various known types of plasticizers can be widely used. Examples include low molecular weight compounds such as phthalates, adipicates, phosphates, trimelliticates, and citrates, as well as polymers such as polyethers, polyesters, and polyacetal polymers described in Japanese Patent Application Publication No. 2013-253227. When adding a plasticizer, the amount added is preferably 1 to 100 parts, more preferably 5 to 30 parts, per 100 parts of the compound.

[0144] Furthermore, the organic film-forming material of the present invention preferably uses, as an additive to impart embedding / planarization properties in the same way as a plasticizer, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a pyrolytic polymer having a weight loss rate of 40% by mass or more between 30°C and 250°C and a weight-average molecular weight of 300 to 200,000. This pyrolytic polymer preferably contains repeating units having an acetal structure represented by the following general formulas (DP1) and (DP1a). When adding these pyrolytic polymers, the amount added is preferably 1 to 100 parts, more preferably 5 to 30 parts, per 100 parts of the compound.

[0145] [ka] (In the formula, Ra is a hydrogen atom or a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, which may be substituted. L is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.)

[0146] [ka] (In the formula, Rb is an alkyl group having 1 to 4 carbon atoms. Z is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms, which may have an ether bond. t represents the average number of repeating units, which is between 3 and 500.)

[0147] Furthermore, the following fluidity enhancers can be used as additives to improve the embedding / planarization properties similar to those described above. One or more compounds selected from the following general formulas (i) to (iii) can be used as fluidity enhancers. When adding these fluidity enhancers, the amount added is preferably 1 to 100 parts, more preferably 5 to 30 parts, per 100 parts of the compound. [ka] (In the formula, Ra is independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 10 carbon atoms, which may be substituted. W1 is a phenylene group or a divalent group represented by the following general formula (i-1). W2 and W3 are divalent groups that are either single bonds or represented by the following general formula (i-2). m1 is an integer from 1 to 10, and na is an integer from 0 to 5.) [ka] (In the formula, * indicates a bond position, Rb, Rc, Rd, and Re are hydrogen atoms, hydroxyl groups, or organic groups having 1 to 10 carbon atoms. W10 and W11 are independently single bonds or carbonyl groups. m10 and m11 are integers from 0 to 10, and m10 + m11 ≥ 1.) [ka] (In the formula, * indicates a bonding position.)

[0148] [ka] (In the formula, Rf is independently a hydrogen atom or an organic group having 1 to 10 carbon atoms, which may be substituted. W4 is a divalent group represented by the following general formula (ii-1). W5 is a divalent group that is either a single bond or represented by the following general formula (ii-2). m2 is an integer from 2 to 10, and nc is an integer from 0 to 5.) [ka] (In the formula, * indicates a bond position, Rg, Rh, Ri, and Rj are hydrogen atoms, hydroxyl groups, or organic groups with 1 to 10 carbon atoms. m20 and m21 are integers from 0 to 10, and m20 + m21 ≥ 1.)

[0149] [ka] (In the formula, Rk and Rl are hydrogen atoms, hydroxyl groups, or optionally substituted organic groups having 1 to 10 carbon atoms, which may bond to form a cyclic structure. Rm and Rn are organic groups having 1 to 10 carbon atoms, where Rm is a group containing either an aromatic ring or a divalent group represented by the following general formula (iii-1). W6 and W7 are divalent groups that are either single bonds or represented by the following general formula (iii-2), with at least one being a divalent group represented by either (iii-2).) [ka] (In the formula, * indicates a bond position, and W30 is an organic group with 1 to 4 carbon atoms.) [ka] (In the formula, * indicates a bonding position.)

[0150] As described above, the organic film forming material of the present invention hardens without generating by-products even when forming films in an inert gas that prevents substrate corrosion, exhibits good adhesion to the substrate, and possesses heat resistance of, for example, 400°C or higher, as well as advanced embedding / planarization properties. Therefore, the organic film forming material of the present invention is extremely useful as an organic film forming material for multilayer resist methods such as the two-layer resist method, the three-layer resist method using a silicon-containing resist interlayer or inorganic hard mask (e.g., a silicon-containing inorganic hard mask), and the four-layer resist method using a silicon-containing resist interlayer or inorganic hard mask and an organic anti-reflective film. Furthermore, because the organic film forming material of the present invention does not generate by-products even when forming films in an inert gas and has excellent embedding / planarization properties, it can also be suitably used as a planarization material in semiconductor device manufacturing processes other than the multilayer resist method. In other words, the organic film forming material of the present invention can be suitably used in semiconductor device manufacturing processes.

[0151] <Substrates for semiconductor device manufacturing> Furthermore, the present invention provides a substrate for manufacturing a semiconductor device, characterized in that a cured organic film of the organic film-forming material of the present invention is formed on the substrate.

[0152] The semiconductor device manufacturing substrate of the present invention can also be described as comprising a substrate and an organic film formed on the substrate, which is a cured product of the organic film forming material of the present invention.

[0153] Such semiconductor manufacturing substrates contain an organic film that combines high heat resistance, good adhesion to the substrate, and advanced embedding / planarization characteristics, resulting in a good yield of semiconductor devices when used in the semiconductor manufacturing process.

[0154] <Organic film formation method> The present invention further provides a method for forming an organic film, applicable in the manufacturing process of semiconductor devices, using the organic film forming material of the present invention. Specifically, the following methods can be cited. (Single-stage bake process (in inert gas)) A method for forming an organic film applicable in the manufacturing process of a semiconductor device, characterized by rotating the application of the organic film-forming material of the present invention onto a workpiece substrate, and then heat-treating the workpiece substrate coated with the organic film-forming material in an inert gas atmosphere at a temperature of 50°C to 600°C for a range of 5 to 7200 seconds to obtain a cured film. (Two-stage bake process (in air - in inert gas)) A method for forming an organic film applicable in the manufacturing process of a semiconductor device, characterized by: rotating the application of the organic film-forming material of the present invention onto a workpiece substrate; heat-treating the workpiece substrate coated with the organic film-forming material in air at a temperature of 50°C to 300°C for 5 to 600 seconds to form a coated film; and subsequently applying heat treatment in an inert gas atmosphere at a temperature of 200°C to 600°C for 10 to 7200 seconds to obtain a cured film.

[0155] In the method for forming an organic film according to the present invention, first, the above-described organic film-forming material of the present invention is applied to the substrate to be processed by rotational coating (spin coating).

[0156] In the method for forming an organic film of the present invention, the substrate to be processed, to which the organic film-forming material has been coated, is then subjected to heat treatment (heating film formation step) to obtain a cured film.

[0157] The heat deposition process for forming a cured film can be a single-stage bake, a two-stage bake, or a multi-stage bake of three or more stages, but a single-stage bake or a two-stage bake is economically preferable.

[0158] Film deposition by single-stage baking is preferably carried out at a temperature of 50°C to 600°C for a period of 5 to 7200 seconds, preferably at a temperature of 150°C to 500°C for 10 to 7200 seconds (more preferably at 10 to 3600 seconds). Heat treatment under these conditions promotes planarization and crosslinking reactions due to thermal fluidity. In the multilayer resist method, a coated silicon-containing resist interlayer or a CVD hard mask may be formed on the obtained film. When applying a coated silicon-containing resist interlayer, deposition at a temperature higher than the deposition temperature of the silicon-containing resist interlayer is preferred. Typically, silicon-containing resist interlayers are deposited at 100°C to 400°C, preferably at 150°C to 350°C. Deposition of the organic film at a temperature higher than this prevents dissolution of the organic film by the silicon-containing resist interlayer material, allowing for the formation of an organic film that does not mix with the material.

[0159] When applying a CVD hard mask, it is preferable to deposit the organic film at a temperature higher than the temperature at which the CVD hard mask is formed. Examples of temperatures for forming the CVD hard mask include temperatures between 150°C and 500°C.

[0160] Furthermore, examples of the atmosphere during baking include inert gases such as nitrogen, argon, and helium. With the material of the present invention, even when fired in such an inert gas atmosphere, a sufficiently hardened organic film can be formed without the generation of sublimation products. Moreover, with the material of the present invention, hardening can be achieved without generating by-products even when forming a film in an inert gas atmosphere, which prevents corrosion of the substrate.

[0161] In other words, one aspect of the method for forming an organic film according to the present invention is a method for forming an organic film applied in the manufacturing process of a semiconductor device, characterized by rotating the application of the organic film forming material of the present invention onto a workpiece substrate, and then heat-treating the workpiece substrate coated with the organic film forming material in an inert gas atmosphere at a temperature of 50°C to 600°C for a range of 5 to 7200 seconds to obtain a cured film.

[0162] On the other hand, in film formation by two-stage baking, for example, a first-stage bake can be performed in which the substrate to be processed, coated with the organic film-forming material of the present invention, is heat-treated in air, followed by a second-stage bake in an inert gas atmosphere.

[0163] For the first stage of baking, considering the effect of oxygen in the air on substrate corrosion, the upper limit of the processing temperature in air should be 300°C or less, preferably 250°C or less, and the process should be carried out for a period of 5 to 600 seconds. The lower limit of the processing temperature in air can be, for example, 50°C.

[0164] Examples of the atmosphere during the second baking stage include inert gases such as nitrogen, argon, and helium. With the material of the present invention, even when fired in such an inert gas atmosphere, a sufficiently hardened organic film can be formed without the generation of sublimation products. Furthermore, with the material of the present invention, hardening can be achieved without generating by-products even when film formation is performed in an inert gas atmosphere, which prevents corrosion of the substrate.

[0165] The second bake temperature should be higher than the first bake temperature, for example, 200°C or higher, and preferably 600°C or lower, more preferably 500°C or lower, for a period of 10 to 7200 seconds. In the multilayer resist method, a coated silicon-containing resist interlayer or a CVD hard mask may be formed on the obtained film. When a coated silicon-containing resist interlayer is applied, it is preferable to form the film at a temperature higher than the temperature at which the silicon-containing resist interlayer is formed. Typically, silicon-containing resist interlayers are formed at 100°C to 400°C, preferably 150°C to 350°C. Forming the organic film at a temperature higher than this prevents the dissolution of the organic film by the silicon-containing resist interlayer material, and allows for the formation of an organic film that does not mix with the material.

[0166] When applying a CVD hard mask using a two-stage bake process, it is preferable to deposit the organic film at a temperature higher than the temperature at which the CVD hard mask is formed. Examples of temperatures for forming the CVD hard mask include 150°C to 500°C.

[0167] In other words, one aspect of the method for forming an organic film according to the present invention is a method for forming an organic film applied in the manufacturing process of a semiconductor device, characterized by rotatingly coating a substrate with the organic film forming material of the present invention onto a substrate to be processed, heat-treating the substrate coated with the organic film forming material in air at a temperature of 50°C to 300°C for 5 to 600 seconds to form a coated film, and then applying heat treatment in an inert gas atmosphere at a temperature of 200°C to 600°C for 10 to 7200 seconds to obtain a cured film.

[0168] It is preferable that the oxygen concentration in the above-mentioned inert gas be 1% by volume or less. The organic film-forming material of the present invention hardens sufficiently without generating sublimation even when heated (heat-treated) in such an inert gas atmosphere, and can form an organic film with excellent adhesion to the substrate. Furthermore, heating in such an inert gas atmosphere can prevent corrosion of the substrate being processed.

[0169] In other words, the present invention provides a method for forming an organic film that functions as an organic film used in the manufacturing process of semiconductor devices, wherein, in order to prevent corrosion of the substrate to be processed, the heat treatment under an inert gas atmosphere is performed by heat-treating the substrate to be processed in an atmosphere with an oxygen concentration of 1 volume% or less to form a cured film.

[0170] In this method for forming an organic film, first, the organic film-forming material of the present invention described above is rotary-coated onto the substrate to be processed. After rotary coating, in a two-stage bake, first, the material is baked in air at 300°C or below, and then the second stage of baking is performed in an atmosphere with an oxygen concentration of 1 volume% or less. In the case of a single-stage bake, the first stage of baking in air can be skipped. Examples of atmospheres during baking include inert gases such as nitrogen, argon, and helium. With the material of the present invention, even when fired in such an inert gas atmosphere, a sufficiently hardened organic film can be formed without the generation of sublimation.

[0171] Furthermore, the method for forming an organic film of the present invention can be used with a substrate having a structure or step with a height of 30 nm or more. As described above, the organic film forming material of the present invention has excellent embedding / planarization properties, so a flat cured film can be formed even if the substrate has a structure or step (unevenness) with a height of 30 nm or more. In other words, the method for forming an organic film of the present invention is particularly useful when forming a flat organic film on such a substrate.

[0172] The thickness of the formed organic film is selected as appropriate, but is preferably 30 to 20,000 nm, and particularly preferably 50 to 15,000 nm.

[0173] Furthermore, the above-described method for forming an organic film is applicable to both cases: when forming an organic film for organic films using the organic film forming material of the present invention, and when forming an organic film for planarization films.

[0174] For example, one variation of the method for forming an organic film according to the present invention is a method for forming an organic film that can flatten the surface of a stepped substrate used in the manufacturing process of a semiconductor device, wherein the above-mentioned organic film forming material of the present invention is rotary coated onto a substrate to be processed, the substrate coated with the organic film forming material is heat-treated in air at a temperature of 50°C to 300°C for 5 to 600 seconds, and then heat-treated in an inert gas atmosphere at a temperature of 200°C to 600°C for 10 to 7200 seconds to form a cured organic film.

[0175] In this method for forming an organic film, first, the organic film-forming material of the present invention described above is applied to the substrate to be processed by spin coating. By using the spin coating method, good embedding characteristics can be obtained. After spin coating, baking (heat treatment) is performed to promote planarization by thermal fluid and crosslinking reaction. Furthermore, since this baking process allows the solvent in the material to evaporate, mixing can be prevented even when forming a resist upper layer film or a silicon-containing resist interlayer film on the organic film.

[0176] <Pattern Formation Method> The organic film forming material of the present invention can be suitably used in various pattern formation methods, such as a three-layer resist process using a silicon-containing resist interlayer or an inorganic hard mask, or a four-layer resist process using an organic anti-reflective film in addition to these. By forming circuit patterns using such a pattern formation method of the present invention in the semiconductor device manufacturing process, semiconductor devices can be manufactured with a high yield. Examples of pattern formation methods using the organic film forming material of the present invention are given below.

[0177] (1) A pattern formation method characterized by forming an organic film on a workpiece using the organic film forming material of the present invention, forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material, forming a resist upper layer on the silicon-containing resist interlayer using a photoresist composition, forming a circuit pattern on the resist upper layer, transferring the pattern to the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask. (2) A pattern formation method characterized by forming an organic film on a workpiece using the organic film forming material of the present invention, forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material, forming an organic anti-reflective film on the silicon-containing resist interlayer, forming a resist upper layer on the organic anti-reflective film using a photoresist composition to form a four-layer film structure, forming a circuit pattern on the resist upper layer, transferring the pattern to the organic anti-reflective film and the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask. (3) A pattern formation method characterized by forming an organic film on a workpiece using the organic film forming material of the present invention, forming an inorganic hard mask selected from silicon oxide film, silicon nitride film, silicon oxynitride film, titanium oxide film, and titanium nitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a photoresist composition to form a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask. (4) A pattern formation method characterized by forming an organic film on a workpiece using the organic film forming material of the present invention, forming an inorganic hard mask selected from silicon oxide film, silicon nitride film, silicon oxynitride film, titanium oxide film, and titanium nitride film on the organic film, forming an organic anti-reflective film on the inorganic hard mask, forming a resist upper layer film on the organic anti-reflective film using a photoresist composition to form a four-layer film structure, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic anti-reflective film and the inorganic hard mask by etching using the resist upper layer film on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern is transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern is transferred as a mask. The following examples illustrate pattern formation methods, but they are not limited to these.

[0178] [Three-layer resist method using silicon-containing resist interlayer] Furthermore, the present invention provides a pattern formation method characterized by forming an organic film on a workpiece using the organic film forming material of the present invention described above, forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material, forming a resist upper layer on the silicon-containing resist interlayer using a photoresist composition, forming a circuit pattern on the resist upper layer, etching the silicon-containing resist interlayer using the resist upper layer on which the pattern is formed as a mask to transfer the pattern to the silicon-containing resist interlayer, etching the organic film using the silicon-containing resist interlayer on which the pattern has been transferred as a mask to transfer the pattern to the organic film, and further etching the workpiece using the organic film on which the pattern has been transferred as a mask to transfer the pattern to the workpiece.

[0179] Preferably, the workpiece is a semiconductor device substrate, or a semiconductor device substrate on which any of the following films are deposited: a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film. More specifically, although not particularly limited, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., or a substrate on which the above-mentioned metal films, etc., are deposited as the workpiece layer, can be used.

[0180] Various low-k films and their stopper films, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, can be used as the workpiece layer, and can typically be formed to a thickness of 50 to 10,000 nm, and especially 100 to 5,000 nm. When forming the workpiece layer, the substrate and the workpiece layer are made of different materials.

[0181] Furthermore, it is preferable that the metal constituting the workpiece includes silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof.

[0182] Furthermore, a workpiece can be a structure with a height of 30 nm or more, or a workpiece substrate having steps or other differences.

[0183] When forming an organic film on a workpiece using the organic film-forming material of the present invention, the organic film-forming method of the present invention described above may be applied.

[0184] Next, a resist interlayer (silicon-containing resist interlayer) is formed on the organic film using a resist interlayer material containing silicon atoms. A polysiloxane-based interlayer material is preferred as the silicon-containing resist interlayer material. By giving the silicon-containing resist interlayer an anti-reflective effect, reflection can be suppressed. In particular, for 193nm exposure, if a material containing many aromatic groups and having high etching selectivity with the substrate is used as the organic film formation material, the k value will be high and substrate reflection will be high. However, by giving the silicon-containing resist interlayer an absorption that results in an appropriate k value, reflection can be suppressed, and substrate reflection can be reduced to 0.5% or less. As silicon-containing resist interlayers with an anti-reflective effect, anthracene is preferred for 248nm and 157nm exposure, and a polysiloxane having phenyl groups or absorbent groups having silicon-silicon bonds in a pendant structure or polysiloxane structure, which can be crosslinked with acid or heat, is preferred for 193nm exposure.

[0185] Next, a resist upper film is formed on the silicon-containing resist interlayer using a resist upper film material consisting of a photoresist composition. The resist upper film material can be either positive or negative type, and the same photoresist compositions commonly used can be used. After spin-coating the resist upper film material, it is preferable to perform a pre-bake at 60-180°C for 10-300 seconds. Then, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain the resist upper film pattern. The thickness of the resist upper film is not particularly limited, but 30-500 nm is preferred, and 50-400 nm is particularly preferred.

[0186] Next, a circuit pattern (resist upper layer pattern) is formed on the resist upper layer. In forming the circuit pattern, it is preferable to form the circuit pattern by lithography using light with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0187] Examples of exposure light include high-energy rays with wavelengths of 300 nm or less, specifically far ultraviolet light, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 laser light (157 nm), Kr2 laser light (146 nm), Ar2 laser light (126 nm), soft X-rays (EUV) in the 3-20 nm range, electron beams (EB), ion beams, and X-rays.

[0188] Furthermore, in forming the circuit pattern, it is preferable to develop the circuit pattern with an alkali or an organic solvent.

[0189] Next, the silicon-containing resist interlayer is etched using the resist upper layer with the circuit pattern as a mask to transfer the pattern to the silicon-containing resist interlayer. It is preferable to use a fluorocarbon-based gas for etching the silicon-containing resist interlayer using the resist upper layer pattern as a mask. This forms the silicon-containing resist interlayer pattern.

[0190] Next, the pattern is transferred to the organic film by etching the silicon-containing resist interlayer, which is used as a mask. Since the silicon-containing resist interlayer exhibits higher etching resistance to oxygen or hydrogen gas compared to the organic film, it is preferable to use an etching gas mainly composed of oxygen or hydrogen gas when etching the organic film using the silicon-containing resist interlayer pattern as a mask. This allows for the formation of the organic film pattern.

[0191] Next, the workpiece is etched using the organic film on which the pattern has been transferred as a mask, thereby transferring the pattern to the workpiece. The subsequent etching of the workpiece (workpiece layer) can be performed by conventional methods. For example, if the workpiece is SiO2, SiN, or a silica-based low dielectric constant insulating film, etching is performed mainly with a fluorocarbon gas; if it is p-Si, Al, or W, etching is performed mainly with a chlorine-based or bromine-based gas. When substrate processing is performed by etching with a fluorocarbon gas, the silicon-containing resist interlayer pattern is removed simultaneously with the substrate processing. On the other hand, when substrate processing is performed by etching with a chlorine-based or bromine-based gas, dry etching with a fluorocarbon gas is required separately after substrate processing to remove the silicon-containing resist interlayer pattern.

[0192] The organic film obtained using the organic film forming material of the present invention can have excellent etching resistance when the workpiece is etched as described above.

[0193] [Four-layer resist method using silicon-containing resist interlayer and organic anti-reflective coating] Furthermore, the present invention provides a pattern formation method characterized by forming an organic film on a workpiece using the organic film forming material of the present invention described above, forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material, forming an organic anti-reflective film on the silicon-containing resist interlayer, forming a resist upper layer on the organic anti-reflective film using a photoresist composition to form a four-layer structure, forming a circuit pattern on the resist upper layer, etching the organic anti-reflective film and the silicon-containing resist interlayer using the resist upper layer on which the pattern is formed as a mask to transfer the pattern to the organic anti-reflective film and the silicon-containing resist interlayer, etching the organic film using the silicon-containing resist interlayer on which the pattern has been transferred as a mask to transfer the pattern to the organic film, and further etching the workpiece using the organic film on which the pattern has been transferred as a mask to transfer the pattern to the workpiece.

[0194] This method can be carried out in the same manner as the three-layer resist method using the silicon-containing resist interlayer described above, except that an organic anti-reflective coating (BARC) is formed between the silicon-containing resist interlayer and the resist upper layer.

[0195] Organic anti-reflective coatings can be formed by spin coating using known organic anti-reflective coating materials.

[0196] [Three-layer resist method using inorganic hard masks] Furthermore, the present invention provides a pattern formation method using the organic film forming material of the present invention described above, which is characterized by forming an organic film on a workpiece using the organic film forming material of the present invention, forming an inorganic hard mask selected from silicon oxide film, silicon nitride film, silicon oxynitride film, titanium oxide film, and titanium nitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a photoresist composition, forming a circuit pattern on the resist upper layer film, etching the inorganic hard mask using the resist upper layer film on which the pattern is formed as a mask to transfer the pattern to the inorganic hard mask, etching the organic film using the inorganic hard mask on which the pattern has been transferred as a mask to transfer the pattern to the organic film, and further etching the workpiece using the organic film on which the pattern has been transferred as a mask to transfer the pattern to the workpiece.

[0197] This method can be carried out in the same manner as the three-layer resist method using the silicon-containing resist interlayer described above, except that an inorganic hard mask is formed on top of the organic film instead of a silicon-containing resist interlayer.

[0198] Inorganic hard masks selected from silicon oxide films, silicon nitride films, and silicon oxynitride films (SiON films) can be formed by CVD or ALD methods. Methods for forming silicon nitride films are described, for example, in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. Among inorganic hard masks, the SiON film, which has a high anti-reflective effect, is most preferably used. Since the substrate temperature when forming the SiON film is 300 to 500°C, the organic film needs to withstand temperatures of 300 to 500°C. The organic film formed using the organic film forming material of the present invention has high heat resistance and can withstand high temperatures of 300 to 500°C, making it possible to combine an inorganic hard mask formed by CVD or ALD with an organic film formed by rotary coating.

[0199] Inorganic hard masks selected from titanium oxide films and titanium nitride films can also be formed by CVD, ALD, and other methods.

[0200] [Four-layer resist method using inorganic hard mask and organic anti-reflective coating] Furthermore, the present invention provides a pattern formation method using the organic film forming material of the present invention described above, which is characterized by forming an organic film on a workpiece using the organic film forming material of the present invention, forming an inorganic hard mask selected from silicon oxide film, silicon nitride film, silicon oxynitride film, titanium oxide film, and titanium nitride film on the organic film, forming an organic anti-reflective film on the inorganic hard mask, forming a resist upper layer film on the organic anti-reflective film using a photoresist composition to form a four-layer film structure, forming a circuit pattern on the resist upper layer film, etching the organic anti-reflective film and the inorganic hard mask using the resist upper layer film on which the pattern is formed as a mask to transfer the pattern to the organic anti-reflective film and the inorganic hard mask, etching the organic film using the inorganic hard mask on which the pattern has been transferred as a mask to transfer the pattern to the organic film, and further etching the workpiece using the organic film on which the pattern has been transferred as a mask to transfer the pattern to the workpiece.

[0201] This method can be carried out in the same manner as the three-layer resist method using the inorganic hard mask described above, except that an organic anti-reflective coating (BARC) is formed between the inorganic hard mask and the resist upper layer.

[0202] In particular, when a SiON film is used as an inorganic hard mask, the two-layer anti-reflective coating of the SiON film and BARC makes it possible to suppress reflection even in immersion lithography with high NA values ​​exceeding 1.0. Another advantage of forming BARC is that it reduces the trailing of the resist upper layer pattern directly above the SiON film.

[0203] Here, an example of the pattern formation method by the three-layer resist method of the present invention is shown in FIGS. 2(A) to (F). In the case of the three-layer resist method, as shown in FIG. 2(A), after forming the organic film 3 on the processed layer 2 formed on the substrate 1 using the material for forming the organic film of the present invention, a silicon-containing resist intermediate film 4 is formed, and a resist upper layer film 5 is formed thereon. Next, as shown in FIG. 2(B), the exposed portion 6 of the resist upper layer film 5 is exposed, and PEB (post-exposure bake) is performed. Next, as shown in FIG. 2(C), development is performed to form a resist upper layer film pattern 5a. Next, as shown in FIG. 2(D), using the resist upper layer film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is dry-etched using a fluorocarbon gas to form a silicon-containing resist intermediate film pattern 4a. Next, as shown in FIG. 2(E), after removing the resist upper layer film pattern 5a, the organic film 3 is etched with oxygen plasma using the silicon-containing resist intermediate film pattern 4a as a mask to form an organic film pattern 3a. Further, as shown in FIG. 2(F), after removing the silicon-containing resist intermediate film pattern 4a, the processed layer 2 is etched using the organic film pattern 3a as a mask to form a pattern 2a.

[0204] When forming an inorganic hard mask, the silicon-containing resist intermediate film 4 may be changed to an inorganic hard mask. When forming a BARC, a BARC may be formed between the silicon-containing resist intermediate film 4 and the resist upper layer film 5. The etching of the BARC may be continuously performed prior to the etching of the silicon-containing resist intermediate film 4, or the etching of only the BARC may be performed first, and then the etching of the silicon-containing resist intermediate film 4 may be performed after changing the etching apparatus or the like.

[0205] As described above, in the pattern formation method of the present invention, a fine pattern can be formed on the processed object with high precision by the multi-layer resist method.

Example

[0206] The present invention will be further described below with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited thereto. The molecular weight and dispersion were determined by calculating the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in polystyrene terms using gel permeation chromatography (GPC) with tetrahydrofuran as the eluent, and then determining the dispersion (Mw / Mn).

[0207] Synthesis Example: Synthesis of Compounds for Organic Film Formation The following fluorenols (B1) to (B7), phenols, and naphthols (C1) to (C4) were used in the synthesis of the organic film-forming compounds (A1) to (A13).

[0208] Fluorenol derivatives: [ka]

[0209] Phenols or naphthols: [ka]

[0210] The following is an example of the synthesis of fluorenol compounds, specifically (B1). [Synthesis Example 1] Synthesis of fluorenols (B1) [ka] A mixture of 189.9 g of tris(4-bromophenyl)amine (D1), 1000 mL of MTBE (t-butyl methyl ether), and 1000 mL of THF (tetrahydrofuran), cooled to -20°C under an N2 atmosphere, was mixed with 500 mL of 2.60 M hexane solution of n-butyllithium and stirred at -20°C for 20 minutes. A 25 wt% THF solution of 191.7 g of 9-fluorenone, pre-dissolved in THF, was slowly added dropwise, and the mixture was gradually heated to room temperature and stirred at room temperature for 4 hours. After stopping the reaction with the addition of 1000 mL of saturated ammonium chloride aqueous solution, 2000 mL of MTBE was added, and the separated aqueous layer was removed. The organic layer was then washed five times with 500 mL of pure water, and the solvent was removed by distillation. After distillation, 500 g of THF was added, followed by 2000 g of methanol, and recrystallization was performed. The precipitated crystals were separated by filtration, washed twice with 500 g of methanol, and recovered. Compound (B1) was obtained by vacuum drying the recovered crystals at 70°C.

[0211] Other fluorenols (B2) to (B7) were synthesized using the fluorenol sources shown below. Specifically, the compound corresponding to the starting material (D1) used in Synthesis Example 1 was replaced with the corresponding brominated compounds (D2) to (D7) according to the structure of the target product, and the molar ratios of n-butyllithium solution and 9-fluorenone were carried out in the same manner as in Synthesis Example 1 to synthesize (B2) to (B7). Note that for (B5), the ketone (D8) was used instead of 9-fluorenone for synthesis.

[0212] Fluorenol-based raw materials: [ka]

[0213] [Synthesis Example 2] Synthesis of Compound (A1) [ka] Under a nitrogen atmosphere, 30.0 g of compound (B1), 55.0 g of compound (C1), and 400 g of 1,2-dichloroethane were added and made into a homogeneous dispersion at an internal temperature of 60°C. 22.0 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70°C for 1 hour. After the reaction was completed, it was cooled to room temperature, 1000 ml of MIBK (methyl isobutyl ketone) was added, and it was washed 6 times with 200 ml of pure water. The organic layer was dried under reduced pressure. After adding 200 g of THF to the residue to make a homogeneous solution, it was crystallized in 2000 g of IPE (diisopropyl ether). The precipitated crystals were separated by filtration and washed 2 times with 500 g of IPE and recovered. The recovered crystals were dried under vacuum at 70°C to obtain compound (A1). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (A1): Mw = 1350, Mw / Mn = 1.04

[0214] [Synthesis Example 3] Synthesis of Compound (A2) [Chemical formula] [[ID=,15]]Under a nitrogen atmosphere, 30.0 g of compound (B2), 19.9 g of compound (C1), and 250 g of 1,2-dichloroethane were added and made into a homogeneous dispersion at an internal temperature of 60°C. 20.4 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70°C for 3 hours. After the reaction was completed, it was cooled to room temperature, 1000 ml of MIBK was added, and it was washed 6 times with 200 ml of pure water. The organic layer was dried under reduced pressure. After adding 100 g of THF to the residue to make a homogeneous solution, it was crystallized in 1000 g of IPE (diisopropyl ether). The precipitated crystals were separated by filtration and washed 2 times with 300 g of IPE and recovered. The recovered crystals were dried under vacuum at 70°C to obtain compound (A2). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (A2): Mw = 1520, Mw / Mn = 1.04

[0215] [Synthesis Example 4] Synthesis of Compound (A3) [Chemical formula] Under a nitrogen atmosphere, 10.0 g of compound (A1), 10.3 g of potassium carbonate, and 60 g of DMF (N,N-dimethylformamide) were added, and a homogeneous dispersion was prepared at an internal temperature of 50°C. 8.8 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 150 ml of MIBK was added, and the mixture was washed six times with 50 ml of pure water. The organic layer was dried under reduced pressure. 40 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 200 g of MeOH (methanol). The precipitated crystals were separated by filtration, washed twice with 100 g of MeOH, and recovered. Compound (A3) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A3): Mw=1590, Mw / Mn=1.04

[0216] [Synthesis Example 5] Synthesis of Compound (A4) [ka] Under a nitrogen atmosphere, 10.0 g of compound (A2), 9.8 g of potassium carbonate, and 60 g of DMF were added and a homogeneous dispersion was prepared at an internal temperature of 50°C. 8.4 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 150 ml of MIBK was added, and the mixture was washed six times with 50 ml of pure water. The organic layer was dried under reduced pressure. 40 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 200 g of MeOH. The precipitated crystals were separated by filtration, washed twice with 100 g of MeOH, and recovered. Compound (A4) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A4): Mw=1830, Mw / Mn=1.04

[0217] [Synthesis Example 6] Synthesis of Compound (A5) [ka] Under a nitrogen atmosphere, 20.0 g of compound (B3), 21.5 g of compound (C1), and 200 g of 1,2-dichloroethane were added, and a homogeneous dispersion was prepared at an internal temperature of 60°C. 12.9 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, 1000 ml of MIBK was added, and the mixture was washed six times with 200 ml of pure water. The organic layer was dried under reduced pressure. 100 g of THF was added to the residue to make a homogeneous solution, and then 300 g of hexane was added dropwise while stirring to precipitate a gluten-like precipitate. After standing for a while, the clear supernatant was decanted. Another 100 g of THF was added to make a homogeneous solution, and 300 g of hexane was added to precipitate a gluten-like precipitate. After standing, the supernatant was decanted. DMF was added to the precipitate to make a homogeneous solution, then removed by reduced pressure distillation, and DMF was added to adjust the yield to a 30 wt% DMF solution. 23.9 g of potassium carbonate was added to the obtained DMF solution, and a homogeneous dispersion was prepared under a nitrogen atmosphere at an internal temperature of 50°C. 20.6 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 300 ml of MIBK was added, and the mixture was washed six times with 100 ml of pure water. The organic layer was dried under reduced pressure. 80 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 400 g of MeOH. The precipitated crystals were separated by filtration, washed twice with 200 g of MeOH, and recovered. Compound (A5) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A5): Mw=1750, Mw / Mn=1.05

[0218] [Synthesis Example 7] Synthesis of Compound (A6) [ka] Under a nitrogen atmosphere, 20.0 g of compound (B4), 17.5 g of compound (C1), and 190 g of 1,2-dichloroethane were added, and a homogeneous solution was prepared at an internal temperature of 60°C. 10.5 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, 1000 ml of MIBK was added, and the mixture was washed six times with 200 ml of pure water. The organic layer was dried under reduced pressure. 100 g of THF was added to the residue to make a homogeneous solution, and then 300 g of hexane was added dropwise while stirring to precipitate a gluten-like precipitate. After standing for a while, the clear supernatant was decanted. Another 100 g of THF was added to make a homogeneous solution, and 300 g of hexane was added to precipitate a gluten-like precipitate. After standing, the supernatant was decanted. DMF was added to the precipitate to make a homogeneous solution, then removed by distillation under reduced pressure, and DMF was added to adjust the yield to a 30 wt% DMF solution. 22.6 g of potassium carbonate was added to the obtained DMF solution, and a homogeneous dispersion was prepared under a nitrogen atmosphere at an internal temperature of 50°C. 19.5 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 300 ml of MIBK was added, and the mixture was washed six times with 100 ml of pure water. The organic layer was dried under reduced pressure. 80 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 400 g of MeOH. The precipitated crystals were separated by filtration, washed twice with 200 g of MeOH, and recovered. Compound (A6) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A6): Mw=1870, Mw / Mn=1.03

[0219] [Synthesis Example 8] Synthesis of Compound (A7) [ka] Under a nitrogen atmosphere, 20.0 g of compound (B5), 12.8 g of compound (C1), and 160 g of 1,2-dichloroethane were added, and a homogeneous solution was prepared at an internal temperature of 60°C. 7.7 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, 1000 ml of MIBK was added, and the mixture was washed six times with 200 ml of pure water. The organic layer was dried under reduced pressure. 100 g of THF was added to the residue to make a homogeneous solution, and then 300 g of hexane was added dropwise while stirring to precipitate a gluten-like precipitate. After standing for a while, the clear supernatant was decanted. Another 100 g of THF was added to make a homogeneous solution, and 300 g of hexane was added to precipitate a gluten-like precipitate. After standing, the supernatant was decanted. DMF was added to the precipitate to make a homogeneous solution, then removed by reduced pressure distillation, and DMF was added to adjust the yield to a 30 wt% DMF solution. 16.6 g of potassium carbonate was added to the obtained DMF solution and a homogeneous dispersion was prepared under a nitrogen atmosphere at an internal temperature of 50°C. 14.3 g of propargyl bromide was slowly added and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 300 ml of MIBK was added and the mixture was washed six times with 100 ml of pure water, and the organic layer was dried under reduced pressure. 80 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 400 g of MeOH. The precipitated crystals were separated by filtration and recovered after washing twice with 200 g of MeOH. Compound (A7) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A7): Mw=2320, Mw / Mn=1.05

[0220] [Synthesis Example 9] Synthesis of Compound (A8) [ka] Under a nitrogen atmosphere, 20.0 g of compound (B6), 18.5 g of compound (C1), and 200 g of 1,2-dichloroethane were added, and a homogeneous dispersion was prepared at an internal temperature of 60°C. 11.1 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, 1000 ml of MIBK was added, and the mixture was washed six times with 200 ml of pure water. The organic layer was dried under reduced pressure. 100 g of THF was added to the residue to make a homogeneous solution, and then 300 g of hexane was added dropwise while stirring to precipitate a gluten-like precipitate. After standing for a while, the clear supernatant was decanted. Another 100 g of THF was added to make a homogeneous solution, and 300 g of hexane was added to precipitate a gluten-like precipitate. After standing, the supernatant was decanted. DMF was added to the precipitate to make a homogeneous solution, then removed by reduced pressure distillation, and DMF was added to adjust the yield to a 30 wt% DMF solution. 26.5 g of potassium carbonate was added to the obtained DMF solution and a homogeneous dispersion was prepared under a nitrogen atmosphere at an internal temperature of 50°C. 23.2 g of allyl bromide was slowly added and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 300 ml of MIBK was added and the mixture was washed six times with 100 ml of pure water, and the organic layer was dried under reduced pressure. 80 g of MIBK was added to the residue to make a homogeneous solution, and the mixture crystallized in 400 g of MeOH. The precipitated crystals were separated by filtration and recovered after washing twice with 200 g of MeOH. Compound (A8) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A8): Mw=2110, Mw / Mn=1.05

[0221] [Synthesis Example 10] Synthesis of Compound (A9) [ka] Under a nitrogen atmosphere, 20.0 g of compound (B1), 41.7 g of compound (C2), and 300 g of 1,2-dichloroethane were added, and a homogeneous dispersion was prepared at an internal temperature of 60°C. 22.0 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70°C for 1 hour. After the reaction was complete, the mixture was cooled to room temperature, 1000 ml of MIBK (methyl isobutyl ketone) was added, and the mixture was washed six times with 200 ml of pure water. The organic layer was dried under reduced pressure. 200 g of THF was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 2000 g of IPE (diisopropyl ether). The precipitated crystals were separated by filtration, washed twice with 500 g of IPE, and recovered. Compound (A9) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A9): Mw=1300, Mw / Mn=1.02

[0222] [Synthesis Example 11] Synthesis of Compound (A10) [ka] Under a nitrogen atmosphere, 10.0 g of compound (A2), 6.5 g of potassium carbonate, and 60 g of DMF were added and a homogeneous dispersion was prepared at an internal temperature of 50°C. 2.8 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 150 ml of MIBK was added, and the mixture was washed six times with 50 ml of pure water. The organic layer was dried under reduced pressure. 40 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 200 g of MeOH. The precipitated crystals were separated by filtration, washed twice with 100 g of MeOH, and recovered. Compound (A10) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A10): Mw=1690, Mw / Mn=1.07

[0223] [Synthesis Example 12] Synthesis of Compound (A11) [ka] Under a nitrogen atmosphere, 20.0 g of compound (B3), 25.2 g of compound (C3), and 200 g of 1,2-dichloroethane were added, and a homogeneous dispersion was prepared at an internal temperature of 60°C. 12.9 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, 1000 ml of MIBK was added, and the mixture was washed six times with 200 ml of pure water. The organic layer was dried under reduced pressure. 100 g of THF was added to the residue to make a homogeneous solution, and then 300 g of hexane was added dropwise while stirring to precipitate a gluten-like precipitate. After standing for a while, the clear supernatant was decanted. Another 100 g of THF was added to make a homogeneous solution, and 300 g of hexane was added to precipitate a gluten-like precipitate. After standing, the supernatant was decanted. DMF was added to the precipitate to make a homogeneous solution, then removed by reduced pressure distillation, and DMF was added to adjust the yield to a 30 wt% DMF solution. 15.4 g of potassium carbonate was added to the obtained DMF solution, and a homogeneous dispersion was prepared under a nitrogen atmosphere at an internal temperature of 50°C. 13.3 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 300 ml of MIBK was added, and the mixture was washed six times with 100 ml of pure water. The organic layer was dried under reduced pressure. 80 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 400 g of MeOH. The precipitated crystals were separated by filtration, washed twice with 200 g of MeOH, and recovered. Compound (A11) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A11): Mw=1330, Mw / Mn=1.06

[0224] [Synthesis Example 13] Synthesis of Compound (A12) [ka] Under a nitrogen atmosphere, 20.0 g of compound (B4), 12.0 g of compound (C4), and 160 g of 1,2-dichloroethane were added, and a homogeneous solution was prepared at an internal temperature of 60°C. 10.5 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, 1000 ml of MIBK was added, and the mixture was washed six times with 200 ml of pure water. The organic layer was dried under reduced pressure. 100 g of THF was added to the residue to make a homogeneous solution, and then 300 g of hexane was added dropwise while stirring to precipitate a gluten-like precipitate. After standing for a while, the clear supernatant was decanted. Another 100 g of THF was added to make a homogeneous solution, and 300 g of hexane was added to precipitate a gluten-like precipitate. After standing, the supernatant was decanted. DMF was added to the precipitate to make a homogeneous solution, then removed by reduced pressure distillation, and DMF was added to adjust the yield to a 30 wt% DMF solution. 22.6 g of potassium carbonate was added to the obtained DMF solution, and a homogeneous dispersion was prepared under a nitrogen atmosphere at an internal temperature of 50°C. 19.5 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 300 ml of MIBK was added, and the mixture was washed six times with 100 ml of pure water. The organic layer was dried under reduced pressure. 80 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 400 g of MeOH. The precipitated crystals were separated by filtration, washed twice with 200 g of MeOH, and recovered. Compound (A12) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A12): Mw=1540, Mw / Mn=1.03

[0225] [Synthesis Example 14] Synthesis of Compound (A13) [ka] Under a nitrogen atmosphere, 20.0 g of compound (B7), 15.1 g of compound (C1), and 200 g of 1,2-dichloroethane were added, and a homogeneous solution was prepared at an internal temperature of 60°C. 9.1 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 70°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, 1000 ml of MIBK was added, and the mixture was washed six times with 200 ml of pure water. The organic layer was dried under reduced pressure. 120 g of THF was added to the residue to make a homogeneous solution, and then 350 g of hexane was added dropwise while stirring to precipitate a gluten-like precipitate. After standing for a while, the clear supernatant was decanted. Again, 120 g of THF was added to make a homogeneous solution, and 350 g of hexane was added to precipitate a gluten-like precipitate. After standing, the supernatant was decanted. DMF was added to the precipitate to make a homogeneous solution, then removed by reduced pressure distillation, and DMF was added to adjust the yield to a 30 wt% DMF solution. 29.3 g of potassium carbonate was added to the obtained DMF solution, and a homogeneous dispersion was prepared under a nitrogen atmosphere at an internal temperature of 50°C. 25.2 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was complete, 400 ml of MIBK was added, and the mixture was washed six times with 100 ml of pure water. The organic layer was dried under reduced pressure. 100 g of MIBK was added to the residue to make a homogeneous solution, and the crystals were then crystallized in 500 g of MeOH. The precipitated crystals were separated by filtration, washed twice with 200 g of MeOH, and recovered. Compound (A13) was obtained by vacuum drying the recovered crystals at 70°C. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (A13): Mw=1810, Mw / Mn=1.04

[0226] The comparative compounds (R1) to (R3) were synthesized using the following compounds (a1) to (a3). [ka]

[0227] [Comparative Synthesis Example 1] Synthesis of Compound (R1) for Comparative Example [ka] Under a nitrogen atmosphere, 10.00 g of compound (a1), 4.76 g of potassium carbonate, and 50 g of DMF were dispersed into a homogeneous dispersion at an internal temperature of 50°C under a nitrogen atmosphere. 3.72 g of propargyl bromide was slowly added dropwise, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After cooling to room temperature, 100 g of methyl isobutyl ketone and 50 g of pure water were added to form a homogeneous solution, and the aqueous layer was removed. The organic layer was then washed twice with 30 g of 3.0% aqueous nitric acid solution and five times with 30 g of pure water, and the organic layer was dried under reduced pressure. 30 g of THF was added to the residue, and crystals were allowed to form with 100 g of methanol. The crystals were separated by filtration, washed twice with 60 g of methanol, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain (R1). The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (R1): Mw=960, Mw / Mn=1.07

[0228] [Comparative Synthesis Example 2] Synthesis of Comparative Compound (R2) [ka] Under a nitrogen atmosphere, 78.8 g of compound (a2), 21.6 g of 37% formalin solution, and 250 g of 1,2-dichloroethane were mixed into a homogeneous solution at 70°C. Then, 5 g of methanesulfonic acid was slowly added, and the mixture was stirred at 80°C for 12 hours. After cooling to room temperature, 500 g of MIBK was added, and the organic layer was washed five times with 200 g of pure water. The organic layer was then dried under reduced pressure. 300 mL of THF was added to the residue, and the polymer was reprecipitated with 2000 mL of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain compound (R2). The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (R2): Mw=2720, Mw / Mn=1.55

[0229] [Comparative Synthesis Example 3] Synthesis of Comparative Compound (R3) [ka] Under a nitrogen atmosphere, 90.1 g of compound (a3), 10.5 g of 37% formalin solution, and 270 g of 2-methoxy-1-propanol were mixed into a homogeneous solution at a liquid temperature of 80°C. Then, 18 g of 20% p-toluenesulfonic acid solution in 2-methoxy-1-propanol was slowly added, and the mixture was stirred at a liquid temperature of 110°C for 8 hours. After cooling to room temperature, 600 g of MIBK was added, and the organic layer was washed five times with 200 g of pure water. The organic layer was then dried under reduced pressure. 320 g of THF was added to the residue, and the polymer was reprecipitated with 1350 g of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain compound (R3). The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using GPC, and the following results were obtained. (R3): Mw=3700, Mw / Mn=2.82

[0230] Tables 1 and 2-1 show the structural formulas, weight-average molecular weight (Mw), and dispersion (Mw / Mn) of the compounds obtained above. Table 2-2 also shows the structural formulas, Mw, and Mw / Mn of the comparative compounds (R1) to (R3).

[0231] [Table 1]

[0232] [Table 2-1]

[0233] [Table 2-2]

[0234] Preparation of materials for forming organic films (UDL-1 to 19, comparative examples UDL-1 to 3) Compounds (A1) to (A13) and (R1) to (R3) were dissolved in a solvent containing 0.1% by mass of the surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 3, and the mixtures were filtered through a 0.1 μm fluororesin filter to prepare organic film-forming materials (UDL-1 to 19, comparative examples UDL-1 to 3). For the preparation of UDL-1 to 15, propylene glycol monomethyl ether acetate (PGMEA) was used as the solvent. For the preparation of UDL-16 to 19, a mixture of PGMEA and either (S1) 1,6-diacetoxyhexane (boiling point 260°C) or (S2) tripropylene glycol monomethyl ether (boiling point 242°C) as a high-boiling point solvent was used as the solvent. For the preparation of comparative examples UDL-1 to 3, PGMEA was used as the solvent.

[0235] [Table 3]

[0236] Example 1 Solvent resistance measurement (Examples 1-1 to 1-19, Comparative Examples 1-1 to 1-3) The organic film-forming materials prepared above (UDL-1 to 19, comparative UDL-1 to 3) were coated onto a silicon substrate and baked at 400°C for 60 seconds under a nitrogen stream with an oxygen concentration controlled to 0.2 volume% or less. The film thickness (a [Å]) was then measured. PGMEA solvent was dispensed onto the substrate, left for 30 seconds to spin-dry, and baked at 100°C for 60 seconds to evaporate the PGMEA. The film thickness (b [Å]) was then measured. The difference in film thickness before and after PGMEA treatment (residual film percentage: (b / a) × 100) was calculated. The results are shown in Table 4 below.

[0237] [Table 4]

[0238] As shown in Table 4, the organic film-forming materials of the present invention (Examples 1-1 to 1-19) have a residual film rate of 99.5% or more after PGMEA treatment, indicating that crosslinking reactions occur even under a nitrogen atmosphere and that sufficient solvent resistance is exhibited. In contrast, Comparative Example 1-3 lacks substituents that act as crosslinking groups, resulting in a residual film rate of less than 50% after PGMEA treatment and the absence of a curing reaction, thus failing to exhibit solvent resistance. These results indicate that the substituent represented by OR3 introduced as a substituent functions effectively as a thermal crosslinking group.

[0239] Example 2: Evaluation of heat resistance properties (Examples 2-1 to 2-19, Comparative Examples 2-1 to 2-3) The above organic film-forming materials (UDL-1 to 19, comparative UDL-1 to 3) were each coated onto a silicon substrate and fired in air at 180°C to form a 200 nm coated film, and the film thickness (A (Å)) was measured. This substrate was further fired at 400°C for 10 minutes under a nitrogen atmosphere with an oxygen concentration controlled to 0.2 volume% or less, and the film thickness (B (Å)) was measured. The residual film percentage was calculated by dividing film thickness B by film thickness A. These results are shown in Table 5.

[0240] [Table 5]

[0241] As shown in Table 5, the organic film-forming materials of the present invention (Examples 2-1 to 2-19) showed a film thickness reduction of less than 3% even after firing at 400°C for 10 minutes, indicating that the organic film-forming materials of the present invention maintain their film thickness even after firing at 400°C, demonstrating high heat resistance. Among these, Examples 2-1 to 2-5, 2-11, and 2-16 to 2-18, which contain compounds with an n2=1 and n3=2 structure, showed even less film thickness reduction. In contrast, Comparative Example 2-1, which is a divalent compound, and Comparative Example 2-2, which does not have a fluorene structure, showed a large film thickness reduction of more than 10%, and Comparative Example 2-3, which does not have a crosslinking group, also showed a film thickness reduction of more than 10%. From these results, it can be seen that a polyvalent skeleton and Benzene or It can be seen that a dense and highly heat-resistant film is formed by compounds having a naphthalene structure.

[0242] Example 3: Evaluation of Embedding Characteristics (Examples 3-1 to 3-19, Comparative Examples 3-1 to 3-3) As shown in Figure 3, the above-mentioned organic film-forming materials (UDL-1 to 19, comparative UDL-1 to 3) were each applied to an SiO2 wafer substrate having a dense hole pattern (hole diameter 0.16 μm, hole depth 0.50 μm, distance between the centers of two adjacent holes 0.32 μm). The materials were then baked on a hot plate at 400°C for 60 seconds under a nitrogen atmosphere with an oxygen concentration controlled to 0.2 volume% or less to form an organic film 8. The substrate used was a base substrate 7 (SiO2 wafer substrate) having a dense hole pattern as shown in Figure 3(G) (overhead view) and (H) (cross-sectional view). The cross-sectional shape of each obtained wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with organic film without any voids (gaps). The results are shown in Table 6. When an organic film-forming material with inferior filling characteristics was used, voids were generated inside the holes in this evaluation. When an organic film-forming material with good embedding properties is used, the organic film fills the inside of the holes without voids, as shown in Figure 3(I) in this evaluation.

[0243] [Table 6]

[0244] As shown in Table 6, the organic film-forming materials of the present invention (Examples 3-1 to 3-19) were found to be able to fill hole patterns without generating voids and to have good embedding characteristics. In Comparative Examples 3-1 and 3-2, although insufficient heat resistance was observed as shown in the heat resistance evaluation results, no voids were observed. On the other hand, in Comparative Example 3-3, not only was there insufficient heat resistance, but voids were generated due to insufficient crosslinking ability, and it was confirmed that the embedding characteristics were poor. From these results, it was confirmed that the organic film-forming materials of the present invention have good embedding characteristics.

[0245] Example 4: Evaluation of Planarization Characteristics (Examples 4-1 to 4-19, Comparative Examples 4-1 to 4-3) Organic film-forming materials (UDL-1 to 19, comparative UDL-1 to 3) were each coated onto a substrate 9 (SiO2 wafer substrate) having a large isolated trench pattern (Figure 4(J), trench width 10 μm, trench depth 0.10 μm). After firing at 400°C for 60 seconds under a nitrogen atmosphere controlled to an oxygen concentration of 0.2 volume% or less, the step difference in the organic film 10 between the trenched and non-trenched areas (delta 10 in Figure 4(K)) was observed using a Park Systems NX10 atomic force microscope (AFM). The results are shown in Table 7. In this evaluation, a smaller step difference indicates better planarization characteristics. In this evaluation, a trench pattern with a depth of 0.10 μm was planarized using an organic film-forming material with a typical film thickness of approximately 0.2 μm, making it a strict evaluation condition for assessing the superiority of planarization characteristics.

[0246] [Table 7]

[0247] As shown in Table 7, the organic film-forming materials of the present invention (Examples 4-1 to 4-19) were found to have a smaller step difference between the trenched and non-trenched portions of the organic film and superior planarization characteristics compared to Comparative Examples 4-1 to 4-3. Comparative Examples 4-1 to 4-2 lacked sufficient heat resistance, as shown in the heat resistance evaluation, and although embedding was ensured, as shown in the embedding characteristics evaluation, the film shrunk during high-temperature baking, resulting in a deterioration of flatness. In addition, Comparative Example 4-3 did not exhibit good planarization characteristics due to insufficient crosslinking ability. Furthermore, comparing Examples 4-15 to 4-19, which had a high-boiling point solvent added, with Examples 4-1, 4-2, 4-4, and 4-6, which did not, it can be seen that the addition of the high-boiling point solvent further improved flatness. From these results, it can be seen that the organic film-forming materials of the present invention have excellent heat resistance, which suppresses film shrinkage during high-temperature baking and exhibits excellent planarization characteristics.

[0248] Example 5: Adhesion Test (Examples 5-1 to 5-15, Comparative Examples 5-1 to 5-2) The above organic film-forming materials (UDL-1 to 15, comparative UDL-1 to 2) were applied to an SiO2 wafer substrate, and an organic film with a thickness of 200 nm was formed by baking at 400°C for 60 seconds under a nitrogen atmosphere with an oxygen concentration controlled to 0.2 volume% or less. The wafer with this organic film was cut into 1 x 1 cm squares, and aluminum pins with epoxy adhesive were attached to the cut wafers using a special jig. Then, the wafers were heated in an oven at 150°C for 1 hour to bond the aluminum pins to the substrate. After cooling to room temperature, the initial adhesion was evaluated by resistance using a thin film adhesion strength measuring device (Sebastian Five-A). Note that the adhesion test could not be performed on comparative example UDL-3, which did not have sufficient solvent resistance in Example 1.

[0249] Figure 5 shows an explanatory diagram illustrating the adhesion measurement method. In Figure 5, 11 is the silicon wafer (substrate), 12 is the cured film, 13 is the aluminum pin with adhesive, 14 is the support base, 15 is the grip, and 16 indicates the tensile direction. The adhesion force is the average value of 12 measurements, and a higher value indicates better adhesion of the adhesive film to the substrate. The adhesion was evaluated by comparing the obtained values. The results are shown in Table 8.

[0250] [Table 8]

[0251] As shown in Examples 5-1 to 5-15 of Table 8, the organic film materials using the compounds of the present invention exhibit higher adhesion compared to Comparative Examples 5-1 and 5-2. Among these, Examples 5-1 to 5-6, 5-8, 5-10 to 5-15, which contain the n3=2 structure, showed high adhesion, and Examples 5-8, 5-12, and 5-13, which contain the R3=H structure, showed particularly high adhesion. On the other hand, Comparative Examples 5-1 and 5-2 exhibited low adhesion due to insufficient heat resistance. From these results, it can be seen that the compounds of the present invention exhibit high heat resistance and adhesion to substrates.

[0252] Example 6 Pattern Formation Test 1 (Examples 6-1 to 6-19, Comparative Example 6-1) The above organic film-forming materials (UDL-1 to UDL-19, comparative UDL-1) were each applied to a silicon wafer substrate on which a 300 nm SiO2 film had been formed. The materials were then baked at 400°C for 60 seconds under a nitrogen atmosphere with an oxygen concentration controlled to 0.2 volume% or less to form an organic film (resist underlayer). A CVD-SiON hard mask was then formed on top of this, and an organic anti-reflective film material (ARC-29A: manufactured by Nissan Chemical Corporation) was applied and baked at 210°C for 60 seconds to form an organic anti-reflective film with a thickness of 80 nm. An ArF single-layer resist, which is a resist toplayer material, was then applied on top of this and baked at 105°C for 60 seconds to form a photoresist film (resist toplayer) with a thickness of 100 nm. An immersion protective film material (TC-1) was applied to the photoresist film and baked at 90°C for 60 seconds to form a protective film with a thickness of 50 nm. Furthermore, comparative examples UDL-2 and UDL-3 had poor heat resistance and crosslinking properties, making it impossible to form CVD-SiON hard masks, and therefore they could not proceed to the subsequent pattern formation tests.

[0253] The resist upper layer material (single-layer resist for ArF) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in the proportions shown in Table 9 in a solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Co., Ltd.), and filtering the mixture through a 0.1 μm fluororesin filter.

[0254] [Table 9]

[0255] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) used are shown below.

[0256] [ka]

[0257] The immersion protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent in the proportions shown in Table 10 and filtering it through a 0.1 μm fluororesin filter.

[0258] [Table 10]

[0259] The polymer used (PP1) is shown below. [ka]

[0260] Next, the images were exposed using an ArF immersion lithography system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s polarized illumination, 6% halftone phase shift mask), baked (PEB) at 100°C for 60 seconds, and developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 55 nm 1:1 positive line-and-space pattern.

[0261] Next, using a Tokyo Electron Telius etching system, the resist pattern was used as a mask to etch the organic anti-reflective film and the CVD-SiON hard mask by dry etching to form a hard mask pattern. The resulting hard mask pattern was then used as a mask to etch the organic film to form an organic film pattern, and the resulting organic film pattern was used as a mask to etch the SiO2 film. The etching conditions are as follows.

[0262] Conditions for transferring the resist pattern to a SiON hard mask. Chamber pressure 10.0 Pa RF Power 1,500W CF4 gas flow rate: 75 sccm O2 gas flow rate: 15 sccm Time 15sec

[0263] Transfer conditions for hard mask patterns onto organic films. Chamber pressure 2.0 Pa RF Power 500W Ar gas flow rate: 75 sccm O2 gas flow rate: 45 sccm Time 120sec

[0264] Transfer conditions for organic film patterns onto SiO2 films. Chamber pressure 2.0 Pa RF Power 2,200W C5F 12 Gas flow rate: 20 sccm C2F6 gas flow rate: 10 sccm Ar gas flow rate: 300 sccm O2 gas flow rate: 60 sccm Time 90sec

[0265] Table 11 shows the results of observing the pattern cross-section using an electron microscope (S-4700) manufactured by Hitachi, Ltd.

[0266] [Table 11]

[0267] As shown in Table 11, the results for the organic film forming material of the present invention (Examples 6-1 to 6-19) showed that in all cases the resist upper layer film pattern was successfully transferred to the substrate, confirming that the organic film forming material of the present invention is suitable for use in microfabrication by the multilayer resist method. In Comparative Example 6-1, although the heat resistance was insufficient, it was still possible to form a pattern.

[0268] Furthermore, the organic film forming materials (UDL1-19) of the present invention can form organic films that exhibit excellent adhesion to the substrate, thereby suppressing delamination of the CVD-SiON hard mask formed directly on the organic film and the resist upper layer film formed thereon. As a result, in Examples 6-1 to 6-19, as described above, the resist upper layer film pattern was successfully transferred to the substrate.

[0269] Example 7 Pattern Formation Test 2 (Examples 7-1 to 7-19, Comparative Example 7-1) The above organic film-forming materials (UDL-1 to UDL-19, comparative UDL-1) were each coated onto an SiO2 wafer substrate having a trench pattern (trench width 10 μm, trench depth 0.10 μm), and the coated films were formed in the same manner as in pattern formation test 1, except that they were fired at 400°C for 60 seconds under a nitrogen atmosphere with an oxygen concentration controlled to 0.2 volume% or less. Patterning and dry etching were then performed, and the shape of the resulting patterns was observed. The results are shown in Table 12.

[0270] [Table 12]

[0271] As shown in Table 12, the results for the organic film forming material of the present invention (Examples 7-1 to 7-19) showed that in all cases the resist upper layer film pattern was successfully transferred to the substrate, confirming that the organic film forming material of the present invention is suitable for use in microfabrication using the multilayer resist method. On the other hand, in Comparative Example 7-1, as shown in the planarization characteristic evaluation results, the planarization characteristics were poor, resulting in pattern collapse during pattern processing, and ultimately a good pattern could not be obtained.

[0272] Furthermore, the organic film forming materials of the present invention (Examples 7-1 to 7-19) can form organic films that exhibit excellent adhesion to the substrate, thereby suppressing delamination of the CVD-SiON hard mask formed directly on the organic film and the resist upper layer film formed thereon. As a result, in Examples 7-1 to 7-19, as described above, the resist upper layer film pattern was successfully transferred to the substrate.

[0273] From the above, it has become clear that the organic film-forming material of the present invention, which contains the organic film-forming compound of the present invention, is extremely useful as an organic film-forming material for use in the multilayer resist method because it possesses heat resistance of 400°C or higher even under an oxygen-free inert gas, excellent adhesion to the substrate, and advanced embedding / planarization characteristics. Furthermore, it has become clear that the pattern formation method of the present invention using this material can form fine patterns with high precision even on substrates that have steps.

[0274] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

[0275] This specification includes the following embodiments: [1]: A material for forming an organic film, (A) an organic film-forming compound represented by the following general formula (1A), and (B) an organic solvent An organic film-forming material characterized by containing the following: [ka] (In the formula, Y is an n1-valent organic group, a trivalent nitrogen atom, or a tetravalent carbon atom, n1 is an integer from 3 to 8, and X is a substructure represented by the following general formula (1B).) [ka] (In the formula, dashed lines represent bonds. R1 and R2 represent halogen atoms, C1-C4 alkyl groups, C1-C4 alkyloxy groups, C2-C4 alkynyl groups, or C2-C4 alkenyl groups, and the hydrogen atoms on the carbon atoms constituting the alkyl groups, alkyloxy groups, alkynyl groups, or alkenyl groups may be substituted with fluorine atoms. Furthermore, aromatic rings that can be substituted by R1 may form a bridging structure via single bonds or via a divalent group obtained by removing one hydrogen atom from R1. n4 and n5 represent integers from 0 to 2. Ar1 and Ar2 represent a benzene ring or a naphthalene ring, respectively. n2 represents 0 or 1, n3 represents 1 or 2, and R3 represents a hydrogen atom or a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group.) [2]: The organic film-forming material of [1], characterized in that R3 in the general formula (1B) is one of those shown in the following formula (1C). [ka] (The dashed lines in the above equation represent connections.) [3]: An organic film-forming material according to [1] or [2], characterized in that n1 in the general formula (1A) is 3 or 4. [4]: Any one of the organic film-forming materials from [1] to [3], characterized in that n2 in the general formula (1B) is 1. [5]: An organic film-forming material from any one of [1] to [4], characterized in that Y in the general formula (1A) is one of the substructures shown in the following formula (1D). [ka] (In the above formula, the dashed lines represent bonding bonds, and R4 represents a hydrogen atom or a methyl group.) [6]: Any one of the organic film-forming materials from [1] to [5], characterized in that the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of component (A) as determined by gel permeation chromatography is 1.00 ≤ Mw / Mn ≤ 1.10. [7]: The organic film-forming material according to any one of [1] to [6], characterized in that the (B) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher. [8]: The organic film-forming material is characterized in that it further contains one or more of (C) an acid generator, (D) a surfactant, (E) a crosslinking agent, and (F) a plasticizer, as one of any one of [1] to [7]. [9]: A substrate for manufacturing a semiconductor device, characterized in that an organic film is formed on the substrate by curing one of the organic film-forming materials from [1] to [8].

[10] : A method for forming an organic film applicable in the manufacturing process of a semiconductor device, characterized by rotating coating one of the organic film forming materials from [1] to [8] onto a workpiece substrate, and then heat-treating the workpiece substrate coated with the organic film forming material in an inert gas atmosphere at a temperature of 50°C to 600°C for a range of 5 seconds to 7200 seconds to obtain a cured film.

[11] : A method for forming an organic film applicable in the manufacturing process of a semiconductor device, characterized by rotating coating one of the organic film forming materials from [1] to [8] onto a workpiece substrate, heat-treating the workpiece substrate coated with the organic film forming material in air at a temperature of 50°C to 300°C for 5 to 600 seconds to form a coated film, and subsequently applying heat treatment in an inert gas atmosphere at a temperature of 200°C to 600°C for 10 to 7200 seconds to obtain a cured film.

[12] : A method for forming an organic film according to

[10] or

[11] , characterized in that the oxygen concentration in the inert gas is 1 volume% or less.

[13] : A method for forming an organic film according to any one of

[10] to

[12] , characterized in that the substrate to be processed is a substrate to be processed having a structure or step with a height of 30 nm or more.

[14] : A pattern formation method characterized by forming an organic film on a workpiece using one of the organic film forming materials from [1] to [8], forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material, forming a resist upper layer on the silicon-containing resist interlayer using a photoresist composition, forming a circuit pattern on the resist upper layer, transferring the pattern to the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[15] : A method for forming a pattern, characterized by forming an organic film on a workpiece using one of the organic film forming materials from [1] to [8], forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material, forming an organic anti-reflective film on the silicon-containing resist interlayer, forming a resist upper layer on the organic anti-reflective film using a photoresist composition to form a four-layer structure, forming a circuit pattern on the resist upper layer, transferring the pattern to the organic anti-reflective film and the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[16] : A pattern formation method characterized by forming an organic film on a workpiece using one of the organic film forming materials from [1] to [8], forming an inorganic hard mask selected from silicon oxide film, silicon nitride film, silicon oxynitride film, titanium oxide film, and titanium nitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a photoresist composition to form a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[17] : A pattern formation method characterized by forming an organic film on a workpiece using one of the organic film forming materials from [1] to [8], forming an inorganic hard mask selected from silicon oxide film, silicon nitride film, silicon oxynitride film, titanium oxide film, and titanium nitride film on the organic film, forming an organic anti-reflective film on the inorganic hard mask, forming a resist upper layer film on the organic anti-reflective film using a photoresist composition to form a four-layer film structure, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic anti-reflective film and the inorganic hard mask by etching using the resist upper layer film on which the pattern is formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern is transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern is transferred as a mask.

[18] : The pattern forming method according to

[16] or

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

[19] : A pattern formation method from any one of

[14] to

[18] , characterized in that the circuit pattern is formed by lithography using light with a wavelength of 10 nm to 300 nm, direct drawing with an electron beam, nanoimprinting, or a combination thereof.

[20] : A pattern formation method from any one of

[14] to

[19] , characterized in that the circuit pattern is developed by alkaline development or an organic solvent.

[21] : A pattern formation method from any one of

[14] to

[20] , characterized in that the workpiece is a semiconductor device substrate, or a semiconductor device substrate on which a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film is formed.

[22] : The pattern forming method according to

[21] , characterized in that the workpiece contains silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof.

[23] : Compounds represented by the following general formula (1A). [ka] (In the formula, Y is an n1-valent organic group, a trivalent nitrogen atom, or a tetravalent carbon atom, n1 is an integer from 3 to 8, and X is a substructure represented by the following general formula (1B).) [ka] (In the formula, dashed lines represent bonds. R1 and R2 represent halogen atoms, C1-C4 alkyl groups, C1-C4 alkyloxy groups, C2-C4 alkynyl groups, or C2-C4 alkenyl groups, and the hydrogen atoms on the carbon atoms constituting the alkyl groups, alkyloxy groups, alkynyl groups, or alkenyl groups may be substituted with fluorine atoms. Furthermore, aromatic rings that can be substituted by R1 may form a bridging structure via single bonds or via a divalent group obtained by removing one hydrogen atom from R1. n4 and n5 represent integers from 0 to 2. Ar1 and Ar2 represent a benzene ring or a naphthalene ring, respectively. n2 represents 0 or 1, n3 represents 1 or 2, and R3 represents a hydrogen atom or a C1-C4 alkyl group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group.)

[24] : The compound according to

[23] , characterized in that R3 in the general formula (1B) is one of those represented by the following formula (1C). [ka] (The dashed lines in the above equation represent connections.)

[25] : A compound of

[23] or

[24] characterized in that n1 in the general formula (1A) is 3 or 4.

[26] : Any one of the compounds from

[23] to

[25] characterized in that n2 in the general formula (1B) is 1.

[27] : Any one of the compounds from

[23] to

[26] characterized in that Y in the general formula (1A) is one of the substructures shown in the following formula (1D). [ka] (In the above formula, the dashed lines represent bonding bonds, and R4 represents a hydrogen atom or a methyl group.) [Explanation of Symbols]

[0276] 1...Substrate, 2...Layer to be processed, 2a...Pattern formed on the layer to be processed, 3...Organic film, 3a...Organic film pattern, 3'...Material for forming organic film, 4...Silicon-containing resist interlayer, 4a...Silicon-containing resist interlayer pattern, 5...Resist top layer, 5a...Resist top layer pattern, 6...Required area (exposed area), 7...Underlayment substrate with dense hole pattern, 8...Organic film, 9...Underlayment substrate with large isolated trench pattern, 10...Organic film, delta 10...Difference in film thickness of resist interlayer between trench and non-trench areas. 11...Silicon wafer, 12...Cured film, 13...Aluminum pin with adhesive, 14...Support base, 15...Gripping, 16...Tensile direction.

Claims

1. A material for forming organic films, (A) A compound for forming an organic film represented by the following general formula (1A), and (B) an organic solvent An organic film-forming material characterized by containing the following: 【Chemistry 1】 (In the formula, Y is an n1-valent organic group, a trivalent nitrogen atom, or a tetravalent carbon atom, n1 is an integer from 3 to 8, and X is a substructure represented by the following general formula (1B).) 【Chemistry 2】 (In the formula, dashed lines represent connections. R １ , R ２ R represents a halogen atom, a C1-C4 alkyl group, a C1-C4 alkyloxy group, a C2-C4 alkynyl group, or a C2-C4 alkenyl group, and the hydrogen atoms on the carbon atoms constituting the alkyl group, alkyloxy group, alkynyl group, or alkenyl group may be substituted with fluorine atoms. １ Aromatic rings that can be substituted are connected by single bonds or the R １ A bridging structure may be formed via a divalent group obtained by removing one hydrogen atom from the original group. n4 and n5 represent integers from 0 to 2. Ar1 and Ar2 represent a benzene ring or a naphthalene ring, respectively. n2 represents 0 or 1, n3 represents 1 or 2, and R ３ (This is one of the options shown in the following formula (1C).) 【Transformation 3】 (The dashed lines in the above equation represent connections.)

2. The organic film-forming material according to claim 1, characterized in that n1 in the general formula (1A) is 3 or 4.

3. The organic film-forming material according to claim 1, characterized in that n2 in the general formula (1B) is 1.

4. The organic film-forming material according to claim 1, characterized in that Y in the general formula (1A) is any of the substructures shown in the following formula (1D). 【Chemistry 4】 (The dashed lines in the above formula represent bonds, R ４ (This represents a hydrogen atom or a methyl group.)

5. The organic film-forming material according to claim 1, characterized in that the ratio Mw / Mn of the weight-average molecular weight Mw to the number-average molecular weight Mn of component (A) as determined by gel permeation chromatography is 1.00 ≤ Mw / Mn ≤ 1.

10.

6. The organic film-forming material according to claim 1, characterized in that the (B) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

7. The organic film-forming material according to claim 1, characterized in that the organic film-forming material further contains one or more of (C) an acid generator, (D) a surfactant, (E) a crosslinking agent, and (F) a plasticizer.

8. A substrate for manufacturing a semiconductor device, characterized in that an organic film formed on the substrate is obtained by curing an organic film material according to any one of claims 1 to 7.

9. A method for forming an organic film applicable in the manufacturing process of a semiconductor device, characterized by rotatingly coating a workpiece substrate with an organic film-forming material described in any one of claims 1 to 7, and then heat-treating the workpiece substrate coated with the organic film-forming material in an inert gas atmosphere at a temperature of 50°C to 600°C for a range of 5 seconds to 7200 seconds to obtain a cured film.

10. A method for forming an organic film applicable in the manufacturing process of a semiconductor device, characterized by: rotatingly coating a workpiece substrate with an organic film-forming material described in any one of claims 1 to 7; heat-treating the workpiece substrate coated with the organic film-forming material in air at a temperature of 50°C to 300°C for 5 to 600 seconds to form a coated film; and subsequently applying heat treatment in an inert gas atmosphere at a temperature of 200°C to 600°C for 10 to 7200 seconds to obtain a cured film.

11. The method for forming an organic film according to claim 9, characterized in that the oxygen concentration in the inert gas is 1 volume percent or less.

12. The method for forming an organic film according to claim 9, characterized in that the substrate to be processed is a substrate having a structure or step with a height of 30 nm or more.

13. A pattern forming method characterized by forming an organic film on a workpiece using an organic film forming material according to any one of claims 1 to 7; forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material; forming a resist upper layer on the silicon-containing resist interlayer using a photoresist composition; forming a circuit pattern on the resist upper layer; transferring the pattern to the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern is formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

14. A pattern forming method characterized by forming an organic film on a workpiece using an organic film forming material according to any one of claims 1 to 7; forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material; forming an organic anti-reflective film on the silicon-containing resist interlayer; forming a resist upper layer on the organic anti-reflective film using a photoresist composition to form a four-layer film structure; forming a circuit pattern on the resist upper layer; transferring the pattern to the organic anti-reflective film and the silicon-containing resist interlayer by etching using the resist upper layer on which the pattern is formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist interlayer on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

15. A pattern forming method characterized by forming an organic film on a workpiece using an organic film forming material according to any one of claims 1 to 7; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a titanium oxide film, and a titanium nitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the pattern is formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

16. A pattern forming method characterized by forming an organic film on a workpiece using an organic film forming material according to any one of claims 1 to 7; forming an inorganic hard mask selected from silicon oxide film, silicon nitride film, silicon oxynitride film, titanium oxide film, and titanium nitride film on the organic film; forming an organic anti-reflective film on the inorganic hard mask; forming a resist upper layer film on the organic anti-reflective film using a photoresist composition to form a four-layer film structure; forming a circuit pattern on the resist upper layer film; transferring the pattern to the organic anti-reflective film and the inorganic hard mask by etching using the resist upper layer film on which the pattern is formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

17. The pattern forming method according to claim 15, characterized in that the inorganic hard mask is formed by a CVD method or an ALD method.

18. The pattern formation method according to claim 13, characterized in that the circuit pattern is formed by lithography using light with a wavelength of 10 nm to 300 nm, direct drawing with an electron beam, nanoimprinting, or a combination thereof.

19. The pattern forming method according to claim 13, characterized in that the circuit pattern is developed using alkaline development or an organic solvent in the formation of the circuit pattern.

20. The pattern forming method according to claim 13, characterized in that the workpiece is a semiconductor device substrate, or a semiconductor device substrate on which any of the following films is formed: a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film.

21. The pattern forming method according to claim 20, characterized in that the workpiece contains silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof.

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