Material for forming organic film, substrate for manufacturing semiconductor device, method for forming organic film, method for forming pattern, compound for forming organic film, and aromatic carboxylic acid anhydride

Abstract

The invention relates to a material for forming an organic film, a substrate for manufacturing a semiconductor device, a method for forming an organic film, a method for forming a pattern, a compound for forming an organic film, and an aromatic carboxylic acid anhydride. The present invention provides: a film-forming agent which can be cured not only in air but also under a film-forming condition in a blunt gas; a material for forming an organic film containing the compound; a substrate for manufacturing a semiconductor device using the material; a method for forming an organic film; a method for forming a pattern; a material for forming an organic film, which contains (A) a compound represented by general formula (1A) and (B) an organic solvent. In the formula, W1 is an n1-valent organic group, n1 represents an integer of 2-4, and X1 is a group represented by formula (1B). In the formula, n2 is 1 or 2, and R1 is any one of the groups represented by formula (1C).

Description

TECHNICAL FIELD

[0001] The present application relates to a material for forming an organic film, a substrate for manufacturing a semiconductor device, a method for forming an organic film, a pattern forming method, a compound for forming an organic film, and an aromatic carboxylic anhydride. BACKGROUND

[0002] In the past, high integration and high speed of semiconductor devices have been achieved by miniaturization of pattern size due to shortening of wavelength of light sources in photolithography technology (optical lithography) using light exposure as a general-purpose technology. In order to form such a fine circuit pattern on a semiconductor device substrate (processed substrate), a method of using a patterned photoresist film as an etching mask and processing the processed substrate by dry etching is generally used. However, there is no dry etching method that can achieve complete etching selectivity between the photoresist film and the processed substrate in terms of practicality, and therefore, in recent years, substrate processing using a multi-layer resist method has become widespread. This method is a method of inserting an anti-etching lower layer film that is different in etching selectivity from a photoresist film (hereinafter also referred to as an upper resist film) between the upper resist film and the processed substrate, obtaining a pattern on the upper resist film, transferring the pattern to the lower resist film by dry etching using the upper resist film pattern as a dry etching mask, and further transferring the pattern to the processed substrate by dry etching using the lower resist film as a dry etching mask.

[0003] One of multi-layer resist methods, a 3-layer resist method that can be performed using a general resist composition used in a single-layer resist method. The method is to perform coating and firing on a substrate to be processed using an organic underlayer film material composed of a composition containing an organic resin, thereby forming an organic underlayer film (hereinafter also referred to as an organic film), on which coating and firing are performed using a resist intermediate film material composed of a composition containing a silicon-containing resin, thereby forming a silicon-containing film (hereinafter also referred to as a silicon-containing resist intermediate film), on which a general organic photoresist film (hereinafter also referred to as a resist upper layer film) is formed. After the resist upper layer film is patterned, if dry etching using a fluorine-based gas plasma is performed, the organic resist upper layer film can achieve a good etching selectivity with respect to the silicon-containing resist intermediate film, so that the resist upper layer film pattern can be transferred to the silicon-containing resist intermediate film. According to this method, even if a resist upper layer film that does not have a sufficient film thickness to directly process a substrate to be processed, or a resist upper layer film that does not have a sufficient dry etching resistance for processing of a substrate to be processed is used, the silicon-containing resist intermediate film is generally equal to or less than the resist upper layer film in film thickness, so that the pattern can be easily transferred to the silicon-containing resist intermediate film. Then, as long as the silicon-containing resist intermediate film on which the pattern is transferred is used as a dry etching mask to transfer the pattern to the organic film by dry etching using an oxygen-based or hydrogen-based gas plasma, the pattern can be transferred to the organic film that has a sufficient dry etching resistance for processing of a substrate. The pattern-transferred organic film can transfer the pattern to a substrate by dry etching using a fluorine-based gas or a chlorine-based gas, or the like.

[0004] On the other hand, miniaturization in the manufacturing steps of semiconductor devices is gradually approaching the essential limit derived from the wavelength of the light source for optical lithography. Therefore, in recent years, high integration of semiconductor devices independent of miniaturization has been under study, and as one of the methods thereof, semiconductor devices having a complex structure such as a multi-gate structure have been under study, and some of them have been put into practical use. In the case where such a structure is formed by a multi-layer resist method, an organic film material that fills small patterns such as holes, trenches, fins, and the like formed on a processed substrate without voids, or that planarizes high and low portions or pattern-dense portions and regions without patterns with a film can be used. By forming a flat organic film surface on a high and low substrate by using such an organic film material, variation in film thickness of a silicon-containing resist intermediate film or an upper resist film formed thereon can be suppressed, and a decrease in margin of focus of optical lithography or in the processing steps of the processed substrate thereafter can be suppressed. Thereby, semiconductor devices can be manufactured with good yield. On the other hand, in a single-layer resist method, in order to fill high and low portions or patterned processed substrates, the film thickness of the upper resist film is thickened, which leads to collapse of the pattern after exposure and development, or deterioration of the pattern shape due to reflection from the substrate at the time of exposure, and the like, and the margin for pattern formation at the time of exposure is narrowed, and it is difficult to manufacture semiconductor devices with good yield.

[0005] In addition, as a method for high speed of next-generation semiconductor devices, for example, the use of novel materials having high electron mobility such as strained silicon or gallium arsenide, or the use of precise materials such as ultra-thin polycrystalline silicon controlled at the order of micrometers have also been under study. However, a processed substrate using such novel precise materials is under a condition for forming a planarization film using an organic film material as described above, for example, under a film formation condition of 300°C or higher in air, and the material of the processed substrate can be corroded by oxygen in the air, and there is a possibility that high speed of semiconductor devices cannot exhibit performance as designed by the material, and yield as a production in industry cannot be achieved. Therefore, in order to avoid a decrease in yield due to corrosion of the substrate caused by air under such a high temperature condition, an organic film material that can be formed in an inert gas is desired.

[0006] In the past, condensation resins of carbonyl compounds such as ketones or aldehydes or aromatic alcohols have been known as materials for forming an organic film for a multi-layer resist method using phenol-based or naphthol-based compounds. For example, fluorene bisphenol novolak resins described in Patent Document 1, bisphenol compounds and novolak resins thereof described in Patent Document 2, phenol novolak resins of adamantane phenol compounds described in Patent Document 3, bisnaphthol compounds and novolak resins thereof described in Patent Document 4, and the like can be exemplified. Such materials are hardened by cross-linking by a methylol compound as a cross-linking agent or cross-linking by oxidation at the α-position of the aromatic ring by oxygen in the air and subsequent condensation, and are formed into a film as a film having solvent resistance with respect to a coating film material used in a subsequent step.

[0007] In addition, organic film materials in which a triple bond is used as an intermolecular cross-linking group of a hardening resin are known. For example, Patent Documents 5 to 16 and the like are known. These materials are cross-linked not only by the above-mentioned cross-linking from methylol but also by polymerization of a triple bond, whereby a hardened film having solvent resistance is formed. However, although these organic film-forming materials are excellent in heat resistance, characteristics such as planarity, adhesion to a substrate, and the like are not sufficient and there is room for improvement.

[0008] Prior Art Documents

[0009] Patent Documents

[0010] [Patent Document 1] Japanese Patent Application Laid-Open (JP-A) No. 2005-128509

[0011] [Patent Document 2] Japanese Patent Application Laid-Open (JP-A) No. 2006-293298

[0012] [Patent Document 3] Japanese Patent Application Laid-Open (JP-A) No. 2006-285095

[0013] [Patent Document 4] Japanese Patent Application Laid-Open (JP-A) No. 2010-122656

[0014] [Patent Document 5] Japanese Patent Application Laid-Open (JP-A) No. Hei 11-512430

[0015] [Patent Document 6] Japanese Patent Application Laid-Open (JP-A) No. 2005-041938

[0016] [Patent Document 7] Japanese Patent Application Laid-Open (JP-A) No. 2009-206447

[0017] [Patent Document 8] Japanese Patent Application Laid-Open (JP-A) No. 2010-181605

[0018] [Patent Document 9] Japanese Patent Application Laid-Open (JP-A) No. 2012-215842

[0019] [Patent Literature 1] International Publication No. 2014 / 208324

[0020] [Patent Literature 2] Japanese Patent Application Laid-Open (kokai) No. 2016-044272

[0021] [Patent Literature 3] Japanese Patent Application Laid-Open (kokai) No. 2016-060886

[0022] [Patent Literature 4] Japanese Patent Application Laid-Open (kokai) No. 2017-014193

[0023] [Patent Literature 5] Japanese Patent Application Laid-Open (kokai) No. 2017-119671

[0024] [Patent Literature 6] Japanese Patent Application Laid-Open (kokai) No. 2018-092170

[0025] [Patent Literature 7] International Publication No. 2019 / 146378 SUMMARY

[0026] [Problems to be Solved by the Invention]

[0027] The present application was achieved in view of the above-described circumstances, and aims to provide an organic film forming compound and an organic film forming material containing the same, which not only harden under film forming conditions in air, but also harden under film forming conditions in an inert gas, and which not only have excellent heat resistance and filling or planarization properties of a pattern formed on a substrate, but also form an organic film having excellent film formability and adhesion to a substrate. Further, the present application also provides a substrate for manufacturing a semiconductor device using the above-described material, a method for forming an organic film, and a method for forming a pattern. In addition, an aromatic carboxylic anhydride having a crosslinkable site, which is expected to be a raw material useful in industry such as electronic materials and aerospace materials, is provided.

[0028] [Means for Solving the Problems]

[0029] To solve the above-described problems, the present application provides an organic film forming material containing: (A) a compound represented by the following general formula (1A), and (B) an organic solvent.

[0030] [Chemical Formula 1]

[0031]

[0032] (In the formula, W1 is an n1-valent organic group, n1 represents an integer of 2 to 4, and X1 is a group represented by the following general formula (1B).

[0033] [Chemical Formula 2]

[0034]

[0035] (In the formula, n2 is 1 or 2, R1 is any one of groups represented by the following formula (1C), and a substituent can be present on the aromatic ring, and two or more kinds of R1 of the end structure can be used in combination.)

[0036] [Chemical 3]

[0037]

[0038] As long as the organic film-forming material is hardened under film-forming conditions in not only air but also an inert gas, an organic film-forming material having high heat resistance, good film-forming properties for a substrate, tight adhesion, and high filling / plane characteristics can be formed.

[0039] Further, the present application is preferably a compound represented by the following general formula (1D) for the component (A) described above.

[0040] [Chemical 4]

[0041]

[0042] (In the formula, W2 is a single bond or a divalent organic group, n3, n4 are integers satisfying 2 ≤ n3 + n4 ≤ 4, and a substituent can be present on the benzene ring in the formula, and the organic group in W2 and the substituent on the benzene ring can be bonded to form a cyclic organic group; X1 is the same as described above.)

[0043] In the compound contained in the organic film-forming material, not only the hardening property due to the end structure as described above, but also the physical properties and the like can be adjusted in accordance with the required properties such as heat resistance and etching resistance by combining various structures of W2 adjacent to the benzene ring structure. As examples, there can be mentioned a method of moderating the interaction between molecules by introducing a substituent that imparts flexibility to W2, thereby inhibiting crystallinity, thereby improving solubility in an organic solvent and film-forming properties, a method of improving filling / plane characteristics by introducing a substituent that imparts fluidity, and the like.

[0044] At this time, W2 in the general formula (1D) described above is preferably a single bond or any one of groups represented by the following formula (1E).

[0045] [Chemical 5]

[0046]

[0047] (In the formula, a substituent can be present on the aromatic ring.)

[0048] The compound contained in the organic film-forming material has a partial structure as described above, and is preferable in view of heat resistance and solvent solubility.

[0049] Further, in the present application, n3 and n4 in the above general formula (1D) are preferably those satisfying the relationships 1 ≤ n3 ≤ 2, 1 ≤ n4 ≤ 2, and 2 ≤ n3 + n4 ≤ 4.

[0050] By using a compound satisfying the above relationships, the compound contained in the organic film-forming material can form an organic film having not only heat resistance but also excellent burying / planarization properties.

[0051] Further, in the present application, the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the above (A) component, as measured by gel permeation chromatography in terms of polystyrene, is preferably 1.00 ≤ Mw / Mn ≤ 1.10.

[0052] By controlling the Mw / Mn of the compound contained in the organic film-forming material to be within such a range, an organic film having excellent burying properties and planarization properties can be formed.

[0053] Further, in the present application, the above (B) component 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 more.

[0054] As long as it is such an organic film-forming material, by imparting heat flowability to the compound by adding a high-boiling solvent, it becomes an organic film-forming material having higher degrees of burying and planarization properties.

[0055] Further, in the present application, the above organic film-forming material preferably further contains one or more of (C) an acid generator, (D) a surfactant, (E) a crosslinking agent, and (F) a plasticizer.

[0056] The organic film-forming material of the present application can contain one or more of the above (C) to (F) components in order to achieve the object thereof.

[0057] Further, the present application provides a substrate for semiconductor device production, characterized by having formed thereon an organic film hardened from the above-described organic film-forming material.

[0058] As long as it is the organic film-forming material of the present application, by having high degrees of burying / planarization properties, it becomes an organic film having no small voids due to burying defects or no unevenness on the surface of the organic film due to insufficient planarization. By the substrate for semiconductor device production planarized by the organic film-forming material of the present application, the process margin when patterning the substrate is widened, and semiconductor devices can be produced with good yield.

[0059] Further, the present application provides a method for forming an organic film, which is a method for forming an organic film suitable for use in a manufacturing step of a semiconductor device, and which comprises spin-coating the above-mentioned organic film-forming material on a substrate to be processed, and applying heat treatment to the coated substrate to be processed in a non-reactive gas atmosphere at a temperature of 50°C or higher and 600°C or lower for a period of 10 seconds to 7200 seconds to form an organic film.

[0060] Further, the present application provides a method for forming an organic film, which is a method for forming an organic film suitable for use in a manufacturing step of a semiconductor device, and which comprises spin-coating the above-mentioned organic film-forming material on a substrate to be processed, and applying heat treatment to the coated substrate to be processed in a non-reactive gas atmosphere at a temperature of 50°C or higher and 600°C or lower for a period of 10 seconds to 7200 seconds to form an organic film.

[0061] The organic film formed by the method for forming an organic film of the present application has high heat resistance and high degree of filling / plane characteristics, and if used in a manufacturing step of a semiconductor device, the yield of the semiconductor device becomes good.

[0062] At this time, the oxygen concentration in the non-reactive gas atmosphere is preferably 1% or less.

[0063] As long as it is the organic film-forming material of the present application, even if heated in such a non-reactive gas atmosphere, no sublimates are generated and hardening is sufficiently performed, and in addition, an organic film having excellent adhesion to a substrate can be formed.

[0064] Further, as the substrate to be processed, a substrate to be processed having a structure or a step difference of 30 nm or more in height is preferably used.

[0065] The method for forming an organic film of the present application is particularly useful in the case of forming a flat organic film on a substrate to be processed having such a concave-convex structure.

[0066] Further, the present application provides a method for forming a pattern, which comprises forming an organic film on a substrate to be processed using the above-mentioned organic film-forming material, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring a pattern to the silicon-containing resist intermediate film by etching using the patterned resist upper layer film as a mask, transferring a pattern to the organic film by etching using the pattern-transferred silicon-containing resist intermediate film as a mask, and further transferring a pattern to the substrate to be processed by etching using the pattern-transferred organic film as a mask.

[0067] Further, the present application provides a pattern forming method, in which an organic film is formed on a processed body using the above-described material for forming an organic film, an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a titanium oxide film, and a titanium nitride film is formed on the organic film, an organic antireflection film is formed on the inorganic hard mask intermediate film, a resist upper layer film is formed on the organic antireflection film using a photoresist composition to make a four-layer film structure, a circuit pattern is formed on the resist upper layer film, a pattern is transferred to the above-described organic antireflection film and the above-described inorganic hard mask intermediate film by etching using the pattern-formed resist upper layer film as a mask, a pattern is transferred to the above-described organic film by etching using the pattern-transferred inorganic hard mask intermediate film as a mask, and further, a pattern is transferred to the above-described processed body by etching using the pattern-transferred organic film as a mask.

[0068] Further, the present application provides a pattern forming method, in which an organic film is formed on a processed body using the above-described material for forming an organic film, an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a titanium oxide film, and a titanium nitride film is formed on the organic film, an organic antireflection film is formed on the inorganic hard mask intermediate film, a resist upper layer film is formed on the organic antireflection film using a photoresist composition to make a four-layer film structure, a circuit pattern is formed on the resist upper layer film, a pattern is transferred to the above-described organic antireflection film and the above-described inorganic hard mask intermediate film by etching using the pattern-formed resist upper layer film as a mask, a pattern is transferred to the above-described organic film by etching using the pattern-transferred inorganic hard mask intermediate film as a mask, and further, a pattern is transferred to the above-described processed body by etching using the pattern-transferred organic film as a mask.

[0069] Further, the present application provides a pattern forming method, in which an organic film is formed on a processed body using the above-described material for forming an organic film, an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a titanium oxide film, and a titanium nitride film is formed on the organic film, an organic antireflection film is formed on the inorganic hard mask intermediate film, a resist upper layer film is formed on the organic antireflection film using a photoresist composition to make a four-layer film structure, a circuit pattern is formed on the resist upper layer film, a pattern is transferred to the above-described organic antireflection film and the above-described inorganic hard mask intermediate film by etching using the pattern-formed resist upper layer film as a mask, a pattern is transferred to the above-described organic film by etching using the pattern-transferred inorganic hard mask intermediate film as a mask, and further, a pattern is transferred to the above-described processed body by etching using the pattern-transferred organic film as a mask.

[0070] The organic film forming material of the present application can be suitably used in various pattern forming methods such as a 3-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask intermediate film, or a 4-layer resist process using these in addition to an organic anti-reflective film, and the like. In the manufacturing steps of a semiconductor device, as long as a circuit pattern is formed by the pattern forming method of the present application as such, a semiconductor device can be manufactured with good yield.

[0071] At this time, the inorganic hard mask intermediate film is preferably formed by a CVD method or an ALD method.

[0072] The pattern forming method of the present application, for example, can form an inorganic hard mask intermediate film by such a method.

[0073] Further, in the formation of the circuit pattern, the present application is preferably performed by photolithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprint, or a combination thereof.

[0074] Further, in the formation of the circuit pattern, the present application is preferably performed by photolithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprint, or a combination thereof.

[0075] The pattern forming method of the present application can suitably use such a means for forming a circuit pattern and a means for developing.

[0076] Further, the present application is preferably used as the processed object, a semiconductor device substrate, or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film is formed.

[0077] At this time, the processed object is preferably one containing silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof.

[0078] As long as it is the pattern forming method of the present application, a processed substrate as described above can be processed to form a pattern.

[0079] Further, the present application provides an organic film forming compound represented by the following general formula (1A).

[0080] [Chemical Formula 6]

[0081]

[0082] (In the formula, W1 is an n1-valent organic group, n1 represents an integer of 2 to 4, and X1 is a group represented by the following general formula (1B).)

[0083] [Chemical Formula 7]

[0084]

[0085] (In the formula, n2 is 1 or 2, and R1 is any of the groups represented by the following formula (1C). It may also have substituents on the aromatic ring, and R1 may be used in combination with two or more terminal structures.)

[0086] [Chemistry 8]

[0087]

[0088] Such organic film-forming compounds can be hardened not only in air but also in inert gas conditions to form films with high heat resistance and high degree of packing / planarization properties. Furthermore, through the effect of the dioxin structure containing oxygen heterocycles, organic film-forming compounds with excellent film-forming properties or adhesion to the substrate are formed.

[0089] Furthermore, in this invention, the compound for forming the organic film is preferably represented by the following general formula (1D).

[0090] [Chemistry 9]

[0091]

[0092] (In the formula, W2 is a single bond or a divalent organic group, n3 and n4 are integers that satisfy 2≤n3+n4≤4. Substituents may also be present on the benzene ring in the formula. The organic group in W2 and the substituents on the benzene ring may also bond to form a cyclic organic group; X1 is the same as above.)

[0093] As long as it is an organic film-forming compound, it will have curing properties not only in air but also in inert gas conditions, and will exhibit excellent heat resistance regardless of the film-forming conditions.

[0094] In this case, W2 in the above general formula (1D) should preferably be a single bond or any of the groups represented by the following formula (1E).

[0095] [Chemistry 10]

[0096]

[0097] (In this formula, the aromatic ring may also have substituents.)

[0098] As long as it is an organic film-forming compound, it will have curing properties not only in air but also in inert gas conditions, and will exhibit excellent heat resistance regardless of the film-forming conditions.

[0099] Furthermore, the present invention is preferably one in which n3 and n4 in the above general formula (1D) satisfy the relationship 1≤n3≤2, 1≤n4≤2, 2≤n3+n4≤4.

[0100] As long as the compound for forming an organic film is as described above, it becomes a compound for forming an organic film that suppresses film shrinkage at the time of hardening and has excellent burying / planarizing properties.

[0101] Further, the present application provides an aromatic carboxylic anhydride represented by the following general formula (1F).

[0102] [Chemical 11]

[0103]

[0104] (In the formula, n2 is 1 or 2, R1 is any one of groups represented by the following formula (1G), a substituent can also be present on the aromatic ring, and two or more kinds of R1 having different end structures can also be used in combination.)

[0105] [Chemical 12]

[0106]

[0107] As long as the aromatic carboxylic anhydride is as described above, it becomes an aromatic carboxylic anhydride that contains an ether structure and a crosslinking group as an end structure and does not contain a large number of polar groups. Such an aromatic carboxylic anhydride not only imparts heat resistance and crosslinkability to an imide material containing polyimide, but also imparts high Tg and processability (film formability, etc.) such opposite properties. Therefore, as an imide material, it not only imparts heat resistance, but also imparts the properties required in electronic materials or aerospace materials that require low dielectric constant, hardening properties, etc., and as a capping agent for polyimide, imide compounds, it becomes a very useful candidate in industry.

[0108] [Effects of the Invention]

[0109] As explained above, the organic film forming compound of the present application, even if film formation in a passivation gas for preventing corrosion of a substrate is performed, does not generate a by-product and is hardened, and is a useful compound for forming an organic film having high degree of filling and planarization characteristics, heat resistance, etching resistance, film formability, and adhesion. Further, the organic film forming material containing the compound has excellent filling / planarization characteristics, and becomes a material for forming an organic film having various characteristics such as heat resistance, etching resistance, adhesion to a substrate, film formability, and the like. Therefore, it is extremely useful, for example, as an organic film material in a multilayer resist method such as a 2-layer resist method, a 3-layer resist method using a silicon-containing resist intermediate film, a 4-layer resist method using a silicon-containing resist intermediate film and an organic antireflection film, and the like, or as a planarization material for semiconductor device manufacturing. Further, the organic film formed from the organic film forming material of the present application is excellent in heat resistance, and therefore even if an inorganic hard mask intermediate film is formed on the organic film, film thickness variation due to thermal decomposition does not occur, and is suitable for pattern formation. Further, the aromatic carboxylic anhydride used in the terminal structure introduction can be expected to be used as an end-capping agent for a polyimide, an imide compound used in electronic materials or aerospace materials, as an industrially useful material. BRIEF DESCRIPTION OF DRAWINGS

[0110] [ Figure 1 ] Figure 1 is a diagram for explaining planarization characteristics in the present application.

[0111] [ Figure 2 ] Figure 2 is a diagram for explaining an example of a pattern formation method using a 3-layer resist method in the present application.

[0112] [ Figure 3 ] Figure 3 is a diagram for explaining a method for evaluating filling characteristics in the examples.

[0113] [ Figure 4 ] Figure 4 is a diagram for explaining a method for evaluating planarization characteristics in the examples. DETAILED DESCRIPTION

[0114] As explained above, development of an organic film forming material for film formation in a passivation gas for preventing corrosion of a substrate, for example, an organic film forming compound useful in a pattern formation method using the material, which does not generate a by-product even at 300°C or higher, and can form an organic film excellent not only in filling or planarization characteristics of a pattern formed on a substrate, but also in dry etching resistance during substrate processing, and in which film thickness variation of the organic film due to thermal decomposition does not occur even if an inorganic hard mask intermediate film is formed on the organic film, is sought.

[0115] Generally, when forming an organic film, a composition is prepared by dissolving an organic film-forming compound in an organic solvent, and the composition is applied to a substrate on which a structure or wiring for forming a semiconductor device and the like is formed, and then calcination is performed to form an organic film. The composition forms a coating film following the shape of the uneven structure on the substrate immediately after application, and if the coating film is calcined, most of the organic solvent evaporates during the period until hardening, and an organic film is formed from the organic film-forming compound remaining on the substrate. The present inventors have conceived that if the organic film-forming compound remaining on the substrate at this time has sufficient thermal fluidity, the uneven shape immediately after application is planarized by thermal fluidity, and a planar film can be formed.

[0116] The present inventors have further repeated intensive investigations, and have found that if the organic film-forming compound represented by the following general formula (1A) is used, thermal hardening properties equivalent to those of conventional resist underlayer film materials are obtained not only in air but also in an inert gas by the action of the substituent represented by R1, and general polyimide and imide compounds such as solvent solubility, adhesion, thermal fluidity, high degree of embedding / planarization properties, and the like are imparted without impairing heat resistance by introducing a crosslinking structure connected by an ether linkage to the terminal, and thus an organic film-forming material having not only planarity on a processed substrate but also heat resistance that does not cause variation in the thickness of a coating film due to thermal decomposition even when an inorganic hard mask intermediate film is formed has been obtained, and the present application has been completed.

[0117] That is, the present application is an organic film-forming material containing (A) a compound represented by the following general formula (1A), and (B) an organic solvent.

[0118] [Chemical Formula 13]

[0119]

[0120] (In the formula, W1 is an n1-valent organic group, n1 represents an integer of 2 to 4, and X1 is a group represented by the following general formula (1B).

[0121] [Chemical Formula 14]

[0122]

[0123] (In the formula, n2 is 1 or 2, R1 is any one of groups represented by the following formula (1C), and can have a substituent on the aromatic ring, and two or more kinds of R1 can be used in combination.

[0124] [Chemical Formula 15]

[0125]

[0126] The present application will be described in detail below, but the present application is not limited to these.

[0127] <Compound for organic film formation>

[0128] The compound for organic film formation of the present application is a compound for organic film formation represented by the following general formula (1A).

[0129] [Chemical Formula 16]

[0130]

[0131] (In the formula, W1 is an n1-valent organic group, n1 represents an integer of 2 to 4, and X1 is a group represented by the following general formula (1B).

[0132] [Chemical Formula 17]

[0133]

[0134] (In the formula, n2 is 1 or 2, R1 is any one of groups represented by the following formula (1C), can have a substituent on the aromatic ring, and two or more kinds of R1 of the terminal structure can be combined and used.

[0135] [Chemical Formula 18]

[0136]

[0137] R1 represented by the above formula (1C) functions as a thermal crosslinking group. Considering the hardening property, heat resistance, and ease of procurement of raw materials, it is preferable to be an ethynyl group or an ethynylphenyl group. As a substituent on the aromatic ring, halogen atoms such as fluorine, bromine, and iodine, alkyl groups such as a methyl group, an ethyl group, and a propyl group, and the like can be exemplified, and considering the ease of procurement of raw materials, it is preferable to be fluorine as a substituent.

[0138] The terminal structure represented by the above general formula (1B) is a pre-closed ring imide structure. A polyimide varnish used as a film material is generally used as a polyimide film after being coated as an intermediate amic acid, being heat-closed to form a film, and the compound represented by the above general formula (1A) of the organic film-forming compound of the present application is a soluble imide compound that is pre-closed. Therefore, there is no elimination reaction such as dehydration generated when heat-closing the amic acid precursor of the imide compound, and film shrinkage is suppressed without impairing the planarity of the organic film. Furthermore, by pre-preparing a stable imide compound, decomposition and the like caused by the equilibrium reaction of the imide compound precursor such as amic acid is suppressed, and there is also an advantage in terms of storage stability. Furthermore, by bonding the imide structure and the terminal structure having a cross-linking group structure via an ether group, flowability can be imparted without impairing heat resistance, and the heat flowability at the time of film formation can be imparted while maintaining high heat resistance. Furthermore, in the organic film-forming compound of the present application, the terminal structure represented by general formula (1B) containing an imide structure is also consistent with the design concept of a polyimide material having low dielectric constant, low moisture absorption, high processability, and the like, and is expected to be applicable not only to planarization for semiconductor substrates, but also to a wide range of material fields in which polyimide & imide compounds are used for electronic material applications, aerospace material applications, and the like.

[0139] In general formula (1B), n2 is 1 or 2, and it is preferable that n2 = 1 in terms of ease of raw material procurement and production. As the substituents on the aromatic ring, halogen atoms such as fluorine, bromine, and iodine, alkyl groups such as methyl, ethyl, and propyl, and the like can be exemplified, and in the case where the number of substituents on the aromatic ring of the imide structure is N1, the relationship 0 ≤ N1 ≤ 3 is satisfied. Furthermore, in the case where the number of substituents on the aromatic ring having R1 is N2, the relationship 0 ≤ N2 ≤ 3, 1 ≤ n2 ≤ 2, and 1 ≤ n2 + N2 ≤ 4 is satisfied. In terms of ease of raw material procurement, it is preferable that the substituents be fluorine.

[0140] Further, the terminal structure represented by R1 that functions as a cross-linking group is a cross-linking catalyst such as a thermal acid generator or the like that is generally used as a cross-linking agent, and does not generate a sharp hardening reaction due to the action of the catalyst during heat treatment at the time of film formation, and does not generate a sharp decrease in heat flowability, and is advantageous in terms of imparting heat flowability and becomes an organic film-forming compound having excellent burying / planarization properties. Further, hardening is performed by cyclization of the triple bonds with each other and polymerization of the double bonds with each other, and is a cross-linking method that does not involve elimination reactions and the like, and becomes an organic film-forming compound that can form an organic film having excellent planarization properties with suppressed film shrinkage at the time of hardening.

[0141] In the above general formula (1A), n1 is an integer of 2 to 4.

[0142] W1in the above general formula (1A) is an n1-valent organic group, and examples thereof include the following structural formulae, and the aromatic ring thereof can also have a substituent. Further, as the substituent, a hydroxyl group, a trifluoromethyl group, an alkyl group having a carbon number of 1 to 10, an alkynyl group or an alkenyl group having a carbon number of 3 to 10, an alkyloxy group having a carbon number of 1 to 10, an alkynyl oxy group or an alkenyl oxy group having a carbon number of 3 to 10, an aryl group having a carbon number of 6 to 10, a thiol group, a nitro group, a halogen group, a nitrile group, a sulfonic acid group, an alkoxycarbonyl group having a carbon number of 2 to 10, an alkanoyloxy group having a carbon number of 2 to 10, and the like can be exemplified.

[0143] [Chemical Formula 19]

[0144]

[0145] [Chemical Formula 20]

[0146]

[0147] [Chemical Formula 21]

[0148]

[0149] [Chemical Formula 22]

[0150]

[0151] In the present application, the above-mentioned compound for forming an organic film is preferably represented by the following general formula (1D).

[0152] [Chemical Formula 23]

[0153]

[0154] (In the formula, W2is a single bond or a 2-valent organic group, n3, n4are integers satisfying 2 ≤ n3 + n4 ≤ 4, and the benzene ring in the formula can also have a substituent, and the organic group in W2and the substituent on the benzene ring can also be bonded to form a cyclic organic group. X1is the same as described above.)

[0155] Further, the compound for forming an organic film of the present application is preferably W2in the above-mentioned general formula (1D) is a single bond, or any one of the groups represented by the following formula (1E). Among these, from the viewpoint of imparting solvent solubility and fluidity, it is preferable that it is a single bond, or has an ether bond, an isopropylidene structure, a hexafluoroisopropylidene structure, a fluorene structure, or an indane structure formed by the aromatic ring bonded to the imide ring.

[0156] [Chemical Formula 24]

[0157]

[0158] (In the formula, the aromatic ring can also have a substituent.)

[0159] Further, the present application is preferably one in which n3 and n4 in the above general formula (1D) satisfy the relationship 1 < n3 < 2, 1 < n4 < 2, and 2 < n3 + n4 < 4.

[0160] By satisfying such a relationship between n3 and n4, a compound for forming an organic film having both burying / planarizing properties, without impairing heat hardenability and heat resistance, is obtained. Particularly, one in which 1 < n3 < 2, 1 < n4 < 2, and 3 < n3 + n4 < 4 is preferable from the viewpoint of heat resistance. Of these, one in which the above relationship is satisfied, and W2 in the above general formula (1D) is a single bond, or any one of an ether bond, an isopropylidene structure, a hexafluoroisopropylidene structure, and a fluorene structure is preferable, and more preferably a single bond, an ether bond, or a fluorene structure. In this case, X1 is a substituent on a benzene ring, and when there are two or more X1 on one aromatic ring, that is, when n3 = 2 and / or n4 = 2, it is more preferable that the substituents X1 on the two aromatic rings are adjacent on one aromatic ring. When this relationship is satisfied, not only is the solubility in a solvent improved due to steric hindrance between the imide groups, but also heat resistance and heat flowability, which are conflicting functions in imide compounds, can be satisfied.

[0161] [Chemical Formula 25]

[0162]

[0163] (In the formula, W2 and X1 are the same as above.)

[0164] In the present application, the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the compound for forming an organic film, as measured by gel permeation chromatography in terms of polystyrene, is preferably 1.00 < Mw / Mn < 1.10. By controlling the Mw / Mn of the compound for forming an organic film to be within this range, an organic film having excellent burying properties and planarization can be formed.

[0165] Even if it is a mixture of single-molecule compounds containing a plurality of end structures and main skeleton structures, as long as it is within the range of Mw / Mn as described above, the heat flowability of the compound for forming an organic film is further improved, and thus, when blended in the material for forming an organic film described below, not only can the fine structures formed on a substrate be excellently buried, but also an organic film in which the entire substrate becomes flat can be formed.

[0166] Method for producing a compound for forming an organic film

[0167] As a means for obtaining the organic film-forming compound of the present application, an amic acid compound can be obtained by reacting an amine compound represented by the following formula with an aromatic carboxylic anhydride (STEP 1), and then by performing thermal or chemical imidization (STEP 2). The amine compound or the aromatic carboxylic anhydride used in the synthesis of the amic acid compound can be used alone or two or more kinds thereof can be used. These can be appropriately selected and combined in accordance with the desired properties. In the following formula, W1, R1, n1, and n2 are the same as described above. Furthermore, not limited to the planarization of semiconductor substrates, when forming an organic film for electronic materials or the like, the amic acid compound itself can be used as an organic film-forming compound without performing imidization.

[0168] STEP 1: Synthesis of amic acid compound

[0169] [Chemical Formula 26]

[0170]

[0171] STEP 2: Synthesis of imide compound

[0172] [Chemical Formula 27]

[0173]

[0174] The synthesis of the amic acid compound represented by STEP 1 can generally be performed in an organic solvent at room temperature or under cooling or heating as required. As the solvent that can be used, alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; chlorine-based solvents such as dichloromethane, chloroform, and dichloroethane; hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, and γ-butyrolactone; aprotic polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide; and the like can be used alone or two or more kinds thereof can be used in combination. These solvents can be used in a range of 0 to 2,000 parts by mass with respect to 100 parts by mass of the raw material of the reaction, and the reaction temperature is preferably about -50°C to the boiling point of the solvent, and more preferably room temperature to 150°C. The reaction time is preferably appropriately selected from 0.1 to 100 hours.

[0175] As the base catalyst, inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, potassium phosphate, and the like, and organic bases such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, and the like can be used. These can be used alone or in combination of two or more. The amount used is preferably 0.01 to 20 moles, and more preferably 0.05 to 10 moles, relative to the number of moles of the aromatic carboxylic anhydride as the raw material.

[0176] As the reaction method, there are a method in which the amine compound and the aromatic carboxylic anhydride are added together into a solvent, a method in which the amine compound and the aromatic carboxylic anhydride are separately or mixed, and are added by being dropped while being dispersed or dissolved in a solvent, a method in which one of the amine compound and the aromatic carboxylic anhydride is dispersed or dissolved in a solvent, and the other is added by being dropped, and the like. Further, in a case where the amine compound and the aromatic carboxylic anhydride are added in plural, there is a method in which they are mixed in advance and allowed to react, and there is also a method in which they are allowed to react sequentially. In a case where a catalyst is used, there are a method in which the catalyst is added together with the amine compound or the aromatic carboxylic anhydride, and a method in which the catalyst is dispersed or dissolved in advance and then added by being dropped. The obtained amic acid solution can be subjected to the dehydration imidization reaction of STEP 2. Further, the obtained amic acid solution is not limited to a use for a semiconductor material, and can be used directly as a compound for forming an organic film, and can be diluted in an organic solvent, subjected to liquid-liquid separation and washing, and recovered, in order to remove unreacted raw materials, a catalyst, and the like present in the system.

[0177] As the organic solvent used in the liquid-liquid separation and washing, there is no particular limitation as long as it is a solvent in which the compound is soluble and is separated into two layers when mixed with water, and there are, for example, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and the like, esters such as ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, and the like, ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, methyl isobutyl ketone, and the like, ethers such as diethyl ether, diisopropyl ether, methyl-tert-butyl ether, ethyl cyclopentyl methyl ether, and the like, chlorine-based solvents such as dichloromethane, chloroform, dichloroethane, trichloroethylene, and the like, and mixtures thereof. As the washing water used at this time, deionized water or ultrapure water can be used. The number of times of washing is preferably one or more, and is more preferably about 1 to 5.

[0178] In the liquid-liquid separation and washing, in order to remove unreacted raw materials and acidic components in the system, washing with an aqueous alkali solution can be performed. As the alkali, specifically, there are, for example, hydroxides of alkali metals, carbonates of alkali metals, hydroxides of alkaline earth metals, carbonates of alkaline earth metals, ammonia, and organic amines.

[0179] Further, in order to remove unreacted raw materials, metal impurities, and base components from the system during the liquid-liquid washing, washing with an acidic aqueous solution can also be performed. As the acid, 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 can be exemplified.

[0180] The liquid-liquid washing with the basic aqueous solution and the acidic aqueous solution can be performed only one of them, or can be performed in combination. From the viewpoint of removing metal impurities, the liquid-liquid washing is preferably performed in the order of the basic aqueous solution and the acidic aqueous solution.

[0181] After the liquid-liquid washing with the basic aqueous solution and the acidic aqueous solution, washing with neutral water can also be performed. The number of times of washing is one or more, and is preferably about 1 to 5. As the neutral water, deionized water, ultrapure water, or the like described above can be used. The number of times of washing is one or more, but the number of times is sometimes insufficient to remove the base components and the acidic components. Even if washing is performed 10 or more times, the effect of the number of times of washing is not necessarily obtained, and thus the number of times is preferably about 1 to 5.

[0182] Further, the reaction product after the liquid-liquid operation can be recovered as a powder by concentration and drying or crystallization under reduced pressure or normal pressure. In order to improve the handleability in the production of the organic film-forming material of the present application described later, the reaction product can also be prepared as a solution at an appropriate concentration. The concentration is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass. As long as the concentration is within this range, the viscosity does not easily increase, and thus the handleability can be prevented from being deteriorated. Further, the amount of the solvent does not become excessive, and thus the economy is improved.

[0183] As the solvent at this time, there is no particular limitation as long as the compound can be dissolved, and if specific examples are exemplified, ketones such as cyclohexanone and methyl-2-pentyl 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, 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 mono-tert-butyl ether acetate can be exemplified. These can be used alone or in combination of two or more.

[0184] The imide compound obtained in STEP 2 can be synthesized by thermal or chemical imidization. These methods can be appropriately selected in accordance with the thermal stability of the crosslinking group of the imide compound as the object, the substituent introduced, and the reactivity of the reagent used at the time of chemical imidization.

[0185] In the case of performing thermal imidization, to the reaction solution of the amic acid compound obtained in STEP 1 (in the case of recovering as a powder, it can be dissolved in a soluble solvent in advance), a solvent that can be azeotroped with water is added, and heating is performed at 100°C to 250°C, and imidization is performed by dehydration ring closure reaction while removing the generated water.

[0186] As the solvent that can be azeotroped with water, esters such as γ-butyrolactone, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, and N,N-dimethylformamide, nonpolar solvents such as benzene, toluene, xylene, and mesitylene, and the like can be used, and these solvents can be heated alone or in a mixture, and dehydration is preferably performed while distilling the water generated by ring closure to the outside of the system. These solvents can be used in a range of 0 to 2,000 parts by mass with respect to 100 parts by mass of the reaction raw material.

[0187] In the case of performing chemical imidization, to the reaction solution of the amic acid compound obtained in STEP 1 (in the case of recovering as a powder, it can be dissolved in a soluble solvent in advance), an acid anhydride or the like as a dehydrating agent and a base catalyst are added, and imidization is performed at a temperature of 0°C to 120°C.

[0188] As the base catalyst used in chemical imidization, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like can be exemplified, and pyridine is preferable because it has appropriate basicity for the reaction. As the dehydrating agent, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride, trifluoroacetic anhydride, polyphosphoric acid, phosphorus pentoxide, phosphorus pentachloride, thionyl chloride, and the like can be exemplified, and acetic anhydride is preferable from the viewpoint of purification after the reaction. The amount of use of these catalysts is in a range of 0.1 to 20 moles with respect to the number of moles of the acid anhydride of the raw material, and is preferably in a range of 0.2 to 10 moles. In addition, the base catalyst and the dehydrating agent can be used alone or in a mixture of two or more, and these can be appropriately controlled by adjusting the amount of the catalyst, the amount of the dehydrating agent, the reaction temperature, and the reaction time in accordance with the properties required for the compound as the object.

[0189] As the solvent used at this time, there is no particular limitation as long as it is a solvent that is inert to the above reaction, and examples include ethers such as diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, and the like; chlorine-based solvents such as dichloromethane, chloroform, dichloroethane, trichloroethylene, and the like; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene, and the like; nitriles such as acetonitrile and the like; ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone, cyclohexanone, and the like; esters such as methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, γ-butyrolactone, and the like; aprotic polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, hexamethylphosphoric triamide, and the like; and the like, which can be used alone or in combination. These solvents can be used in a range of 0 to 2,000 parts by mass with respect to 100 parts by mass of the reaction raw material.

[0190] As for the reaction method and the method for recovering the compound, the method described in the paragraph on the amide acid compound can be used.

[0191] As described above, as long as it is the organic film-forming compound of the present application, it becomes to give an organic film-forming material that has both heat resistance of 400°C or higher and a high degree of filling / plane characteristics.

[0192] Further, in the present application, the plane characteristics refer to the performance of planarizing the surface of a substrate. As long as it is the organic film-forming material containing the organic film-forming compound of the present application, for example, as shown in Figure 1 As shown in the above, the organic film-forming material 3' is applied to the substrate 1, and the organic film 3 is formed by heating, whereby the 100 nm height difference in the substrate 1 can be reduced to 30 nm or less. Further, Figure 1 The height difference shape shown in the above is a typical example of the height difference shape in a substrate for semiconductor device manufacturing, and the height difference shape of the substrate that can be planarized by the organic film-forming material containing the organic film-forming compound of the present application is, of course, not limited to this height difference shape.

[0193] <aromatic carboxylic anhydride>

[0194] The aromatic carboxylic anhydride of the present application is represented by the following general formula (1F).

[0195] [Chemical Formula 28]

[0196]

[0197] (In the formula, n2 is 1 or 2, R1 is any one of the groups represented by the following formula (1G), a substituent can also be present on the aromatic ring, and two or more kinds of R1 of the end structure can also be used in combination.)

[0198] [Chemical Formula 29]

[0199]

[0200] R1 represented by the above formula (1G) functions as a thermal crosslinking group. In terms of curability, heat resistance, and ease of procurement of raw materials, it is preferable to be an ethynyl group, an ethynylphenyl group. As substituents on the aromatic ring, halogen atoms such as fluorine, bromine, and iodine, alkyl groups such as a methyl group, an ethyl group, and a propyl group, and the like can be exemplified, and in terms of ease of procurement of raw materials, it is preferable to be fluorine as a substituent.

[0201] In the above general formula (1F), n2 is 1 or 2, and in terms of ease of procurement and production of raw materials, it is preferable for n2 = 1. As substituents on the aromatic ring, halogen atoms such as fluorine, bromine, and iodine, alkyl groups such as a methyl group, an ethyl group, and a propyl group, and the like can be exemplified, and in the case where the number of substituents on the aromatic ring of the anhydride is N1, the relationship 0 ≤ N1 ≤ 3 is satisfied, and furthermore, in the case where the number of substituents on the aromatic ring having R1 is N2, the relationship 0 ≤ N2 ≤ 3, 1 ≤ n2 ≤ 2, and 1 ≤ n2 + N2 ≤ 4 is satisfied. In terms of ease of procurement of raw materials, it is preferable to be fluorine as a substituent.

[0202] As long as it is an aromatic carboxylic anhydride as described above, it becomes an aromatic carboxylic anhydride containing an ether structure and a crosslinking group as a terminal structure, and not containing a large number of polar groups. Such an aromatic carboxylic anhydride not only imparts heat resistance and crosslinkability to an imide-based material containing a polyimide, but also imparts high Tg and processability (film formability and the like) and such opposite properties. Therefore, not only heat resistance can be imparted to an imide material, but also the properties required for electronic materials or aerospace materials requiring low dielectric constant, curability, and the like can be imparted, and as an end-capping agent for polyimides and imide compounds, it becomes a very useful candidate in industry.

[0203] As the aromatic carboxylic anhydride as described above, the following can be exemplified.

[0204] [Chem. 30]

[0205]

[0206] [Chem. 31]

[0207]

[0208] [Chem. 32]

[0209]

[0210] [Chem. 33]

[0211]

[0212] [Chem. 34]

[0213]

[0214] As above, as long as it is an aromatic carboxylic anhydride of the present application, it is not limited to a raw material of a compound for forming a semiconductor planarization film, and can also be expected as a raw material of a polyimide, imide compound, etc. that can be used in electronic materials or aerospace materials, etc. as an industrially useful compound.

[0215] <Method for producing an aromatic carboxylic anhydride>

[0216] As a means for obtaining the aromatic carboxylic anhydride of the present application, synthesis can be performed by, after etherification by substitution reaction of the phthalonitrile having a fluorine substituent shown below with the phenol having R1 as a substituent (STEP 1), conversion to a carboxylic acid by hydrolysis of the nitrile (STEP 2), and dehydration condensation of the adjacent carboxylic acids with each other (STEP 3). R1, n1, and n2 in the formula below are the same as above. Furthermore, not limited to use in planarization of semiconductor substrates, when forming an organic film for electronic materials, etc., the amic acid compound can also be directly used as a compound for forming an organic film without imidization.

[0217] STEP 1: Substitution reaction

[0218] [Chemical Formula 35]

[0219]

[0220] STEP 2: Hydrolysis

[0221] [Chemical Formula 36]

[0222]

[0223] STEP 3: Dehydration condensation

[0224] [Chemical Formula 37]

[0225]

[0226] The substitution reaction shown in Step 1 is usually carried out in an organic solvent at room temperature or under cooling or heating as required. As the organic solvent that can be used, there can be mentioned alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, etc.; chlorine-based solvents such as dichloromethane, chloroform, dichloroethane, trichloroethylene, etc.; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene, etc.; nitriles such as acetonitrile, etc.; ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone, cyclohexanone, etc.; esters such as methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, γ-butyrolactone, etc.; aprotic polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, hexamethylphosphoric triamide, etc.; and the like, which can be used alone or in combination of two or more kinds. These solvents can be used in a range of 0 to 2,000 parts by mass relative to 100 parts by mass of the reaction raw material, and the reaction temperature is preferably about -50°C to the boiling point of the solvent, more preferably room temperature to 200°C. The reaction time is appropriately selected from 0.1 to 100 hours.

[0227] Their synthesis can also use a base catalyst as required, and as the base catalyst, there can be mentioned inorganic alkali compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, potassium phosphate, etc.; organic bases such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, etc., which can be used alone or in combination of two or more kinds. The amount used is preferably in a range of 0.01 to 20 moles, more preferably 0.05 to 10 moles, relative to the number of moles of the aromatic carboxylic anhydride of the raw material.

[0228] As to the reaction method and the recovery method of the compound, the method described in the paragraph of the amide acid compound can be used. The recovered compound can be refined by recrystallization, crystallization, distillation, etc. in cooperation with the physical properties of the reaction product. In addition, the reaction of the subsequent step can also be carried out without the post-reaction refining step.

[0229] The hydrolysis reaction shown in STEP 2 can be performed using distilled water, ion-exchange water, ultrapure water, or the like, usually at room temperature or under cooling or heating as required. Further, an organic solvent can also be used in addition to the above water, and as an organic solvent that can be used in combination with water, one or a combination of two or more of ethanol, methanol, propanol, acetone, methyl ethyl ketone, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, benzene, toluene, xylene, chloroform, dichloromethane, trichloroethylene, carbon tetrachloride, or the like can be used. There is no particular limitation on the amount of water used, and the amount used is preferably about 1 to 10 moles, and more preferably about 2 to 5 moles, relative to the ether compound of the raw material. As long as the amount of water used is equal to or greater than the lower limit value, the hydrolysis reaction is sufficiently performed. Further, as long as the amount used is equal to or less than the upper limit value, the solvent is not used in a large amount, and improvement in yield can be expected. In the case of using an organic solvent, the amount used is in the range of 0 to 2,000 parts by mass relative to 100 parts by mass of water, and the reaction temperature is preferably about -50°C to the boiling point of the solvent, and more preferably room temperature to 200°C. The reaction time is appropriately selected from 0.1 to 100 hours.

[0230] In these syntheses, an acid or base catalyst can be used as required to perform the hydrolysis reaction. As the acid catalyst used at this time, hydrochloric acid, sulfuric acid, nitric acid, chloric acid, bromic acid, methanesulfonic acid, p-toluenesulfonic acid, or the like can be used, and one or a combination of two or more of these can be used. As the base catalyst, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, or the like can be used, and one or a combination of two or more of these can be used. The amount used is in the range of 0.01 to 20 moles, and preferably 0.05 to 10 moles, relative to the number of moles of the ether compound of the raw material. In this range of the amount of acid or base used, the hydrolysis can be performed more efficiently.

[0231] As for the reaction method and the method for recovering the compound, the method described in the paragraph on the amide acid compound can be used. The recovered compound can be refined by recrystallization, crystallization, distillation, or the like in conjunction with the physical properties of the reaction product. These can also be subjected to the subsequent step without going through the post-reaction refining step.

[0232] The dehydration condensation reaction shown in STEP 3 can be performed by adding a solvent that can be azeotroped with water, and heating to 100°C to 250°C, while removing the generated water, to convert it into an anhydride by a dehydration ring closure reaction.

[0233] As the solvent which can be azeotroped with water, an ester such as γ-butyrolactone, a polar solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, a nonpolar solvent such as benzene, toluene, xylene, mesitylene, and the like can be used, and it is preferable to heat these solvents alone or in a mixture and to remove water generated by the ring closure outside the system. These solvents can be used in a range of 0 to 2,000 parts by mass relative to 100 parts by mass of the reaction raw material.

[0234] As another method of the dehydration condensation reaction, a method using a dehydrating agent can be used, and an acid anhydride or the like as a dehydrating agent can be added and converted into an acid anhydride at a temperature of 0°C to 120°C.

[0235] As the dehydrating agent, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride, trifluoroacetic anhydride, polyphosphoric acid, phosphorus pentoxide, phosphorus pentachloride, thionyl chloride, and the like can be exemplified, and acetic anhydride is preferable from the viewpoint of purification after the reaction. The amount of use of these dehydrating agents is preferably about 1 to 10 moles, and more preferably about 2 to 5 moles, relative to the reaction raw material. As long as the amount of use of the dehydrating agent is equal to or more than the lower limit value, the dehydration condensation reaction is sufficiently performed. In addition, as long as the amount of use is equal to or less than the upper limit value, an excessive amount of the dehydrating agent is not left, and improvement in yield can be expected. Further, an alkali catalyst can be used together with the dehydrating agent at this time, and pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like can be exemplified as the alkali catalyst, and pyridine is preferable because it has an appropriate basicity for the reaction. The amount of use of these alkali catalysts is in a range of 0.1 to 20 moles, and preferably 0.2 to 10 moles, relative to the number of moles of the carboxylic acid of the raw material. In addition, the alkali catalyst and the dehydrating agent can be used alone or in a mixture of two or more, and these can be appropriately controlled in terms of the reactivity, thermal resistance, and the like of the compound of interest by adjusting the amount of the catalyst, the amount of the dehydrating agent, the reaction temperature, and the reaction time.

[0236] As the solvent which can be used at this time, there is no particular limitation as long as it is an inert solvent with respect to the above reaction, and ethers such as diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, chlorine-based solvents such as dichloromethane, chloroform, dichloroethane, trichloroethylene, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene, nitriles such as acetonitrile, ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone, cyclohexanone, esters such as methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, γ-butyrolactone, aprotic polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, hexamethylphosphoric triamide, and the like can be exemplified, and these can be used alone or in a mixture. These solvents can be used in a range of 0 to 2,000 parts by mass relative to 100 parts by mass of the reaction raw material.

[0237] As for the reaction method and the method for recovering the compound, the method described in the paragraph of the amide acid compound can be used. The recovered compound can be refined by recrystallization, crystallization, distillation, and the like in cooperation with the physical properties of the reaction product. In addition, the reaction of the subsequent step can also be performed without the post-reaction refining step.

[0238] <Organic film forming material>

[0239] In addition, the present application provides an organic film forming material containing (A) the organic film forming compound of the present application represented by the above general formula (1A), and (B) an organic solvent. In addition, in the organic film forming material of the present application, the above organic film forming compound of the present application can be used alone or in combination with two or more.

[0240] As the (B) organic solvent that can be used in the organic film forming material of the present application, there is no particular limitation as long as it is a constituent component contained in a material that dissolves the above compound and other additives, and the like. Specifically, a solvent having a boiling point of less than 180°C, such as the solvents described in

[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 a mixture of two or more of these are preferably used. The blending amount of the (B) organic solvent is preferably 200 to 10,000 parts by mass, and more preferably 300 to 5,000 parts by mass, with respect to 100 parts by mass of the (A) above compound.

[0241] As long as it is such an organic film forming material, it can be coated by spin coating, and because it contains the organic film forming compound of the present application as described above, it becomes an organic film forming material that has both heat resistance of 400°C or higher and a high degree of embedding / planarization properties.

[0242] Further, in the material for forming an organic film of the present application, as the organic solvent, a high-boiling solvent having a boiling point of 180°C or higher can be added to the above-mentioned solvent having a boiling point of less than 180°C. That is, the above-mentioned (B) component 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. As the high-boiling solvent, there is no particular limitation as long as it is a solvent that can dissolve the compound for forming an organic film, and examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 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, glycerol, 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 isopropyl ether, diethylene glycol n-butyl ether, diethylene glycol isobutyl ether, diethylene glycol hexyl ether, diethylene glycol phenyl ether, diethylene glycol benzyl 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 n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol n-propyl ether, tripropylene glycol 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-butanediol diacetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dimethyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, and the like, which can be used alone or in combination.

[0243] The boiling point of the high-boiling solvent is preferably 180 to 300°C, more preferably 200 to 300°C. With such a boiling point, there is no risk of the solvent evaporating too quickly during baking (heat treatment) due to the low boiling point, and thus sufficient thermal fluidity can be obtained. Furthermore, with such a boiling point, the solvent does not remain in the film after baking due to the high boiling point, and thus there is no risk of adversely affecting the film properties such as etching resistance.

[0244] Furthermore, in the case of using the above high-boiling solvent, the blending amount of the high-boiling solvent is preferably 1 to 30 parts by mass relative to 100 parts by mass of a solvent having a boiling point of less than 180°C. With such a blending amount, there is no risk of the film failing to exhibit sufficient thermal fluidity during baking due to an insufficient blending amount, or the film properties such as etching resistance deteriorating due to an excessive blending amount.

[0245] With such an organic film-forming material, thermal fluidity is imparted due to the addition of the high-boiling solvent to the above organic film-forming compound, and thus an organic film-forming material having a high degree of burying / planarization properties is obtained.

[0246] Furthermore, the above organic film-forming material preferably contains one or more of (C) an acid generator, (D) a surfactant, (E) a crosslinking agent, and (F) a plasticizer. Each component is described in detail below.

[0247] In the organic film-forming material of the present application, (C) an acid generator can be added in order to further promote the hardening reaction. (C) The acid generator can be any of an acid generator that generates an acid by thermal decomposition, and an acid generator that generates an acid by light irradiation. Specifically, the material described in

[0061] to

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

[0248] The above (C) acid generator can be used alone or in combination with two or more. The addition amount of the (C) acid generator when added is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the above (A) compound.

[0249] In the organic film-forming material of the present application, (D) a surfactant can be added in order to improve the coatability during spin coating. As the (D) surfactant, for example, the one described in

[0142] to

[0147] of Japanese Patent Application Publication No. 2009-269953 can be used. The addition amount of the (D) surfactant when added is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the above (A) compound.

[0250] Further, in the organic film-forming material of the present application, in order to improve the hardenability, (E) a crosslinking agent can also be added to further suppress intermixing with the upper layer film. As the (E) crosslinking agent, there is no particular limitation, and various crosslinking agents of known systems can be widely used. As an example, melamine-based crosslinking agents, acetylene urea-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 can be exemplified.

[0251] As the melamine-based crosslinking agent, specifically, hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxy substituted products, and their partial self-condensates can be exemplified.

[0252] As the acetylene urea-based crosslinking agent, specifically, tetramethoxymethylated acetylene urea, tetrabutoxymethylated acetylene urea, their alkoxy and / or hydroxy substituted products, and their partial self-condensates can be exemplified.

[0253] As the benzoguanamine-based crosslinking agent, specifically, tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy substituted products, and their partial self-condensates can be exemplified.

[0254] As the urea-based crosslinking agent, specifically, dimethoxymethylated dimethoxyethylene urea, their alkoxy and / or hydroxy substituted products, and their partial self-condensates can be exemplified.

[0255] As the β-hydroxyalkylamide-based crosslinking agent, specifically, N,N,N',N'-tetra(2-hydroxyethyl)adipamide can be exemplified.

[0256] As the isocyanurate-based crosslinking agent, specifically, trisepoxypropyl isocyanurate, triallyl isocyanurate can be exemplified.

[0257] As the aziridine-based crosslinking agent, specifically, 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate] can be exemplified.

[0258] ​As the oxazoline-based cross-linking agent, specifically, 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-tert-butyl-2-oxazoline), 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), 2-isopropenyl oxazoline copolymer can be exemplified.

[0259] As the epoxy-based cross-linking agent, specifically, dipropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(epoxypropyl methacrylate), trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, neopentatetraol tetraglycidyl ether can be exemplified.

[0260] The addition amount of the (E) cross-linking agent, with respect to 100 parts by mass of the above (A) compound, is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass.

[0261] Further, in the organic film-forming material of the present application, in order to further improve the planarization / filling properties, a (F) plasticizer can be added. As the (F) plasticizer, there is no particular limitation, and various known plasticizers of systems can be widely used. As an example, low molecular compounds such as phthalate esters, adipate esters, phosphate esters, trimellitate esters, citrate esters, polymer of polyether system, polymer of polyester system, polyoxymethylene-based polymer described in Japanese Patent Application Publication No. 2013-253227, and the like can be exemplified. The addition amount of the (F) plasticizer, with respect to 100 parts by mass of the above (A) compound, is preferably 1 to 100 parts by mass, more preferably 5 to 30 parts by mass.

[0262] Further, in the organic film-forming material of the present application, as to the additive to impart the filling / planarization properties as with the plasticizer, preferably, for example, a liquid additive having a polyethylene glycol, polypropylene glycol structure, or a thermally decomposable polymer having a weight reduction rate of 40% by mass or more between 30°C and 250°C, and a weight average molecular weight of 300 to 200,000 can be used. The thermally decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formula (DP1), (DP1a). The addition amount in the case of adding these liquid additives, with respect to 100 parts by mass of the above (A) compound, is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass.

[0263] [Chemical Formula 38]

[0264]

[0265] (In the formula, X 11 is a hydrogen atom or a monovalent organic group of saturated or unsaturated carbon number 1 to 30 which can also be substituted. Y1is a divalent organic group of saturated or unsaturated carbon number 2 to 30.)

[0266] [Chemical Formula 39]

[0267]

[0268] (In the formula, X a is an alkyl group of carbon number 1 to 4. Y a is a divalent hydrocarbon group of saturated or unsaturated carbon number 4 to 10 which can also have an ether bond. I indicates the average number of repeating units and is 3 to 500.)

[0269] As above, as long as it is the organic film forming material of the present application, it becomes an organic film forming material which has both heat resistance of 400°C or higher and high degree of filling / plane characteristics. Therefore, the organic film forming material of the present application is extremely useful as an organic film forming material for a multilayer resist method such as a 2-layer resist method, a 3-layer resist method using a silicon-containing resist intermediate film or an inorganic hard mask intermediate film, a 4-layer resist method using a silicon-containing resist intermediate film or an inorganic hard mask intermediate film and an organic anti-reflective film. Furthermore, the organic film forming material of the present application does not generate by-products even in film formation in a noble gas, has excellent filling / plane characteristics, and is also suitable for use as a plane material in a semiconductor device manufacturing step other than the multilayer resist method.

[0270] <Substrate for semiconductor device manufacturing>

[0271] Furthermore, the present application provides a substrate for semiconductor device manufacturing on which an organic film hardened from the above-mentioned organic film forming material is formed.

[0272] As long as it is an organic film formed from the organic film forming material of the present application, by having high degree of filling / plane characteristics, it becomes an organic film which does not have a minute void due to filling failure or a concave-convex surface of the organic film due to insufficient plane, by which the process margin when patterning a semiconductor device substrate which is planarized by such an organic film is widened, and a semiconductor device can be manufactured with good yield.

[0273] <Method for forming an organic film>

[0274] The present application provides a method for forming an organic film suitable for use in a semiconductor device manufacturing step, in which an organic film forming material is spin-coated on a substrate to be processed, and the coated substrate is subjected to heat treatment in a non-reactive gas atmosphere at a temperature of 50°C or higher and 600°C or lower for a period of 10 seconds to 7200 seconds to form an organic film (one-stage baking).

[0275] Further, the present application provides a method for forming an organic film for planarizing a surface of a substrate having a step difference used in a semiconductor device manufacturing step, in which an organic film forming material is spin-coated on a substrate to be processed, the coated substrate is subjected to heat treatment in air at a temperature of 50°C or higher and 300°C or lower for a period of 5 seconds to 600 seconds to form a coating film, and then the coated substrate is subjected to heat treatment in a non-reactive gas atmosphere at a temperature of 200°C or higher and 600°C or lower for a period of 10 seconds to 7200 seconds to form an organic film (two-stage baking).

[0276] The method for forming an organic film first spin-coats (spins) the organic film forming material of the present application on a substrate to be processed. By using a spin coating method, good filling properties can be obtained. After spin-coating, baking (heat treatment) is performed to promote planarization and cross-linking reactions caused by heat flow. Further, by the baking, organic solvents in the organic film forming material can be evaporated, so in the case of forming a resist upper layer film or a silicon-containing resist intermediate film on the organic film, mixing can also be prevented.

[0277] The heat treatment step for forming an organic film (organic underlayer film) can use one-stage baking, two-stage baking, or multi-stage baking of three stages or more, and one-stage baking or two-stage baking is more economical.

[0278] In the case of one-stage baking, heat treatment is performed in a non-reactive gas atmosphere at a temperature of 50°C or higher and 600°C or lower for a period of 10 seconds to 7200 seconds, preferably at a temperature of 150°C or higher and 500°C or lower for a period of 10 seconds to 3600 seconds. By heat treatment under these conditions, planarization and cross-linking reactions caused by heat flow can be promoted.

[0279] On the other hand, in the case of two-stage baking, for the first-stage baking, the treatment temperature in air is 50°C or higher and 300°C or lower, preferably 250°C or lower, for a period of 5 seconds to 600 seconds, taking into account the effect of corrosion of the substrate caused by oxygen in air. The second-stage baking is performed in a non-reactive gas, and the baking temperature is higher than that of the first-stage baking, at a temperature of 200°C or higher and 600°C or lower, preferably 250°C or higher and 500°C or lower, for a period of 10 seconds to 7200 seconds.

[0280] In the case of forming a silicon-containing resist intermediate film or an inorganic hard mask intermediate film on the obtained organic film in the multilayer resist method. In the case of using a silicon-containing resist intermediate film, it is preferable to form the organic film at a higher temperature than the temperature at which the silicon-containing resist intermediate film is formed. Generally, the silicon-containing resist intermediate film is formed at a temperature of 100°C or higher and 400°C or lower, preferably at a temperature of 150°C or higher and 350°C or lower. If the organic film is formed at a higher temperature than the temperature, the dissolution of the organic film by the composition for forming a silicon-containing resist intermediate film can be prevented, and an organic film which does not intermix with the above composition can be formed. In the case of using an inorganic hard mask intermediate film, it is preferable to form the organic film at a higher temperature than the temperature at which the inorganic hard mask intermediate film is formed. As the temperature at which the inorganic hard mask intermediate film is formed, a temperature of 150°C or higher and 500°C or lower can be exemplified.

[0281] Further, the present application provides an organic film forming method which is a method for forming an organic film used in a manufacturing step of a semiconductor device, in which a processed substrate is heat-treated in an environment having an oxygen concentration of 1% or less, whereby an organic film is formed. That is, it is preferable that the oxygen concentration in the above-mentioned inert gas environment be 1% or less.

[0282] The organic film forming method first spin-coats the above-mentioned organic film forming material of the present application on a processed substrate. After the spin-coating, 2-stage baking is performed, first by 1st stage baking in air at 300°C or lower, and then by 2nd stage baking in an environment having an oxygen concentration of 1% or less. In the case of 1-stage baking, the initial 1st stage baking in air can be skipped. Further, as the environment in the baking, an inert gas such as nitrogen, argon, helium, etc. can be exemplified. As long as it is the organic film forming material of the present application, even if calcination is performed in such an inert gas environment, no sublimates are generated and a sufficiently hardened organic film can be formed.

[0283] Further, the organic film forming method of the present application can use, as the above-mentioned processed substrate, a processed substrate having a structure or a step difference of 30 nm or more in height. As described above, the organic film forming material of the present application has excellent filling / planarization properties, and even if the processed substrate has a structure or a step difference (unevenness) of 30 nm or more in height, a flat organic film can be formed. That is, the organic film forming method of the present application is particularly useful in the case of forming a flat organic film on such a processed substrate.

[0284] Further, the thickness of the formed organic film is appropriately selected, and is preferably 30 to 20,000 nm, particularly preferably 50 to 15,000 nm.

[0285] Further, the above-mentioned method for forming an organic film can be applied to both a case of forming an organic film for an organic underlayer film using the material for forming an organic film of the present application and a case of forming an organic film for a planarization film.

[0286] <Pattern forming method>

[0287] [3-layer resist method using silicon-containing resist intermediate film]

[0288] The present application provides a pattern forming method of forming an organic film on a processed body using the above-mentioned material for forming an organic film, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring a pattern to the silicon-containing resist intermediate film by etching using the patterned resist upper layer film as a mask, transferring a pattern to the above-mentioned organic film by etching using the pattern-transferred silicon-containing resist intermediate film as a mask, and further transferring a pattern to the above-mentioned processed body by etching using the pattern-transferred organic film as a mask.

[0289] As the processed body, a semiconductor device substrate, or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film is formed as a processed layer is preferably used, and more specifically, a substrate of Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, or the like, or a substrate on which any one of the above-mentioned metal film or the like is formed as a processed layer is used without particular limitation.

[0290] As the processed layer, various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, and stopper films thereof can be used, and can be formed to a thickness of 50 to 10,000 nm in general, and particularly to a thickness of 100 to 5,000 nm. Further, in the case of forming a processed layer, a substrate and a processed layer can be formed of different materials.

[0291] Further, as the processed body, a material containing silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof can be used.

[0292] Further, as the processed body, a processed body having a structure or a step having a height of 30 nm or more is preferably used.

[0293] In the case of forming an organic film on a processed body using the material for forming an organic film of the present application, the above-mentioned method for forming an organic film of the present application can be applied.

[0294] Then, a resist intermediate film material containing a silicon atom is used to form a resist intermediate film (silicon-containing resist intermediate film) on the organic film. As the silicon-containing resist intermediate film material, a polysiloxane-based intermediate film material is preferable. By making the silicon-containing resist intermediate film have an antireflection effect, reflection can be suppressed. In particular, for 193 nm exposure, if a material containing a large amount of an aromatic group and having a high etching selectivity with respect to the substrate is used as the material for forming the organic film, the k value becomes high and the substrate reflection becomes high, and by making the silicon-containing resist intermediate film have an absorption that becomes an appropriate k value, the reflection can be suppressed and the substrate reflection can be made 0.5% or less. As the silicon-containing resist intermediate film having an antireflection effect, for 248 nm and 157 nm exposure, a polysiloxane in which anthracene is bonded to a branch or which has anthracene in the polysiloxane structure and is crosslinked by acid or heat is preferable, and for 193 nm exposure, a polysiloxane in which a phenyl group or an absorption group having a silicon-silicon bond is bonded to a branch or which has a phenyl group or an absorption group having a silicon-silicon bond in the polysiloxane structure and is crosslinked by acid or heat is preferable.

[0295] Then, a resist upper layer film material composed of a photoresist composition is used to form a resist upper layer film on the silicon-containing resist intermediate film. As the resist upper layer film material, either a positive type or a negative type can be used, and the same as the photoresist composition usually used can be used. After the resist upper layer film material is spin-coated, pre-baking at 60 to 180°C for 10 to 300 seconds is preferable. Thereafter, exposure, further post-exposure baking (PEB), and development are performed in accordance with the usual method, and a resist upper layer film pattern is obtained. In addition, the thickness of the resist upper layer film is not particularly limited, and is preferably 30 to 500 nm, and particularly preferably 50 to 400 nm.

[0296] Then, a circuit pattern (resist upper layer film pattern) is formed on the resist upper layer film. In the formation of the circuit pattern, it is preferable that the circuit pattern be formed by photolithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing by electron beam, nanoimprint, or a combination thereof.

[0297] In addition, as the exposure light, high-energy rays having a wavelength of 300 nm or less can be used, and specifically, far ultraviolet rays, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 laser (157 nm), a Kr2 laser (146 nm), an Ar2 laser (126 nm), soft X-rays (EUV) of 3 to 20 nm, an electron beam (EB), an ion beam, X-rays, and the like can be used.

[0298] In addition, in the formation of the circuit pattern, it is preferable that the circuit pattern be developed by alkali development or organic solvent development.

[0299] Then, the circuit patterned resist upper layer film is used as a mask to transfer the pattern to the silicon-containing resist intermediate film by etching. The etching of the silicon-containing resist intermediate film using the resist upper layer film pattern as a mask is preferably performed using a fluorocarbon compound gas. By this, a silicon-containing resist intermediate film pattern is formed.

[0300] Then, the pattern-transferred silicon-containing resist intermediate film is used as a mask to transfer the pattern to the organic film by etching. Since the silicon-containing resist intermediate film exhibits higher etching resistance to oxygen or hydrogen than the organic film, the etching of the organic film using the silicon-containing resist intermediate film pattern as a mask is preferably performed using an etching gas in which oxygen or hydrogen is the main component. By this, an organic film pattern can be formed.

[0301] Then, the pattern-transferred organic film is used as a mask to transfer the pattern to the substrate to be processed by etching. The etching of the substrate to be processed (processed layer) can be performed by a general method, for example, if the substrate to be processed is SiO2, SiN, a silicon dioxide-based low dielectric constant insulating film, etching using a fluorochloroalkane gas as the main component is performed, and if it is p-Si or Al, W, etching using a chlorine-based or bromine-based gas as the main component is performed. In the case where the substrate is processed by etching using a fluorochloroalkane gas, the silicon-containing resist intermediate film pattern is peeled off simultaneously with the processing of the substrate. On the other hand, in the case where the substrate is processed by etching using a chlorine-based or bromine-based gas, in order to peel off the silicon-containing resist intermediate film pattern, dry etching peeling using a fluorochloroalkane gas needs to be additionally performed after the processing of the substrate.

[0302] The organic film obtained using the organic film-forming material of the present application can be one that is excellent in etching resistance at the time of etching of the substrate to be processed as described above.

[0303] [4-layer resist method using a silicon-containing resist intermediate film and an organic antireflection film]

[0304] Further, the present application provides a pattern forming method in which an organic film is formed on a substrate to be processed using the organic film-forming material described above, a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, an organic antireflection film is formed on the silicon-containing resist intermediate film, a resist upper layer film is formed on the organic antireflection film using a photoresist composition to make a 4-layer film structure, a circuit pattern is formed on the resist upper layer film, the pattern is transferred to the above-described organic antireflection film and the above-described silicon-containing resist intermediate film by etching using the patterned resist upper layer film as a mask, the pattern is transferred to the above-described organic film by etching using the pattern-transferred silicon-containing resist intermediate film as a mask, and further, the pattern is transferred to the above-described substrate to be processed by etching using the pattern-transferred organic film as a mask.

[0305] Further, the method can be performed in the same manner as the above-described three-layer resist method using the silicon-containing resist intermediate film, except that an inorganic hard mask intermediate film is formed on the organic film.

[0306] The organic antireflection film can be formed by spin coating using a known organic antireflection film material.

[0307] [Three-layer resist method using inorganic hard mask intermediate film]

[0308] Further, the present application provides a pattern forming method in which an organic film is formed on a processed object using the above-described organic film forming material, an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a titanium oxide film, and a titanium nitride film is formed on the organic film, a resist upper layer film is formed on the inorganic hard mask intermediate film using a photoresist composition, a circuit pattern is formed on the resist upper layer film, the patterned resist upper layer film is used as a mask to transfer a pattern to the above-described inorganic hard mask intermediate film by etching, the pattern-transferred inorganic hard mask intermediate film is used as a mask to transfer a pattern to the above-described organic film by etching, and further, the pattern-transferred organic film is used as a mask to transfer a pattern to the above-described processed object by etching.

[0309] Further, the method can be performed in the same manner as the above-described three-layer resist method using the silicon-containing resist intermediate film, except that an inorganic hard mask intermediate film is formed on the organic film.

[0310] The inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film (SiON film), a titanium oxide film, and a titanium nitride film can be formed by a CVD method, an ALD method, or the like. That is, it is preferable that the above-described inorganic hard mask intermediate film be formed by a CVD method or an ALD method. As a method for forming a silicon nitride film, for example, Japanese Patent Application Publication No. 2002-334869, International Publication No. 2004 / 066377, or the like is described. The film thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, and more preferably 10 to 100 nm. As the inorganic hard mask intermediate film, a SiON film, which has a high effect as an antireflection film, is preferably used. Since the substrate temperature when forming the SiON film becomes 300 to 500°C, the organic film needs to be able to withstand a temperature of 300 to 500°C. The organic film formed using the organic film forming material of the present application has high heat resistance and can withstand a high temperature of 300 to 500°C, and thus can be combined with the inorganic hard mask intermediate film formed by a CVD method or an ALD method and the organic film formed by a spin coating method.

[0311] [Four-layer resist method using inorganic hard mask intermediate film and organic antireflection film]

[0312] Furthermore, the present invention provides a pattern forming method, wherein an organic film is formed on a workpiece using the organic film forming material described above, an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, silicon oxide nitride film, titanium oxide film, and titanium nitride film is formed on the organic film, an organic antireflective film is formed on the inorganic hard mask intermediate film, a photoresist composition is used on the organic antireflective film to form a photoresist top film to form a four-layer film structure, a circuit pattern is formed on the photoresist top film, the patterned photoresist top film is used as a mask to transfer the pattern to the organic antireflective film and the inorganic hard mask intermediate film by etching, the patterned inorganic hard mask intermediate film is used as a mask to transfer the pattern to the organic film by etching, and further, the patterned organic film is used as a mask to transfer the pattern to the workpiece by etching.

[0313] Furthermore, apart from forming an organic antireflective film (BARC) between the inorganic hard mask intermediate film and the upper resist film, this method can be carried out in the same manner as the three-layer resist method using the inorganic hard mask intermediate film described above.

[0314] In particular, when a SiON film is used as the intermediate film in an inorganic hard mask, the two-layer antireflective film of SiON film and BARC can suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another advantage of forming BARC is that it reduces the trailing of the resist pattern on the SiON film.

[0315] Here, an example of the patterning method performed by the three-layer resist method of the present invention is shown. Figure 2 (A) to (F). In the case of the 3-layer resist method, such as Figure 2 As shown in (A), after an organic film 3 is formed on the processed layer 2 formed on the substrate 1 using the organic film forming material of the present invention, a silicon-containing photoresist intermediate film 4 is formed, and a photoresist upper film 5 is formed thereon. Then, as... Figure 2 As shown in (B), the exposed portion 6 of the upper resist film 5 is exposed, and PEB (post-exposure baking) is performed. Then, as... Figure 2 As shown in (C), development is performed to form the resist upper film pattern 5a. Then, as... Figure 2 As shown in (D), using the upper resist film pattern 5a as a mask, the silicon-containing resist intermediate film is dry-etched using a chlorofluorocarbon gas to form the silicon-containing resist intermediate film pattern 4a. Then, as... Figure 2 As shown in (E), after removing the upper resist film pattern, the silicon-containing resist intermediate film pattern 4a is used as a mask to perform oxygen plasma etching on the organic film, forming the organic film pattern 3a. Further, as... Figure 2As shown in (F), after removing the silicon resist intermediate film pattern, the organic film pattern 3a is used as a mask to etch the layer to be processed, forming pattern 2a.

[0316] In the case of forming an inorganic hard mask intermediate film, the silicon-containing resist intermediate film 4 can be replaced with an inorganic hard mask intermediate film. In the case of forming a BARC, a BARC can be formed between the silicon-containing resist intermediate film 4 and the upper resist film 5. The etching of the BARC can be performed continuously before etching the silicon-containing resist intermediate film 4, or the etching of the silicon-containing resist intermediate film 4 can be performed after etching only the BARC, by changing the etching equipment, etc.

[0317] As described above, as long as it is the pattern forming method of the present invention, fine patterns can be formed on the substrate to be processed with high precision by means of a multilayer resist method.

[0318] Example

[0319] The present invention will be described in more detail below with reference to synthetic examples, comparative synthetic examples, examples, and comparative examples, but the present invention is not limited thereto. Furthermore, the molecular weight and dispersity are obtained by calculating the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as the dissolving solution, and the dispersity (Mw / Mn) is then calculated.

[0320] Synthesis of Aromatic Carboxylic Anhydrides

[0321] The synthesis of aromatic carboxylic anhydrides (B1) to (B5) uses the following phenolic compounds (a1) to (a5) and phthalonitrile compounds (b1) to (b2).

[0322] [Phenolic compounds]

[0323] [Chemistry 40]

[0324]

[0325] Phthalate derivatives

[0326] [Chemistry 41]

[0327]

[0328] [Synthetic Example 1] Synthesis of Aromatic Carboxylic Anhydride (B1)

[0329] Synthesis of aromatic carboxylic anhydrides (B1): Synthesis of intermediate (B1-1)

[0330] [Chemistry 42]

[0331]

[0332] To 20.0 g (166 mmol) of compound (al) and 25.3 g (183 mmol) of potassium carbonate, 100 g of N-methylpyrrolidone (NMP) was added to prepare a dispersion under nitrogen at an internal temperature of 70°C, and then 92.4 g of a 25 mass% NMP solution of compound (bl) (bl corresponds to 158 mmol) was slowly added dropwise. Thereafter, the reaction was carried out at an internal temperature of 80°C for 5 hours. After the obtained reaction solution was cooled to room temperature, 300 ml of diisopropyl ether and 200 g of pure water were added to dissolve the precipitated salt. After standing, the separated aqueous layer was removed and the organic layer was recovered, washed once with 100 g of a 1% sodium hydroxide aqueous solution, washed four times with 100 ml of pure water, and then dried under reduced pressure to obtain 33.5 g of (Bl-l).

[0333] Synthesis of aromatic carboxylic anhydride (B1)

[0334] [Chemical Formula 43]

[0335]

[0336] To 33.0 g (134 mmol) of (Bl-l) and 26.5 g of KOH (15% water content) (KOH corresponds to 402 mmol), 100 g of ultrapure water and 100 g of ethanol were added to carry out a reaction under nitrogen at an internal temperature of 80°C for 30 hours. After the obtained reaction solution was cooled to room temperature, it was added dropwise to 176 g of a 10% aqueous hydrochloric acid solution, and then extracted with 500 ml of ethyl acetate. The organic layer was recovered, further washed four times with 100 ml of pure water, and then dried under reduced pressure. After a uniform solution was prepared by adding 100 g of THF to the residue, crystallization was performed from 500 g of hexane. The precipitated crystals were separated by filtration, washed twice with 100 ml of hexane, and then recovered. The recovered crystals were vacuum-dried at 70°C to obtain 29.2 g of (Bl-2).

[0337] Synthesis of aromatic carboxylic anhydride (B1)

[0338] [Chemical Formula 44]

[0339]

[0340] To 27.0 g (94.5 mmol) of (B1-2), 100 g of acetic anhydride was added, and the reaction was carried out at 100°C for 4 hours under nitrogen. After the reaction solution obtained was cooled to room temperature, 300 g of xylene was added, and acetic acid and acetic anhydride generated in the reaction were distilled off. After 50 g of THF was added to the residue obtained after distillation to make a uniform solution, 300 g of hexane was added while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed three times with 200 ml of hexane, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain 23.6 g of (B1).

[0341] [Synthesis Example 2] Synthesis of Aromatic Carboxylic Anhydride (B2)

[0342] Synthesis of Aromatic Carboxylic Anhydride (B2): Synthesis of Intermediate (B2-1)

[0343] [Synthesis Example 2] Synthesis of Aromatic Carboxylic Anhydride (B2)

[0344]

[0345] To 20.0 g (166 mmol) of compound (a2), 25.3 g (183 mmol) of potassium carbonate, and 100 g of N-methylpyrrolidone (NMP), a 52.0 g of a 25 mass% NMP solution of compound (b2) (b2 is equivalent to 79.3 mmol) was added dropwise slowly under nitrogen at 70°C to make a dispersion liquid. Then, the reaction was carried out at 120°C for 5 hours. After the reaction solution obtained was cooled to room temperature, 300 ml of diisopropyl ether and 200 g of pure water were added to dissolve the precipitated salt. After standing, the separated water layer was removed, and the organic layer was recovered, washed once with 100 g of 1% sodium hydroxide aqueous solution, washed four times with 100 ml of pure water, and vacuum-dried to obtain 25.7 g of (B2-1).

[0346] Synthesis of Aromatic Carboxylic Anhydride (B2): Synthesis of Intermediate (B2-2)

[0347] [Synthesis Example 2] Synthesis of Aromatic Carboxylic Anhydride (B2)

[0348]

[0349] To (B2-1) 25.0 g (134 mmol), KOH (15% water content product) 13.6 g (KOH is equivalent to 205 mmol), add ultrapure water 100 g, ethanol 100 g, and perform a reaction for 24 hours at 80°C under nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, add to 10% aqueous hydrochloric acid solution 90 g, and extract with ethyl acetate 400 ml. Recover the organic layer, and wash with pure water 100 ml 4 times, and dry the organic layer under reduced pressure. To the residue, add THF 100 g to make a uniform solution, and add hexane 400 g while stirring to precipitate crystals. Isolate the precipitated crystals by filtration, wash with hexane 100 ml 2 times, and recover. Dry the recovered crystals at 70°C under vacuum to obtain 22.6 g of (B2-2).

[0350] Synthesis of aromatic carboxylic anhydride (B2)

[0351] [Chemical Formula 47]

[0352]

[0353] To (B2-2) 22.0 g (54.7 mmol), add acetic anhydride 60 g, and perform a reaction for 4 hours at 100°C under nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, add xylene 250 g, and distill acetic acid and acetic anhydride generated in the reaction. To the residue after distillation, add THF 40 g to make a uniform solution, and add hexane 300 g while stirring to precipitate crystals. Isolate the precipitated crystals by filtration, wash with hexane 100 ml 3 times, and recover the crystals. Dry the recovered crystals at 70°C under vacuum to obtain 19.7 g of (B2).

[0354] [Synthesis Example 3] Synthesis of aromatic carboxylic anhydride (B3)

[0355] Synthesis of aromatic carboxylic anhydride (B3): Synthesis of intermediate (B3-1)

[0356] [Chemical Formula 48]

[0357]

[0358] To 20.0 g (169 mmol) of compound (a3) and 25.3 g (183 mmol) of potassium carbonate, 100 g of N-methylpyrrolidone (NMP) was added to make a dispersion under a nitrogen atmosphere at an internal temperature of 70°C, and then 94.0 g of a 25 mass% NMP solution of compound (bl) (bl is equivalent to 160.8 mmol) was slowly added dropwise. Thereafter, a reaction was performed at an internal temperature of 80°C for 5 hours. After the obtained reaction solution was cooled to room temperature, 400 ml of diisopropyl ether and 200 g of pure water were added to dissolve the precipitated salt. After standing, the separated aqueous layer was removed and the organic layer was recovered, washed once with 100 g of a 1% sodium hydroxide aqueous solution, washed four times with 100 ml of pure water, and then subjected to a dry distillation under reduced pressure to obtain 35.0 g of (B3-1).

[0359] Synthesis of aromatic carboxylic anhydride (B3)

[0360] [Chemical Formula 49]

[0361]

[0362] To 34.0 g (139 mmol) of (B3-1) and 27.6 g of KOH (15% water content) (KOH is equivalent to 418 mmol), 100 g of ultrapure water and 100 g of ethanol were added to perform a reaction under a nitrogen atmosphere at an internal temperature of 80°C for 24 hours. After the obtained reaction solution was cooled to room temperature, it was added dropwise to 183 g of a 10% hydrochloric acid aqueous solution, and then extracted with 400 ml of ethyl acetate. The organic layer was recovered, further washed four times with 100 ml of pure water, and then subjected to a dry distillation under reduced pressure. After a uniform solution was prepared by adding 100 g of THF to the residue, 400 g of hexane was added while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed twice with 100 ml of hexane, and then recovered. The recovered crystals were vacuum-dried at 70°C to obtain 29.3 g of (B3-2).

[0363] Synthesis of aromatic carboxylic anhydride (B3)

[0364] [Chemical Formula 50]

[0365]

[0366] To 29.0 g (103 mmol) of (B3-2), 105 g of acetic anhydride was added, and the reaction was carried out at 100°C for 4 hours under nitrogen. After the reaction solution obtained was cooled to room temperature, 250 g of xylene was added, and acetic acid and acetic anhydride generated in the reaction were distilled off. After 50 g of THF was added to the residue after distillation to make a uniform solution, 300 g of hexane was added while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed with 100 ml of hexane three times, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain 26.7 g of (B3).

[0367] [Synthesis Example 4] Synthesis of Aromatic Carboxylic Anhydride (B4)

[0368] Synthesis of Aromatic Carboxylic Anhydride (B4): Synthesis of Intermediate (B4-1)

[0369] [Synthesis Example 4] Synthesis of Aromatic Carboxylic Anhydride (B4)

[0370]

[0371]

[0372] To 20.0 g (151 mmol) of compound (a4), 23.0 g (167 mmol) of potassium carbonate, and 100 g of N-methylpyrrolidone (NMP), 84.0 g of a 25 mass% NMP solution of compound (bl) (bl corresponds to 143.8 mmol) was added dropwise slowly under nitrogen at 70°C to make a dispersion liquid. Then, the reaction was carried out at 80°C for 5 hours. After the reaction solution obtained was cooled to room temperature, 400 ml of diisopropyl ether and 200 g of pure water were added to dissolve the precipitated salt. After standing, the separated aqueous layer was removed, and the organic layer was recovered, washed with 100 g of a 1% sodium hydroxide aqueous solution once and with 100 ml of pure water four times, and then dried under reduced pressure to obtain 34.5 g of (B4-1).

[0373] Synthesis of Aromatic Carboxylic Anhydride (B4): Synthesis of Intermediate (B4-2)

[0374] [Synthesis Example 4] Synthesis of Aromatic Carboxylic Anhydride (B4)

[0375]

[0376] To 34.0 g (132 mmol) of (B4-1) and 26.1 g (KOH is equivalent to 395 mmol) of KOH (15% water content) was added 100 g of ultrapure water and 100 g of ethanol, and the mixture was reacted at 80°C for 31 hours under nitrogen. The reaction solution obtained was cooled to room temperature, and then added dropwise to 183 g of 10% aqueous hydrochloric acid, and extracted with 400 ml of ethyl acetate. The organic layer was recovered, and further washed with 100 ml of pure water four times, and then the organic layer was dried under reduced pressure. To the residue was added 100 g of THF to prepare a uniform solution, and then 400 g of hexane was added while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed with 100 ml of hexane twice, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain 27.3 g of (B4-2).

[0377] Synthesis of aromatic carboxylic anhydride (B4)

[0378] [Chemical Formula 53]

[0379]

[0380] To 27.0 g (91.1 mmol) of (B4-2) was added 95 g of acetic anhydride, and the mixture was reacted at 100°C for 4 hours under nitrogen. The reaction solution obtained was cooled to room temperature, and then 250 g of xylene was added to distill acetic acid and acetic anhydride generated in the reaction. To the residue obtained after distillation was added 50 g of THF to prepare a uniform solution, and then 300 g of hexane was added while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed with 100 ml of hexane three times, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain 23.1 g of (B4).

[0381] [Synthesis Example 5] Synthesis of aromatic carboxylic anhydride (B5)

[0382] Synthesis of aromatic carboxylic anhydride (B5): Synthesis of intermediate (B5-1)

[0383] [Chemical Formula 54]

[0384]

[0385] To 20.0 g (94.2 mmol) of compound (a5) and 13.1 g (104 mmol) of potassium carbonate, 100 g of N-methylpyrrolidone (NMP) was added to make a dispersion under a nitrogen atmosphere at an internal temperature of 70°C, and then 52.3 g of a 25 mass% NMP solution of compound (bl) (bl corresponds to 89.5 mmol) was slowly added dropwise. Thereafter, a reaction was performed at an internal temperature of 80°C for 5 hours. After the obtained reaction solution was cooled to room temperature, 400 ml of diisopropyl ether and 200 g of pure water were added to dissolve the precipitated salt. After standing, the separated aqueous layer was removed and the organic layer was recovered, washed once with 100 g of a 1% sodium hydroxide aqueous solution, washed four times with 100 ml of pure water, and then subjected to a dry distillation under reduced pressure to obtain 28.5 g of (B5-1).

[0386] Synthesis of aromatic carboxylic anhydride (B5): Synthesis of intermediate (B5-2)

[0387] [Chemical Formula 55]

[0388]

[0389] To 28.0 g (82.7 mmol) of (B5-1) and 16.4 g of KOH (15% water content) (KOH corresponds to 248 mmol), 100 g of ultrapure water and 100 g of ethanol were added to perform a reaction under a nitrogen atmosphere at an internal temperature of 80°C for 31 hours. After the obtained reaction solution was cooled to room temperature, it was added dropwise to 183 g of a 10% hydrochloric acid aqueous solution, and then extracted with 300 ml of ethyl acetate. The organic layer was recovered, washed four times with 100 ml of pure water, and then subjected to a dry distillation under reduced pressure. After a uniform solution was prepared by adding 80 g of THF to the residue, 400 g of hexane was added while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed twice with 100 ml of hexane, and then recovered. The recovered crystals were vacuum-dried at 70°C to obtain 25.3 g of (B5-2).

[0390] Synthesis of aromatic carboxylic anhydride (B5)

[0391] [Chemical Formula 56]

[0392]

[0393] To 25.0 g (66.4 mmol) of (B5-2), 70 g of acetic anhydride was added, and the reaction was carried out at 100°C for 4 hours under nitrogen. After the reaction solution obtained was cooled to room temperature, 250 g of xylene was added, and acetic acid and acetic anhydride generated in the reaction were distilled off. After 50 g of THF was added to the residue after distillation to make a uniform solution, 300 g of hexane was added while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed with 100 ml of hexane three times, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain 22.1 g of (B5).

[0394] Synthesis of the compound for forming an organic film

[0395] In the synthesis of the compounds for forming an organic film (A1) to (A22), the aromatic carboxylic anhydrides represented by the above synthesis examples shown below: (B1) to (B5) and the amine compound groups: (C1) to (C13) were used. As for (C8), a 60:40 isomer mixture was used.

[0396] Aromatic carboxylic anhydride:

[0397] [Chemical Formula 57]

[0398]

[0399] Amine compound group:

[0400] [Chemical Formula 58]

[0401]

[0402] [Chemical Formula 59]

[0403]

[0404] [Synthesis Example 6] Synthesis of Compound for Forming an Organic Film (A1)

[0405] To 5.33 g (20.0 mmol) of aromatic carboxylic anhydride (B1), 2.00 g (10.0 mmol) of amine compound (C1), 50 g of N-methyl-2-pyrrolidone (NMP) was added, and the reaction was carried out at 40°C for 3 hours under nitrogen atmosphere to obtain an amic acid solution. To the obtained amic acid solution, 0.79 g (10.0 mmol) of pyridine was added, and 3.07 g (30.0 mmol) of acetic anhydride was added dropwise more slowly, and the reaction was carried out at 60°C for 4 hours to carry out imidization. After the reaction was completed, it was cooled to room temperature, and 100 g of methyl isobutyl ketone was added, and the organic layer was washed with 100 g of 3% nitric acid aqueous solution, and further washed with 100 g of pure water 5 times, and the organic layer was dried under reduced pressure. To the residue, 30 g of THF (tetrahydrofuran) was added to make a uniform solution, and crystallization was carried out with 150 g of methanol. The precipitated crystals were separated by filtration, washed with 100 g of methanol 2 times, and recovered. The recovered crystals were vacuum dried at 70°C to thereby obtain (A1).

[0406] The weight average molecular weight (Mw), the dispersity (Mw / Mn) were obtained by GPC, and the results were as follows.

[0407] [Synthesis Example 6]

[0408]

[0409] (A1): Mw = 700, Mw / Mn = 1.01

[0410] [Synthesis Examples 7 to 27] Synthesis of organic film forming compounds (A2) to (A22)

[0411] Using the aromatic carboxylic anhydride, amine compound shown in Tables 1 and 2, and under the same reaction conditions as in Synthesis Example 6, the organic film forming compounds (A2) to (A22) shown in Tables 1 and 2 were obtained as products. The organic film forming compound (A1) is also shown.

[0412] [Table 1]

[0413]

[0414] [Table 2]

[0415]

[0416]

[0417] In the synthesis of the organic film forming compounds (R1) to (R5), the following compounds (D1) to (D8) shown as the synthetic raw materials for comparative synthesis examples were used.

[0418] Synthetic raw material for comparative synthesis example:

[0419] [Chemical 61]

[0420]

[0421] [Comparative Synthesis Example 1] Synthesis of Compound (R1) for Organic Film Formation

[0422] A homogeneous dispersion liquid was prepared by adding 10.00 g of compound (D1), 4.76 g of potassium carbonate, and 50 g of N-methyl-2-pyrrolidone under a nitrogen atmosphere at an internal temperature of 50°C. 3.72 g of propargyl bromide was added dropwise slowly, and a reaction was performed at an internal temperature of 50°C for 16 hours. After cooling to room temperature, a homogeneous solution was prepared by adding 100 g of methyl isobutyl ketone and 50 g of pure water, and the water layer was removed. The organic layer was further washed twice with 30 g of 3.0% nitric acid aqueous solution and five times with 30 g of pure water, and the organic layer was dried under reduced pressure. To the residue, 30 g of THF was added, and crystallization was performed by adding 100 g of methanol. The crystallized 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).

[0423] The weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0424] [Chemical 62]

[0425]

[0426] (R1): Mw = 960, Mw / Mn = 1.07

[0427] [Comparative Synthesis Example 2] Synthesis of Compound (R2) for Organic Film Formation

[0428] An amide acid solution was obtained by adding 10.65 g of compound (D5) and 9.93 g of compound (D2) to 120 g of NMP, and performing a reaction under a nitrogen atmosphere at an internal temperature of 40°C for 3 hours. After cooling to room temperature, a homogeneous solution was prepared by adding 200 g of methyl isobutyl ketone and 100 g of pure water, and the water layer was removed. The organic layer was further washed five times with 100 g of 3.0% nitric acid aqueous solution and 100 g of pure water, and the organic layer was dried under reduced pressure. To the residue, 60 g of THF was added, and crystallization was performed by adding 300 g of hexane. The crystallized crystals were separated by filtration, washed twice with 200 g of hexane, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain (R2).

[0429] The weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0430] [Chemical 63]

[0431]

[0432] (R2): Mw = 1,100, Mw / Mn = 1.03

[0433] [Comparative Synthesis Example 3] Synthesis of organic film forming compound (R3)

[0434] To 6.89 g of the compound (D3) and 8.21 g of the compound (D6), 100 g of NMP (N-methyl-2-pyrrolidone) was added, and the mixture was allowed to react at 40°C for 3 hours under a nitrogen atmosphere to obtain an amic acid solution. To the obtained amic acid solution, 1.58 g of pyridine was added, and further, 6.14 g of acetic anhydride was added dropwise slowly, and the mixture was allowed to react at 60°C for 4 hours to perform imidization. After the reaction, the mixture was cooled to room temperature, and 200 g of methyl isobutyl ketone was added, and the organic layer was washed with 100 g of 3% nitric acid aqueous solution, and further, washed with 100 g of pure water five times. The organic layer was dried under reduced pressure. To the residue, 60 g of THF (tetrahydrofuran) was added to prepare a uniform solution, and the solution was crystallized from 300 g of methanol. The precipitated crystals were separated by filtration, washed with 100 g of methanol twice, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain (R3).

[0435] The weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0436] [Compound 64]

[0437]

[0438] (R3): Mw = 760, Mw / Mn = 1.02

[0439] [Comparative Synthesis Example 4] Synthesis of organic film forming compound (R4)

[0440] To 5.88 g of the compound (D4) and 15.98 g of the compound (D5), 100 g of acetone was added, and the mixture was allowed to react at 40°C for 3 hours under a nitrogen atmosphere. To the obtained reaction solution, 2.46 g of sodium acetate and 15.33 g of acetic anhydride were added dropwise slowly, and the mixture was allowed to react at 50°C for 4 hours. After the reaction, the mixture was cooled to room temperature, and 300 g of methyl isobutyl ketone was added, and the organic layer was washed with 100 g of 3% nitric acid aqueous solution, and further, washed with 100 g of pure water six times. The organic layer was dried under reduced pressure. To the residue, 100 g of THF was added to prepare a uniform solution, and the solution was crystallized from 300 g of diisopropyl ether. The precipitated crystals were separated by filtration, washed with 200 g of diisopropyl ether twice, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain (R4).

[0441] The weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC and were as follows.

[0442] [Chemical 65]

[0443]

[0444] (R4): Mw = 680, Mw / Mn = 1.03

[0445] [Comparative Synthesis Example 5] Synthesis of Organic Film-Forming Compound (R5)

[0446] Under a nitrogen atmosphere, 13.98 g of compound (D7) was dissolved in NMP 192 g, and then 11.46 g of compound (D8) was added, and a reaction was performed at an internal temperature of 40°C for 2 hours. Further, 5.16 g of compound (D3) was added, and a reaction was performed for another 2 hours. To the obtained amide acid solution, 3.16 g of pyridine was added, and further, 10.22 g of acetic anhydride was slowly added dropwise, and a reaction was performed at an internal temperature of 60°C for 4 hours to perform imidization. After cooling to room temperature, crystallization was performed from methanol 600 g. The precipitated crystals were separated by filtration, washed twice with methanol 200 g, and recovered. The recovered crystals were vacuum-dried at 70°C to obtain (R5).

[0447] The weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC and were as follows.

[0448] [Chemical 66]

[0449]

[0450] (R5): Mw = 4,900, Mw / Mn = 1.33

[0451] The structural formula, the weight average molecular weight (Mw), and the dispersity (Mw / Mn) of the above obtained organic film-forming compounds (A1) to (A22) are shown in Tables 3 to 6. Further, the Mw and Mw / Mn of the organic film-forming compounds (R1) to (R5) used in the comparative examples are also shown in Table 7.

[0452] [Table 3]

[0453]

[0454]

[0455] [Table 4]

[0456]

[0457] [Table 5]

[0458]

[0459] [Table 6]

[0460]

[0461]

[0462] [Table 7]

[0463]

[0464]

[0465] Preparation of organic film forming materials (UDL-1 to 25, comparative UDL-1 to 5)

[0466] The above organic film forming compounds (A1) to (A22), and (R1) to (R5), (S1) 1,6-diacetyloxyhexane: boiling point 260°C, (S2) tripropylene glycol monomethyl ether: boiling point 242°C as high boiling point solvents were dissolved in a solvent containing propylene glycol monomethyl ether acetate (PGMEA), FC-4430 (Sumitomo 3M (Co.) Ltd.) 0.1 mass% in the proportions shown in Tables 8, 9, filtered with a filter made of fluorine resin of 0.1 μm, whereby organic film forming materials (UDL-1 to 25, comparative UDL-1 to 5) were prepared respectively.

[0467] [Table 8]

[0468]

[0469]

[0470] [Table 9]

[0471]

[0472] Solvent resistance measurement of Example 1 (Examples 1-1 to 1-25, comparative examples 1-1 to 1-5)

[0473] The above prepared organic film forming materials (UDL-1 to 25, comparative UDL-1 to 5) were coated on a silicon substrate, baked at 450°C for 60 seconds under a nitrogen gas stream with an oxygen concentration controlled to 0.2% or less, the film thickness was measured, PGMEA solvent was dispensed thereon, left for 30 seconds, spin dried, baked at 100°C for 60 seconds to evaporate the PGMEA, the film thickness was measured to obtain the film thickness difference before and after PGMEA treatment. These results are shown in Tables 10, 11.

[0474] [Table 10]

[0475]

[0476] [Table 11]

[0477]

[0478] As shown in Table 10, the residual film ratio after PGMEA treatment of the organic film forming material of the present application (Examples 1-1 to 1-25) was 99.8% or more, and it was found that sufficient solvent resistance was exhibited even under a nitrogen atmosphere due to cross-linking reaction. In contrast, as shown in Table 11, in Comparative Examples 1-1, 1-2, and 1-4, the residual film ratio after PGMEA treatment became less than 99.5% due to insufficient heat resistance. Among these, the residual film ratio of Comparative Example 1-4 was less than 90%. In Comparative Examples 1-3 and 1-5, solvent resistance was exhibited and the residual film ratio became 99.8% or more. It is thought that this is due to the excellent heat resistance of the ethynylbenzene terminal containing an imide ring.

[0479] Evaluation of Heat Resistance (Examples 2-1 to 2-25, Comparative Examples 2-1 to 2-5)

[0480] The above organic film forming materials (UDL-1 to 25, Comparative UDL-1 to 5) were each coated on a silicon substrate, and a 200 nm coating film was formed by calcination at 180°C in air, and the film thickness was measured. The substrate was further baked at 450°C for 10 minutes under a nitrogen gas stream with an oxygen concentration controlled to 0.2% or less, and the film thickness was measured. These results are shown in Tables 12 and 13.

[0481] [Table 12]

[0482]

[0483]

[0484] [Table 13]

[0485]

[0486] As shown in Table 12, the organic film forming material of the present application (Examples 2-1 to 2-25) also had a film thickness reduction of 3% or less after calcination at 450°C for 10 minutes, and the organic film forming material of the present application could form an organic film having high heat resistance even under such a high temperature condition of 450°C. In particular, it was found that Examples 2-2, 2-5, 2-10, 2-13, 2-16, 2-18, and 2-20 to 2-25, which had an ethynyl group in R1, had a film thickness reduction of less than 2% even after baking at 450°C for 10 minutes, and had particularly excellent heat resistance. In contrast, as shown in Table 13, Comparative Examples 2-1, 2-2, and 2-4 had a large film thickness reduction of more than 20%, and it was found that the imide structure had high heat resistance.

[0487] Evaluation of landfill properties (Examples 3-1 to 3-25, Comparative Examples 3-1 to 3-5)

[0488] As shown in Table 12, the organic film forming material of the present application (Examples 2-1 to 2-25) also had a film thickness reduction of 3% or less after calcination at 450°C for 10 minutes, and the organic film forming material of the present application could form an organic film having high heat resistance even under such a high temperature condition of 450°C. In particular, it was found that Examples 2-2, 2-5, 2-10, 2-13, 2-16, 2-18, and 2-20 to 2-25, which had an ethynyl group in R1, had a film thickness reduction of less than 2% even after baking at 450°C for 10 minutes, and had particularly excellent heat resistance. In contrast, as shown in Table 13, Comparative Examples 2-1, 2-2, and 2-4 had a large film thickness reduction of more than 20%, and it was found that the imide structure had high heat resistance. Figure 3 The above organic film forming material (UDL-1 to 25, Comparative UDL-1 to 5) was coated on a SiO2 wafer substrate having a dense hole pattern (hole diameter 0.16 μm, hole depth 0.50 μm, distance between centers of two adjacent holes 0.32 μm), and an organic film was formed by baking at 450°C for 600 seconds under a nitrogen gas stream having an oxygen concentration controlled to 0.2% or less using a hot plate. The substrate used was a base substrate 7 (SiO2 wafer substrate) having a dense hole pattern as shown in (G) (plan view) and (H) (cross-sectional view). Figure 3 The cross-sectional shape of each wafer substrate obtained was observed using a scanning electron microscope (SEM), and it was confirmed whether or not the inside of the hole was filled with the organic film without a gap (void). The results are shown in Tables 14 and 15. In the case of using an organic film material having poor filling properties, a gap was generated in the inside of the hole in this evaluation. In the case of using an organic film forming material having good filling properties, the inside of the hole was filled with the organic film 8 without a gap as shown in (I) in this evaluation. Figure 3

[0489] [Table 14]

[0490]

[0491] [Table 15]

[0492]

[0493] ​As shown in Table 14, it can be confirmed that the organic film forming material of the present invention (Examples 3-1 to 3-25) can fill the pore pattern without gaps, exhibiting excellent landfill characteristics. On the other hand, as shown in Table 15, in Comparative Examples 3-1, 3-2, and 3-4, gaps occurred due to insufficient heat resistance, similar to the results of Example 2. Furthermore, in Comparative Example 3-5, due to its rigid polymer structure and high molecular weight, although the heat resistance was sufficient, the landfill performance was insufficient, and gaps were observed. From these results, it can be confirmed that the organic film forming material of the present invention has excellent landfill characteristics.

[0494] Example 4: Evaluation of Flattening Characteristics (Examples 4-1 to 4-25, Comparative Examples 4-1 to 4-5)

[0495] Organic film forming materials (UDL-1 to 25, comparative UDL-1 to 5) were respectively coated onto... Figure 4 On a substrate 9 (SiO2 wafer substrate) with a large isolated trench pattern (trench width 10 μm, trench depth 0.10 μm) as shown in (J), baking at 450°C for 240 seconds under a nitrogen gas flow with oxygen concentration controlled below 0.2% resulted in the formation of a pattern resembling... Figure 4 After forming the organic film 10 as shown in (K), the height difference delta 10 between the trench and non-trench portions of the organic film was observed using an NX10 atomic force microscope (AFM) manufactured by Park Systems. The results are shown in Tables 16 and 17. In this evaluation, the smaller the height difference, the better the planarization characteristics. Furthermore, this evaluation used a trench pattern with a depth of 0.10 μm to planarize an organic film forming material with a typical film thickness of about 0.2 μm, which is a rigorous evaluation condition for assessing the quality of planarization characteristics.

[0496] [Table 16]

[0497]

[0498]

[0499] [Table 17]

[0500]

[0501] As shown in Table 16, it was confirmed that the organic film forming materials of the present invention (Examples 4-1 to 4-25) exhibited smaller height differences between the grooved and non-grooved portions of the organic film compared to Comparative Examples 4-1 to 4-5 shown in Table 17, resulting in excellent planarization characteristics. In Comparative Examples 4-2 and 4-4, although flowability was imparted through ether bonds, the heat resistance was insufficient, as demonstrated by the heat resistance evaluation of Example 2. Consequently, the film significantly shrank and its planarity deteriorated due to baking at 450°C. Furthermore, in Comparative Example 4-3, although the acetylene group was used as a crosslinking group, resulting in excellent heat resistance, the phenyl ether structure of the present invention was located far from the crosslinking group, thus failing to improve flowability and resulting in poor planarity compared to the similarly structured UDL-10. Additionally, in Comparative Example 4-5, although high heat resistance was achieved through the imide structure, the large molecular weight and lack of a phenyl ether structure prevented improvement in flowability, resulting in poor planarity. Furthermore, comparing Examples 4-23 to 4-25 with added high-boiling-point solvents with Examples 4-10, 4-16, and 4-20 without added solvents, it is evident that adding high-boiling-point solvents further improves flatness. From these results, it can be seen that the organic film-forming material of the present invention exhibits excellent planarization characteristics due to its excellent heat resistance, which suppresses film shrinkage during high-temperature baking.

[0502] Example 5: Pattern Formation Test (Examples 5-1 to 5-25, Comparative Examples 5-1 to 5-2)

[0503] The above-mentioned organic film forming materials (UDL-1 to 25, comparative UDL-3, 5) were respectively coated onto the film. Figure 4 On a substrate 9 (SiO2 wafer substrate) with a large isolated trench pattern formed of SiO2 (trench width 10 μm, trench depth 0.10 μm), as shown in (J), an organic film (lower resist layer) was formed by baking at 450°C for 60 seconds under a nitrogen gas flow with oxygen concentration controlled below 0.2%. A CVD-SiON hard mask was then formed on this substrate, followed by coating with an organic antireflective film material (ARC-29A: manufactured by Nissan Chemical Co., Ltd.) and baking at 210°C for 60 seconds to form an 80 nm thick organic antireflective film. An ArF single-layer resist was then coated on this substrate and baked at 105°C for 60 seconds to form a 100 nm thick photoresist film. Finally, a wettable protective film material (TC-1) was coated on the photoresist film and baked at 90°C for 60 seconds to form a 50 nm thick protective film. Furthermore, regarding the comparison of UDL-1, 2, and 4, as with the results of Example 2, their heat resistance was poor, so they could not form CVD-SiON hard masks and could not be used for subsequent patterning experiments.

[0504] As a resist upper layer film material (ArF single layer resist), polymer (RP1), acid generator (PAG1), and basic compound (Amine 1) were dissolved in a solvent containing FC-430 (Sumitomo 3M (Co. ) ) 0.1 mass% at the proportions of Table 18, filtered with a 0.1 μm fluorine resin filter, and thereby prepared.

[0505] [Table 18]

[0506]

[0507] The polymer (RP1), acid generator (PAG1), and basic compound (Amine 1) used are shown below.

[0508] [Chem. 67]

[0509]

[0510] As a soaking protective film material (TC-1), the protective film polymer (PP1) was dissolved in an organic solvent at the proportions of Table 19, filtered with a 0.1 μm fluorine resin filter, and thereby prepared.

[0511] [Table 19]

[0512]

[0513] The polymer (PP1) used is shown below.

[0514] [Chem. 68]

[0515]

[0516] Then, exposure was performed by an ArF soaking exposure device (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35° dipole s-polarized light illumination, 6% half-step phase shift mask), baking (PEB) was performed at 100°C for 60 seconds, development was performed with 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution for 30 seconds, and a 55 nm 1:1 positive type line and space pattern (resist pattern) was obtained.

[0517] Then, the resist pattern was used as a mask to etch process the organic antireflection film and CVD-SiON hard mask by dry etching using an etching device Telius manufactured by Tokyo Electron Limited to form a hard mask pattern, the obtained hard mask pattern was used as a mask to etch process the organic film to form an organic film pattern, and the obtained organic film pattern was used as a mask to etch process the SiO2 film. The etching conditions are shown below.

[0518] Transfer conditions of resist pattern to SiON hard mask

[0519] Chamber pressure 10.0 Pa

[0520] RF power 1,500 W

[0521] CF4gas flow rate 75 seem

[0522] O2gas flow rate 15 seem

[0523] Time 15 sec

[0524] Transfer conditions of hard mask pattern to organic film

[0525] Chamber pressure 2.0 Pa

[0526] RF power 500 W

[0527] Ar gas flow rate 75 seem

[0528] O2gas flow rate 45 seem

[0529] Time 120 sec

[0530] Transfer conditions of organic film pattern to SiO2film

[0531] Chamber pressure 2.0 Pa

[0532] RF power 2,200 W

[0533] C5F 12 Gas flow rate 20 seem

[0534] C2F6gas flow rate 10 seem

[0535] Ar gas flow rate 300 seem

[0536] O2gas flow rate 60 seem

[0537] Time 90 sec

[0538] The results after observing the pattern profile with a Hitachi, Ltd. electron microscope (S-4700) are shown in Table 20.

[0539] [Table 20]

[0540]

[0541]

[0542] As shown in Table 20, from the results of the organic film forming materials of the present application (Examples 5-1 to 5-25), it was confirmed that the resist upper layer film pattern (resist pattern) was finally well transferred to the substrate in any case, and the organic film forming material of the present application was suitable for use in fine processing using a multi-layer resist method. In Comparative Examples 5-1 and 5-2, defocus occurred at the time of resist exposure due to lack of flatness, and good patterns could not be obtained, so good patterns could not be obtained at the time of transfer.

[0543] Glass transition temperature of Example 6 (Examples 6-1, Comparative Examples 6-1 to 6-2)

[0544] The organic film forming compounds (A5) synthesized in the above Synthesis Example, and the organic film forming compounds (R4), (R5) synthesized in the above Comparative Synthesis Example were each diluted with N-methyl-2-pyrrolidone so that the solid content concentration became 50 mass%, and at this time, 2 mass% of dicumyl peroxide was added to dissolve it, and a varnish of the dissolved organic film forming compound was obtained. After that, microfiltration was performed with a 1.0 μm filter made of Teflon (registered trademark).

[0545] <Preparation of thin film sample>

[0546] The varnish of each of the organic film forming compounds prepared above was spin-coated on an aluminum substrate so that the finished film thickness after hardening became 10 μm. Then, pre-baking was performed at 100°C for 4 minutes on a hot plate, and a photosensitive resin film was obtained. After that, using an oven, hardening was performed at 180°C for 2 hours with nitrogen purge, and a resin hardened film was obtained. Then, the wafer with the attached hardened film was cut into a strip shape of width 10 mm and length 60 mm, the hardened film was peeled from the substrate by immersion in 20 mass% hydrochloric acid, and a thin film sample was obtained.

[0547] <Glass transition temperature (Tg)>

[0548] The glass transition temperature was measured for the thin film sample prepared above using TMA7100 made by Hitachi High-Tech Corporation.. The measurement results are shown in Table 21.

[0549] [Table 21]

[0550]

[0551] The hardened film of the varnish using the organic film-forming compound of the present application of Example 6-1 exhibited a high glass transition temperature. Furthermore, the thin film processability was superior compared to the organic film-forming compounds of Comparative Examples 6-1 and 6-2, and thus the compound can be used not only as an underlayer film material for a resist, but also for a multilayer printed wiring board used in high-frequency band electronic equipment requiring an insulating material having excellent dielectric properties, and the like, as described in the specification, as a raw material for various imide compounds, polyimide compounds, and the like.

[0552] From the above, it is clear that the organic film-forming material of the present application containing the organic film-forming compound of the present application can exhibit both heat resistance of 400°C or higher and a high degree of filling / plane- tizing properties even under a non-oxygen-containing inert gas, and thus is extremely useful as an organic film material for a multilayer resist method, and furthermore, the pattern forming method of the present application using the same can form a fine pattern with high precision even if the substrate to be processed is a substrate having unevenness. Furthermore, the organic film-forming compound synthesized using the aromatic carboxylic anhydride of the present application can be used not only as an organic film material for the above-described multilayer resist method, but also for a multilayer printed wiring board used in high-frequency band electronic equipment requiring an insulating material having excellent dielectric properties, and the like, as described in the specification, as a raw material for various imide compounds, polyimide compounds, and the like, and the like.

[0553] The present specification contains the following aspects.

[0554] [1] An organic film-forming material characterized by containing: (A) a compound represented by the following general formula (1A), and (B) an organic solvent;

[0555] [Chemical Formula 69]

[0556]

[0557] (In the formula, W1 is an n1-valent organic group, n1 represents an integer of 2 to 4, and X1 is a group represented by the following general formula (1B).

[0558] [Chemical Formula 70]

[0559]

[0560] (In the formula, n2 is 1 or 2, R1 is any one of groups represented by the following formula (1C), can have a substituent on the aromatic ring, and two or more kinds of R1 having different end structures can be used in combination.

[0561] [Chemical Formula 71]

[0562]

[0563] [2] The organic film forming material according to [1], wherein the (A) component is a compound represented by the following General Formula (ID).

[0564] [Chemical Formula 72]

[0565]

[0566] (In the formula, W2 is a single bond or a divalent organic group, n3, n4 are integers satisfying 2 ≤ n3 + n4 ≤ 4, a substituent can be present on the benzene ring in the formula, and the organic group in W2 and the substituent on the benzene ring can be bonded to form a cyclic organic group; X1 is the same as described above.)

[0567] [3] The organic film forming material according to [2], wherein W2 in the General Formula (ID) is a single bond, or any one of the groups represented by the following General Formula (IE).

[0568] [Chemical Formula 73]

[0569]

[0570] (In the formula, a substituent can be present on the aromatic ring.)

[0571] [4] The organic film forming material according to [2] or [3], wherein n3, n4 in the General Formula (ID) satisfy the relationships 1 ≤ n3 ≤ 2, 1 ≤ n4 ≤ 2, and 2 ≤ n3 + n4 ≤ 4.

[0572] [5] The organic film forming material according to any one of [1] to [4], wherein the (A) component has a ratio Mw / Mn of a weight average molecular weight Mw to a number average molecular weight Mn, in terms of polystyrene by gel permeation chromatography, of 1.00 ≤ Mw / Mn ≤ 1.10.

[0573] [6] The organic film forming material according to any one of [1] to [5], wherein the (B) component is a mixture of one or more kinds of organic solvents having a boiling point of less than 180°C, and one or more kinds of organic solvents having a boiling point of 180°C or more.

[0574] [7] The organic film forming material according to any one of [1] to [6], wherein the organic film forming material further contains one or more kinds of (C) acid generators, (D) surfactants, (E) crosslinking agents, and (F) plasticizers.

[0575] [8] A substrate for semiconductor device production, characterized by having formed on the substrate an organic film hardened from the organic film forming material according to any one of [1] to [7].

[0576] [9] A method for forming an organic film, which is a method for forming an organic film in a manufacturing step of a semiconductor device, characterized by spin-coating the material for forming an organic film according to any one of [1] to [7] on a substrate to be processed, and applying heat treatment to the coated material for forming an organic film at a temperature of 50°C or higher and 600°C or lower in a non-reactive gas atmosphere for a period of 10 seconds to 7200 seconds to obtain an organic film.

[0577]

[10] A method for forming an organic film, which is a method for forming an organic film in a manufacturing step of a semiconductor device, characterized by spin-coating the material for forming an organic film according to any one of [1] to [7] on a substrate to be processed, and applying heat treatment to the coated material for forming an organic film at a temperature of 50°C or higher and 300°C or lower in air for a period of 5 seconds to 600 seconds to form a coated film, and then applying heat treatment to the coated film at a temperature of 200°C or higher and 600°C or lower in a non-reactive gas atmosphere for a period of 10 seconds to 7200 seconds to obtain an organic film.

[0578]

[11] The method for forming an organic film according to [9] or

[10] , wherein the oxygen concentration in the non-reactive gas atmosphere is 1% or lower.

[0579]

[12] The method for forming an organic film according to any one of [9] to

[11] , wherein a substrate to be processed having a structure with a height of 30 nm or higher or a substrate to be processed having a height difference is used as the substrate to be processed.

[0580]

[13] A method for forming a pattern, characterized by forming an organic film on a substrate to be processed using the material for forming an organic film according to any one of [1] to [7], forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the silicon-containing resist intermediate film by etching using the patterned resist upper layer film as a mask, transferring the pattern to the organic film by etching using the pattern-transferred silicon-containing resist intermediate film as a mask, and further transferring the pattern to the substrate to be processed by etching using the pattern-transferred organic film as a mask.

[0581]

[14] : A pattern forming method characterized by forming an organic film on a processed object using the material for organic film formation according to any one of [1] to [7], forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, forming an organic antireflection film on the silicon-containing resist intermediate film, forming an upper resist film on the organic antireflection film using a photoresist composition to become a 4-layer film structure, forming a circuit pattern on the upper resist film, transferring the pattern to the organic antireflection film and the silicon-containing resist intermediate film by etching with the patterned upper resist film serving as a mask, transferring the pattern to the organic film by etching with the pattern-transferred silicon-containing resist intermediate film serving as a mask, and further transferring the pattern to the processed object by etching with the pattern-transferred organic film serving as a mask.

[0582]

[15] : A pattern forming method characterized by forming an organic film on a processed object using the material for organic film formation according to any one of [1] to [7], forming an inorganic hard mask intermediate film selected from the group consisting of 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 an upper resist film on the inorganic hard mask intermediate film using a photoresist composition, forming a circuit pattern on the upper resist film, transferring the pattern to the inorganic hard mask intermediate film by etching with the patterned upper resist film serving as a mask, transferring the pattern to the organic film by etching with the pattern-transferred inorganic hard mask intermediate film serving as a mask, and further transferring the pattern to the processed object by etching with the pattern-transferred organic film serving as a mask.

[0583]

[16] : A pattern forming method characterized by forming an organic film on a processed object using the material for organic film formation according to any one of [1] to [7], forming an inorganic hard mask intermediate film selected from the group consisting of 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 an organic antireflection film on the inorganic hard mask intermediate film, forming an upper resist film on the organic antireflection film using a photoresist composition to become a 4-layer film structure, forming a circuit pattern on the upper resist film, transferring the pattern to the organic antireflection film and the inorganic hard mask intermediate film by etching with the patterned upper resist film serving as a mask, transferring the pattern to the organic film by etching with the pattern-transferred inorganic hard mask intermediate film serving as a mask, and further transferring the pattern to the processed object by etching with the pattern-transferred organic film serving as a mask.

[0584]

[17] : The pattern forming method according to

[15] or

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

[0585]

[18] The pattern forming method according to any one of

[13] to

[17] , wherein, in the formation of the circuit pattern, the circuit pattern is formed by photolithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing by electron beam, nanoimprint, or a combination of these.

[0586]

[19] The pattern forming method according to any one of

[13] to

[18] , wherein, in the formation of the circuit pattern, the circuit pattern is developed by alkali development or an organic solvent.

[0587]

[20] The pattern forming method according to any one of

[13] to

[19] , wherein, as the workpiece, a semiconductor device substrate or a semiconductor device substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film is formed is used.

[0588]

[21] The pattern forming method according to

[20] , wherein, as the workpiece, one containing silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof is used.

[0589]

[22] An organic film forming compound characterized by being represented by the following general formula (1A).

[0590] [Chemical Formula 74]

[0591]

[0592] (In the formula, W1 is an n1-valent organic group, n1 represents an integer of 2 to 4, and X1 is a group represented by the following general formula (1B).

[0593] [Chemical Formula 75]

[0594]

[0595] (In the formula, n2 is 1 or 2, R1 is any one of groups represented by the following formula (1C), a substituent can be present on the aromatic ring, and two or more kinds of R1 having different end structures can be used in combination.

[0596] [Chemical Formula 76]

[0597]

[0598]

[23] The organic film forming compound according to

[22] , wherein the organic film forming compound is represented by the following general formula (1D).

[0599] [Chemical Formula 77]

[0600]

[0601] (In the formula, W2 is a single bond or a divalent organic group, n3, n4 are integers satisfying 2 ≤ n3 + n4 ≤ 4, and a substituent can be present on the benzene ring in the formula, and the organic group in W2 and the substituent on the benzene ring can be bonded to form a cyclic organic group; X1 is the same as described above.)

[0602]

[24] The organic film-forming compound according to

[23] , wherein W2 in the general formula (1D) is a single bond, or any one of groups represented by the following general formula (1E).

[0603] [Chemical Formula 78]

[0604]

[0605] (In the formula, a substituent can be present on the aromatic ring.)

[0606]

[25] The organic film-forming compound according to

[23] or

[24] , wherein n3, n4 in the general formula (1D) satisfy the relationships 1 ≤ n3 ≤ 2, 1 ≤ n4 ≤ 2, and 2 ≤ n3 + n4 ≤ 4.

[0607]

[26] An aromatic carboxylic anhydride characterized by being represented by the following general formula (1F).

[0608] [Chemical Formula 79]

[0609]

[0610] (In the formula, n2 is 1 or 2, R1 is any one of groups represented by the following general formula (1G), a substituent can be present on the aromatic ring, and two or more kinds of R1 of end structures can be used in combination.)

[0611] [Chemical Formula 80]

[0612]

[0613] Further, the present application is not limited to the above-described embodiments. The above-described embodiments are illustrative, and those having substantially the same configuration as the technical idea recited in the claims of the present application and exerting the same effects are included in the technical scope of the present application.

[0614] Explanation of Reference Signs

[0615] 1: substrate

[0616] 2: layer to be processed

[0617] 2a: pattern (pattern formed on the layer to be processed)

[0618] 3: organic film

[0619] 3': material for forming an organic film

[0620] 3a: organic film pattern

[0621] 4: silicon-containing resist intermediate film

[0622] 4a: silicon-containing resist intermediate film pattern

[0623] 5: resist upper film

[0624] 5a: resist upper film pattern

[0625] 6: exposed portion

[0626] 7: base substrate having a dense hole pattern

[0627] 8: organic film

[0628] 9: base substrate having a large isolated trench pattern

[0629] 10: organic film

[0630] delta 10: height difference of the organic film between the trench portion and the non-trench portion

Claims

1. A material for forming organic films, characterized in that, Contains: (A) a compound represented by the following general formula (1A), and (B) an organic solvent; In the formula, W1 is an n1-valent organic group, n1 represents an integer from 2 to 4, and X1 is a group represented by the following general formula (1B); In the formula, n2 is 1 or 2, and R1 is any of the groups represented by the following formula (1C). It may also have substituents on the aromatic ring, and R1 may be used in combination with two or more terminal structures.

2. The material for forming organic films according to claim 1, wherein, The component (A) is a compound represented by the following general formula (1D); In the formula, W2 is a single bond or a divalent organic group, and n3 and n4 are integers of 2 ≤ n3 + n4 ≤ 4. Substituents may also be present on the benzene ring in the formula. The organic group in W2 and the substituents on the benzene ring may also bond to form a cyclic organic group; X1 is the same as above.

3. The material for forming organic films according to claim 2, wherein, In this general formula (1D), W2 is a single bond or any of the groups represented by the following formula (1E); In this formula, substituents may also be present on the aromatic ring.

4. The material for forming organic films according to claim 2, wherein, In the general formula (1D), n3 and n4 satisfy the relationships 1≤n3≤2, 1≤n4≤2, and 2≤n3+n4≤4.

5. The material for forming organic films according to claim 1, wherein, The ratio of the weight-average molecular weight Mw to the number-average molecular weight Mn of component (A) calculated by gel permeation chromatography is 1.00 ≤ Mw / Mn ≤ 1.

10.

6. The material for forming organic films according to claim 1, wherein, The component (B) is a mixture of one or more organic solvents with a boiling point of less than 180°C and one or more organic solvents with a boiling point of more than 180°C.

7. The material for forming organic films according to claim 1, wherein, The organic film forming material also 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, It is formed on a substrate by hardening an organic film made of an organic film forming material according to any one of claims 1 to 7.

9. A method for forming an organic film, applicable to the organic film formation process in the manufacturing steps of a semiconductor device, characterized in that, An organic film is obtained by spin-coating an organic film forming material according to any one of claims 1 to 7 onto a substrate to be processed, and then subjecting the substrate to which the organic film forming material is coated to heat treatment in a passivating gas environment at a temperature of 50°C to 600°C for a range of 10 seconds to 7200 seconds.

10. A method for forming an organic film, applicable to the organic film formation process in the manufacturing steps of a semiconductor device, characterized in that, An organic film is formed by spin-coating an organic film forming material according to any one of claims 1 to 7 onto a substrate to be processed, and by 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 by heat-treating it in a passivating gas environment at a temperature of 200°C to 600°C for 10 to 7200 seconds to obtain an organic film.

11. The method for forming an organic membrane according to claim 9, wherein, The oxygen concentration in this inert gas environment is below 1%.

12. The method for forming an organic membrane according to claim 9, wherein, As the substrate to be processed, a structure with a height of 30 nm or more or a height difference is used.

13. A method for forming a pattern, characterized in that, An organic film is formed on a workpiece using an organic film forming material according to any one of claims 1 to 7; a silicon-containing photoresist intermediate film is formed on the organic film using a silicon-containing photoresist intermediate film material; a photoresist upper film is formed on the silicon-containing photoresist intermediate film using a photoresist composition; a circuit pattern is formed on the photoresist upper film; the patterned photoresist upper film is used as a mask and the pattern is transferred to the silicon-containing photoresist intermediate film by etching; the patterned silicon-containing photoresist intermediate film is used as a mask and the pattern is transferred to the organic film by etching; further, the patterned organic film is used as a mask and the pattern is transferred to the workpiece by etching.

14. A method for forming a pattern, characterized in that, An organic film is formed on a workpiece using an organic film forming material according to any one of claims 1 to 7; a silicon-containing photoresist intermediate film is formed on the organic film using a silicon-containing photoresist intermediate film material; an organic antireflective film is formed on the silicon-containing photoresist intermediate film; a photoresist upper film is formed on the organic antireflective film using a photoresist composition, thus forming a four-layer film structure; a circuit pattern is formed on the photoresist upper film; the patterned photoresist upper film is used as a mask and the pattern is transferred to the organic antireflective film and the silicon-containing photoresist intermediate film by etching; the patterned silicon-containing photoresist intermediate film is used as a mask and the pattern is transferred to the organic film by etching; furthermore, the patterned organic film is used as a mask and the pattern is transferred to the workpiece by etching.

15. A method for forming a pattern, characterized in that, An organic film is formed on a workpiece using an organic film forming material according to any one of claims 1 to 7. An inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, silicon oxide nitride film, titanium oxide film, and titanium nitride film is formed on the organic film. A photoresist upper film is formed on the inorganic hard mask intermediate film using a photoresist composition. A circuit pattern is formed on the photoresist upper film. The patterned photoresist upper film is used as a mask and the pattern is transferred to the inorganic hard mask intermediate film by etching. The patterned inorganic hard mask intermediate film is used as a mask and the pattern is transferred to the organic film by etching. Further, the patterned organic film is used as a mask and the pattern is transferred to the workpiece by etching.

16. A method for forming a pattern, characterized in that, An organic film is formed on a workpiece using an organic film forming material according to any one of claims 1 to 7. An inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, silicon oxide nitride film, titanium oxide film, and titanium nitride film is formed on the organic film. An organic antireflective film is formed on the inorganic hard mask intermediate film. A photoresist composition is used on the organic antireflective film to form a photoresist upper film, resulting in a four-layer film structure. A circuit pattern is formed on the photoresist upper film. The patterned photoresist upper film is used as a mask, and the pattern is transferred to the organic antireflective film and the inorganic hard mask intermediate film by etching. The patterned inorganic hard mask intermediate film is used as a mask, and the pattern is transferred to the organic film by etching. Further, the patterned organic film is used as a mask, and the pattern is transferred to the workpiece by etching.

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

18. The pattern forming method according to claim 13, wherein, The circuit pattern is formed by photolithography using light with wavelengths between 10 nm and 300 nm, direct drawing by electron beam, nanoimprinting, or a combination thereof.

19. The pattern forming method according to claim 13, wherein, In the formation of this circuit pattern, the circuit pattern is developed using alkaline development or organic solvents.

20. The pattern forming method according to claim 13, wherein, The workpiece is made by using a semiconductor device substrate, or by forming any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film on the semiconductor device substrate.

21. The pattern forming method according to claim 20, wherein, The workpiece may be made of silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof.

22. A compound for forming organic films, characterized in that, It is represented by the following general formula (1A); In the formula, W1 is an n1-valent organic group, n1 represents an integer from 2 to 4, and X1 is a group represented by the following general formula (1B); In the formula, n2 is 1 or 2, and R1 is any of the groups represented by the following formula (1C). It may also have substituents on the aromatic ring, and R1 may be used in combination with two or more terminal structures.

23. The compound for forming organic films according to claim 22, wherein, The compound for forming the organic film is represented by the following general formula (1D); In the formula, W2 is a single bond or a divalent organic group, and n3 and n4 are integers that satisfy 2≤n3+n4≤4. Substituents may also be present on the benzene ring in the formula. The organic group in W2 and the substituents on the benzene ring may also bond to form a cyclic organic group; X1 is the same as above.

24. The compound for forming organic films according to claim 23, wherein, In this general formula (1D), W2 is a single bond or any of the groups represented by the following formula (1E); In this formula, substituents may also be present on the aromatic ring.

25. The compound for forming organic films according to claim 23, wherein, In the general formula (1D), n3 and n4 satisfy the relationships 1≤n3≤2, 1≤n4≤2, and 2≤n3+n4≤4.

26. An aromatic carboxylic anhydride, characterized in that, It is represented by the following general formula (1F); In the formula, n2 is 1 or 2, and R1 is any of the groups represented by the following formula (1G). It may also have substituents on the aromatic ring, and R1 may be used in combination with two or more terminal structures.

Images