Organic film forming material, pattern forming method, and compound

Abstract

The present invention relates to an organic film forming material, a pattern forming method and a compound. The purpose of the present invention is to provide a compound that can form an organic lower layer film that has not only excellent heat resistance, filling and planarization properties of the pattern formed on the substrate, but also good film forming properties and adhesion to the substrate, and to provide an organic film forming material containing the compound. The solution of the present invention is an organic film forming material, characterized in that it contains a compound represented by the following general formula (1) and an organic solvent. #imgabs0# In the general formula (1), R1 is any one of the following formulas (2), R2 represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group, an alkynyloxy group, an alkenyloxy group, a linear, branched or cyclic alkyl group, a trifluoromethyl group, or a trifluoromethyloxy group; n represents 0 or 1, m represents an integer from 1 to 3, p represents 0 or 1, and l represents an integer from 0 to 2; and W is a divalent organic group having 2 to 40 carbon atoms. #imgabs1#

Description

Technical Field

[0001] The present invention relates to an organic film forming material, a pattern forming method, and a compound suitable for use in the above-mentioned material. Existing technology

[0002] With the increasing integration and speed of LSIs, pattern sizes are rapidly becoming smaller. Photolithography technology, along with this miniaturization, has achieved the formation of fine patterns through the shortening of light sources and the appropriate selection of corresponding resist compositions. Central to this development is a single-layer positive photoresist composition. This single-layer positive photoresist composition incorporates a resist resin with a backbone resistant to dry etching using chlorine- or fluorine-based gas plasma, and a switching mechanism that dissolves the exposed portion. This allows the exposed portion to dissolve to form a pattern, and the remaining resist pattern serves as an etching mask for dry etching of the substrate being processed.

[0003] However, when miniaturization is performed while maintaining the film thickness of the photoresist film being used, that is, when the pattern width is further reduced, the resolution performance of the photoresist film decreases. In addition, when the photoresist film is used to develop the pattern with a developer, the aspect ratio becomes too large, resulting in pattern collapse. Therefore, as the pattern becomes miniaturized, the photoresist film thickness is gradually reduced.

[0004] On the other hand, processing of substrates typically involves using a patterned photoresist film as an etching mask and dry etching to process the substrate. However, there is no dry etching method that can achieve complete etching selectivity between the photoresist film and the substrate being processed. Consequently, the resist film can be damaged and broken during substrate processing, preventing the resist pattern from being properly transferred to the substrate being processed. Consequently, with the increasing miniaturization of patterns, photoresist compositions are also being sought to have higher dry etching resistance. However, to improve resolution, the resins used in photoresist compositions are required to have low light absorption at the exposure wavelength. Therefore, as exposure light becomes shorter, such as i-rays, KrF, and ArF, resins have shifted to novolac resins, polyhydroxystyrene, and resins with aliphatic polycyclic backbones. These resins, in fact, exhibit faster etching speeds under the dry etching conditions used during substrate processing. Recent photoresist compositions with higher resolution tend to have weaker etching resistance.

[0005] Due to this fact, it becomes necessary to dry-etch the substrate to be processed through a thinner photoresist film with weaker etching resistance, and it is important to ensure the materials and processing in this processing step.

[0006] One method for solving this problem is the multilayer resist method. This method involves inserting an interlayer film, which has a different etching selectivity from the photoresist film (i.e., the resist upper layer), between the resist upper layer and the substrate being processed. After a pattern is formed on the resist upper layer, the pattern is transferred to the interlayer film by dry etching, using the resist upper layer pattern as a dry etching mask. Furthermore, the pattern is transferred to the substrate being processed by dry etching, using the interlayer film as a dry etching mask.

[0007] One type of multilayer resist method is the three-layer resist method, which can be performed using the typical resist compositions used in the single-layer resist method. This three-layer resist method involves forming an organic film, such as a novolac, as a resist lower layer on a substrate to be processed, forming a silicon-containing film as a silicon-containing resist intermediate film on top of the organic film, and then forming a conventional organic photoresist film as a resist upper layer on top of the organic film. When dry-etched with fluorine-based gas plasma, the organic resist upper layer exhibits a good etching selectivity relative to the silicon-containing resist intermediate film, allowing the resist upper layer pattern to be transferred to the silicon-containing resist intermediate film through dry etching with the fluorine-based gas plasma. According to this method, even when using a resist composition that is difficult to form a pattern having a sufficient film thickness for direct processing of a substrate, or when using a resist composition that does not have sufficient dry etching resistance for processing a substrate, if the pattern can be transferred to a silicon-containing film (resist intermediate film) and then the pattern transfer is performed by dry etching using oxygen-based or hydrogen-based gas plasma, a pattern of an organic film (resist underlayer film) made of a novolac resin or the like having sufficient dry etching resistance for substrate processing can be obtained. As such resist underlayer films, many types are known, such as those described in Patent Document 1.

[0008] On the other hand, in recent years, the manufacture of semiconductor devices with new structures such as multi-gate structures has been actively studied. In response to this, the requirements for the planarization and filling characteristics of the resist lower layer film are becoming increasingly better than before. For example, when the base substrate to be processed has micro-pattern structures such as holes, trenches, and fins, it is necessary to utilize the characteristics of the resist lower layer film to fill the pattern with the film without gaps. In addition, when the base substrate to be processed has height differences, when the pattern-dense part and the area without pattern exist on the same wafer, it is necessary to use the resist lower layer film to flatten the film surface (planarization). By flattening the surface of the lower layer film, the film thickness variation of the resist intermediate film and the resist upper film formed thereon can be suppressed, and the focus tolerance of the lithography and the reduction in tolerance in the subsequent processing steps of the processed substrate can be suppressed.

[0009] Furthermore, organic film materials with excellent filling and planarizing properties are not limited to use as underlayer films for multilayer resists. For example, they can be used as planarizing materials for semiconductor device manufacturing, for example, for substrate planarization prior to patterning using nanoimprint lithography. Furthermore, while CMP is currently the most common method for planarizing the entire surface of a semiconductor device during manufacturing, this is a costly process, leading to the development of materials that can replace it and achieve this goal.

[0010] To form a planarizing film for flattening uneven semiconductor substrates, a resist underlayer film material comprising a polymer obtained by reacting an aromatic compound with a compound having a carbon-oxygen double bond, such as a carbonyl group, has been proposed (Patent Document 2). However, this material is insufficient to meet the requirements of state-of-the-art devices, such as those for flattening wide trenches in substrates. Consequently, a resist underlayer film material with excellent flatness over wider substrate structures is being sought.

[0011] Furthermore, as the structure of the substrate being processed becomes more complex, research is underway to utilize novel materials with high electron mobility, such as strained silicon and gallium arsenide, as well as ultra-thin polysilicon with angstrom-level control. This allows for film formation to accommodate a wide variety of substrate surface shapes and materials. Therefore, to ensure process latitude, not only are excellent fill and planarization characteristics crucial, but also the ability to form films independently of the substrate's material and shape.

[0012] Prior art literature

[0013] Patent Literature

[0014] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-205685

[0015] [Patent Document 2] WO2019-225615 Summary of the Invention

[0016] [Problems to be Solved by the Invention]

[0017] The present invention was created based on the above-mentioned circumstances, and its purpose is to provide a compound that can form an organic lower layer film that not only has excellent heat resistance, filling and planarization properties of the pattern formed on the substrate, but also has good film forming properties and adhesion to the substrate, and to provide an organic film forming material containing the compound.

[0018] [Methods for solving the problem]

[0019] In order to solve the above problems, the present invention provides an organic film forming material.

[0020] Contains a compound represented by the following general formula (1) and an organic solvent.

[0021] [Chemistry 1]

[0022]

[0023] (In the general formula (1), R1 is any one of the following formulas (2); R2 represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; n represents 0 or 1, m represents an integer of 1 to 3, p represents 0 or 1, and l represents an integer of 0 to 2; and W represents a divalent organic group having 2 to 40 carbon atoms)

[0024] [Chemistry 2]

[0025]

[0026] The compound of the present invention represented by the general formula (1) has excellent heat resistance and solubility, so it can be made into an organic film material as a single compound. Compared with high molecular weight compounds, it has better thermal fluidity, so when the organic film is used as a resist underlayer film, it also has excellent filling / planarization properties for patterned substrates. Because the above compound has a cyclic amide structure in the molecule, it does not impair heat resistance and can also improve adhesion to the substrate and film forming properties. In addition, by appropriately selecting the linking portion represented by W, various physical properties of the organic film when used as a resist underlayer film, such as optical properties and etching resistance, can be adjusted to match the required performance.

[0027] Furthermore, the compound represented by the above-mentioned general formula (1) is preferably a compound represented by the following general formula (3).

[0028] [Chemistry 3]

[0029]

[0030] (In the general formula (3), R1, R2, W, l, and p are the same as described above; m' represents an integer of 1 or 2.)

[0031] By introducing such a structure, thermal fluidity can be improved and the filling / planarization performance can be further improved.

[0032] Furthermore, the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the compound in terms of polystyrene determined by gel permeation chromatography is preferably 1.00≤Mw / Mn≤1.10.

[0033] By controlling the Mw / Mn of the compound to fall within such a range, an organic film having excellent filling properties and flatness can be formed.

[0034] Furthermore, the organic solvent is preferably a mixture of one or more organic solvents having a boiling point of less than 180 degrees and one or more organic solvents having a boiling point of 180 degrees or higher.

[0035] When the organic solvent is the mixture, thermal fluidity can be imparted to the organic film by adding a high-boiling-point solvent to the compound, and the organic film forming material can be a material having both high filling and planarizing properties.

[0036] Furthermore, it is preferable to contain one or more of an acid generator, a crosslinking agent, a surfactant, and a plasticizer.

[0037] An organic film-forming material containing the above-mentioned additives can provide a material with more excellent coating properties and filling / planarization characteristics.

[0038] The present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate.

[0039] forming an organic film on a workpiece using the organic film forming material;

[0040] forming a silicon-containing resist interlayer film on the organic film using a silicon-containing resist interlayer material;

[0041] forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition;

[0042] forming a circuit pattern on the upper layer of the resist;

[0043] Using the patterned resist upper layer film as a mask, the pattern is transferred to the silicon-containing resist intermediate film by etching;

[0044] Using the transferred patterned silicon-containing resist intermediate film as a mask, the pattern is transferred to the organic film by etching;

[0045] Furthermore, the object to be processed is etched using the organic film to which the pattern has been transferred as a mask to form a pattern on the object to be processed.

[0046] The pattern forming method using the three-layer resist process described above can form a fine pattern on a substrate to be processed with high precision.

[0047] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, comprising the following steps:

[0048] forming an organic film on a workpiece using the organic film forming material;

[0049] forming a silicon-containing resist interlayer film on the organic film using a silicon-containing resist interlayer material;

[0050] forming an organic anti-reflective film (BARC) on the silicon-containing resist intermediate film;

[0051] A photoresist composition is used to form a resist upper layer film on the BARC to form a four-layer film structure;

[0052] forming a circuit pattern on the upper layer of the resist;

[0053] Using the patterned resist upper layer film as a mask, the pattern is transferred to the BARC film and the silicon-containing resist intermediate film by etching;

[0054] Using the transferred patterned silicon-containing resist intermediate film as a mask, the pattern is transferred to the organic film by etching;

[0055] Furthermore, the object to be processed is etched using the organic film to which the pattern has been transferred as a mask to form a pattern on the object to be processed.

[0056] By using the pattern forming method using the four-layer resist process, a fine pattern can be formed on a substrate to be processed with even higher precision.

[0057] In addition, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, comprising the following steps:

[0058] forming an organic film on a workpiece using the organic film forming material;

[0059] forming an inorganic hard mask film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film;

[0060] forming a resist upper layer film on the inorganic hard mask using a photoresist composition;

[0061] forming a circuit pattern on the upper layer of the resist;

[0062] Using the patterned resist upper layer film as a mask, the inorganic hard mask is etched to transfer the pattern;

[0063] Using the patterned inorganic hard mask as a mask, the organic film is etched to transfer the pattern;

[0064] Furthermore, the object to be processed is etched using the patterned organic film as a mask to form a pattern on the object to be processed.

[0065] This three-layer resist process is used as a pattern forming method, and a fine pattern can be formed on a substrate to be processed with high precision.

[0066] In addition, the present invention provides a pattern forming method, which is a method for forming a pattern on a processed substrate, comprising the following steps:

[0067] forming an organic film on a workpiece using the organic film forming material;

[0068] forming an inorganic hard mask film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film;

[0069] forming an organic anti-reflective film (BARC) on the inorganic hard mask;

[0070] Using a photoresist composition, a resist upper layer film is formed on the BARC to form a four-layer film structure;

[0071] forming a circuit pattern on the upper layer of the resist;

[0072] Using the patterned resist upper layer as a mask, the BARC film and the inorganic hard mask are etched to transfer a pattern;

[0073] Using the patterned inorganic hard mask as a mask, the organic film is etched to transfer the pattern;

[0074] Furthermore, the object to be processed is etched using the patterned organic film as a mask to form a pattern on the object to be processed.

[0075] The pattern forming method using the four-layer resist process can form a fine pattern on a substrate to be processed with higher precision.

[0076] In this case, the inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0077] If the inorganic hard mask is formed by a CVD method or an ALD method, a fine pattern can be formed on a substrate to be processed with higher precision.

[0078] The patterning method of the resist upper layer film is preferably optical lithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0079] If the above method is used in the method of forming a circuit pattern on the resist upper layer film, a fine pattern can be formed on the substrate to be processed with higher precision.

[0080] In addition, the development method in the above-mentioned pattern forming method is preferably alkali development or development using an organic solvent.

[0081] When alkali development or development using an organic solvent is used as a development method, a fine pattern can be formed on a substrate to be processed with higher precision.

[0082] Furthermore, the above-mentioned workpiece is preferably a semiconductor device substrate, or a substrate formed 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 or a metal oxide nitride film on the semiconductor device substrate.

[0083] In the present invention, as the substrate to be processed, for example, the substrates described above can be used.

[0084] Furthermore, the metal is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, cobalt, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, manganese, molybdenum, ruthenium, or an alloy thereof.

[0085] When patterning is performed using the organic film-forming material of the present invention in this manner, the pattern of the upper photoresist layer can be transferred with high precision and formed on a substrate to be processed.

[0086] The present invention provides a compound represented by the following general formula (1).

[0087] [Chemistry 4]

[0088]

[0089] (In the general formula (1), R1 is any one of the following formulas (2); R2 represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; n represents 0 or 1, m represents an integer from 1 to 3, p represents 0 or 1, and l represents an integer from 0 to 2; and W represents a divalent organic group having 2 to 40 carbon atoms)

[0090] [Chemistry 5]

[0091]

[0092] The compound represented by the general formula (1) is a compound for an organic film-forming material capable of forming an organic film having excellent heat resistance, filling / planarization characteristics, and film-forming properties.

[0093] Furthermore, the compound represented by the above general formula (1) is preferably represented by the following general formula (3).

[0094] [Chemistry 6]

[0095]

[0096] (In the general formula (3), R1, R2, W, l, and p are the same as those described above, and m' represents an integer of 1 or 2.)

[0097] Such a compound can further enhance the filling and planarizing properties of the compound for an organic film forming material.

[0098] [Effects of the Invention]

[0099] As explained above, the compound of the present invention can be used to form an organic film having excellent heat resistance, filling / planarization performance and excellent film forming properties. In addition, the organic film forming material containing the compound has various characteristics such as heat resistance, filling / planarization characteristics, and becomes a useful material for forming an organic film that does not have the dependency of processing substrates and can form a film. Therefore, for example, as an organic film forming material in a multilayer resist process such as a 2-layer resist process, a 3-layer resist process using a silicon-containing resist intermediate film, or a 4-layer resist process using a silicon-containing resist intermediate film and an organic anti-reflection film, or as a semiconductor device manufacturing planarization material is extremely useful. In addition, as long as it is the pattern forming method of the present invention, in the multilayer resist process, a fine pattern can be formed on the processed substrate with high precision. BRIEF DESCRIPTION OF THE DRAWINGS

[0100] [ Figure 1 ](A) to (F) are explanatory diagrams of an example of a pattern forming method using a three-layer resist process according to the present invention.

[0101] [ Figure 2 ](G) to (I) Illustrations of the landfill characteristic evaluation method in the embodiments.

[0102] [ Figure 3 ](J), (K) Illustrations of the planarization characteristic evaluation method in the embodiment.

[0103] [ Figure 4 ] Illustration of the adhesion measurement method in the embodiment. DETAILED DESCRIPTION

[0104] As mentioned above, there are organic film-forming materials, pattern-forming methods using the organic film-forming materials, and compounds suitable for the organic film-forming materials that are sought to form an organic film having excellent film-forming properties and flatness even on a processed substrate having a portion particularly difficult to flatten, such as a wide trench structure, in a fine patterning process using a multilayer resist method in the manufacturing steps of a semiconductor device.

[0105] The inventors of the present application have found that the compound of the present invention having a main skeleton formed of a specific heterocyclic structure is useful for forming an organic film having excellent filling / planarization properties, and have completed the present invention.

[0106] That is, the present invention is an organic film-forming material comprising a compound represented by the following general formula (1) and an organic solvent.

[0107] [Chemistry 7]

[0108]

[0109] (In the general formula (1), R1 is any one of the following formulas (2); R2 represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; n represents 0 or 1, m represents an integer of 1 to 3, p represents 0 or 1, and l represents an integer of 0 to 2; and W represents a divalent organic group having 2 to 40 carbon atoms.)

[0110] [Chemistry 8]

[0111]

[0112] The following describes the embodiments of the present invention, but the present invention is not limited to these. In addition, the compounds shown in the specification include their stereoisomers. For example, the compound represented by general formula (1) includes stereoisomers such as cis-trans isomers.

[0113] <Compounds for Organic Film-Forming Materials>

[0114] The compound used as the organic film-forming material of the present invention is a compound represented by the following general formula (1).

[0115] [Chemistry 9]

[0116]

[0117] (In the general formula (1), R1 is any one of the following formulas (2); R2 represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; n represents 0 or 1, m represents an integer of 1 to 3, p represents 0 or 1, and l represents an integer of 0 to 2; and W represents a divalent organic group having 2 to 40 carbon atoms.)

[0118] [Chemistry 10]

[0119]

[0120] W in the general formula (1) is a divalent organic group having 2 to 40 carbon atoms, and specific examples thereof include the following structures. Among these, an alkylene group is preferred from the viewpoint of easy availability of raw materials and imparting thermal fluidity.

[0121] [Chemistry 11]

[0122]

[0123] R1 in the general formula (1) is any one of the following formulas (2). From the viewpoint of imparting thermosetting properties and fluidity, an ethynyl group or a propargyloxy group is preferred.

[0124] [Chemistry 12]

[0125]

[0126] R2 represents a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, an alkynyloxy group having 2 to 4 carbon atoms such as a propargyloxy group, an alkenyloxy group having 2 to 4 carbon atoms such as an allyloxy group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms such as a methyl group, an isobutyl group or a cyclohexyl group, a trifluoromethyl group or a trifluoromethyloxy group.

[0127] Specific examples of the general formula (1) include the following: R1, R2, W, and I are the same as those described above.

[0128] [Chemistry 13]

[0129]

[0130] [Chemistry 14]

[0131]

[0132] Furthermore, m is an integer of 1 to 3, and p is not particularly limited as long as it is a value of 0 or 1. Preferably, m=1 or 2, and p=0.

[0133] Furthermore, the compound is preferably a compound represented by the following general formula (3).

[0134] [Chemistry 15]

[0135]

[0136] (In the above general formula (3), R1, R2, W, l, and p are the same as those described above. m' represents an integer of 1 or 2.)

[0137] Specific examples of the compound of the general formula (3) include the following compounds. Among these, compounds having a propargyloxy group or an ethynyl group as a substituent are particularly preferred from the viewpoint of thermal fluidity and curability. W, R2, and I in the general formula below are the same as those described above.

[0138] [Chemistry 16]

[0139]

[0140] Furthermore, the ratio Mw / Mn of the weight average molecular weight Mw and number average molecular weight Mn of the compound represented by the general formula (1) in terms of polystyrene as determined by gel permeation chromatography is preferably 1.00≤Mw / Mn≤1.10.

[0141] By controlling the Mw / Mn of the compound to fall within such a range, an organic film having excellent filling properties and flatness can be formed.

[0142] The compound of the present invention has a structure containing a large number of aromatic rings, and therefore has excellent heat resistance and etching resistance. It can also be combined with substituents that impart fluidity and hardening properties, heterocyclic structures that impart film-forming properties and adhesion, or linking structures that further enhance fluidity, and is useful as an organic film-forming compound.

[0143] [Method for producing compound]

[0144] As an example of a method for producing a compound represented by general formula (1) of the present invention, there can be exemplified a step (STEP 1) of obtaining a bis(indole-2,3-dione) as an intermediate by a substitution reaction using a base catalyst using a compound represented by XWX having two leaving groups X and an indole-2,3-diones as raw materials, and then a step (STEP 2) of obtaining the target compound by a dehydration condensation reaction using an acid catalyst using an aniline or aminonaphthalene having R1 as a substituent as a raw material. In the reactions used in STEP 1 and STEP 2, the raw materials can be used alone or in combination of two or more, and these can be appropriately selected and combined according to the required properties. R1, R2, W, n, m, l, and p are the same as those described above, and X is a halide, tosylate, or mesylate.

[0145] [Chemistry 17]

[0146]

[0147] Examples of base catalysts for the reaction to obtain the intermediate bis(indole-2,3-diones) shown in STEP 1 include inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate, and organic amine compounds such as triethylamine, pyridine, and N-methylmorpholine. These can be used alone or in combination of two or more. The amount of these catalysts used is, for example, 0.1 to 20 moles, preferably 0.2 to 10 moles, relative to the molar number of the indole-2,3-diones as a raw material.

[0148] The solvent used in this step is not particularly limited as long as it is inert in the above reaction. Examples include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone; and water. These can be used alone or in combination. The amount of these solvents can be in the range of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials. The reaction temperature is preferably between -50°C and about the boiling point of the solvent, more preferably between room temperature and 150°C. The reaction time is appropriately selected from 0.1 to 100 hours.

[0149] Reaction methods include adding the indole-2,3-diones and the compound represented by XWX together to a solvent, adding the indole-2,3-diones and the compound represented by XWX separately or separately, dispersed, or dissolved, and then adding dropwise. Dispersing or dissolving one of the indole-2,3-diones and the compound represented by XWX in a solvent and then adding the other dispersed or dissolved in the solvent dropwise. Furthermore, when adding multiple indole-2,3-diones and the compound represented by XWX, they can be premixed and reacted, or they can be reacted sequentially. When using a catalyst, examples include adding the indole-2,3-diones and the compound represented by XWX together, and adding the catalyst dropwise after predispersing or dissolving it. The reaction solution of the intermediate bis(indole-2,3-dione) can be further subjected to the dehydration condensation reaction of STEP 2, or it can be diluted with an organic solvent to remove unreacted raw materials, catalysts, etc. present in the system as reaction intermediates, and then recovered as a powder by liquid separation and washing or crystallization with a poor solvent.

[0150] As the acid catalyst used in the dehydration condensation reaction shown in STEP 2, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) isopropoxide, and titanium (IV) oxide can be used. The amount of the catalyst used is 0.1 to 20 mol, preferably 0.2 to 10 mol, relative to the molar number of the intermediate bis(indole-2,3-dione).

[0151] The solvent to be used is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; chlorinated solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide. These solvents may be used alone or in combination of two or more. These solvents can be used in an amount of 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw materials. The reaction temperature is preferably -50°C to about the boiling point of the solvent, more preferably room temperature to 150°C. The reaction time is appropriately selected from 0.1 to 100 hours.

[0152] The reaction method includes adding the bis(indole-2,3-dione), aniline, or aminonaphthalene together with the acid catalyst; dispersing or dissolving the bis(indole-2,3-dione), aniline, or aminonaphthalene and then adding the catalyst all at once or in portions; diluting with a solvent and adding dropwise; dispersing or dissolving the catalyst and then adding the bis(indole-2,3-dione), aniline, or aminonaphthalene all at once or in portions; or diluting with a solvent and adding dropwise. Depending on the reactivity of the aniline or aminonaphthalene, the amount of aniline or aminonaphthalene used is preferably 2 or more moles per 1 mole of the bis(indole-2,3-dione). After the reaction is completed, the catalyst is removed by dilution in an organic solvent, followed by separation and washing to recover the desired product.

[0153] The organic solvent used at this time is not particularly limited as long as it can dissolve the target substance and separate into two layers when mixed with water. Examples include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, and ethylcyclopentyl methyl ether; chlorinated solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The washing water used at this time is generally deionized water or ultrapure water. The number of washes may be one or more, but even 10 or more washes may not necessarily achieve the desired cleaning effect. Therefore, the number of washes is preferably about one to five.

[0154] In order to remove the acidic components in the system during liquid separation and cleaning, an alkaline aqueous solution can be used for cleaning. Specific examples of the base include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium.

[0155] Furthermore, in order to remove metal impurities or alkaline components in the system during liquid separation and cleaning, cleaning with an acidic aqueous solution may be performed. Specific examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids, and organic acids such as oxalic acid, fumaric acid, maleic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0156] The liquid separation cleaning using the alkaline aqueous solution or the acidic aqueous solution may be performed alone or in combination. From the perspective of removing metal impurities, the liquid separation cleaning is preferably performed in the order of the alkaline aqueous solution and the acidic aqueous solution.

[0157] After the aforementioned separation and cleaning using an alkaline or acidic aqueous solution, the product may be subsequently cleaned with neutral water. The cleaning frequency may be one or more, preferably about one to five times. Neutral water can be deionized water, ultrapure water, or the like. One or more cleaning cycles are sufficient, but fewer cycles may not remove the alkaline or acidic components. Even 10 or more cleaning cycles may not necessarily achieve the desired cleaning effect, so approximately one to five cycles are preferred.

[0158] Furthermore, the reaction product after the separation operation can be recovered as a powder by concentrating the solvent to dryness or crystallizing it under reduced pressure or normal pressure. This can also be converted into a solution of appropriate concentration to improve operability during the preparation of the organic film-forming composition. The concentration in this case is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. This concentration prevents increased viscosity, thus preventing impairment of operability. Furthermore, the amount of solvent does not become excessive, which is economically advantageous.

[0159] The solvent in this case is not particularly limited as long as it can dissolve the compound. Specific examples include 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, t-butyl acetate, t-butyl propionate, and propylene glycol mono-t-butyl ether acetate. These can be used alone or in combination of two or more.

[0160] [Other methods for producing compounds]

[0161] In addition, another method for producing the compound represented by the general formula (1) used in the organic film-forming material of the present invention can be obtained by performing a method comprising the following steps: a step (STEP1) of obtaining an imine compound as shown below as an intermediate by a dehydration condensation reaction of indole-2,3-diketones with anilines or aminonaphthalenes using an acid catalyst, and further a substitution reaction (STEP2) using a base catalyst using a compound represented by XWX having a leaving group X as a raw material. In this case, XWX can be used alone or in combination of two or more. For example, the film-forming properties and the adhesion to the substrate of the film can be controlled by partially introducing a polar structure. R1, R2, W, X, n, m, l, and p are the same as above.

[0162] [Chemistry 18]

[0163]

[0164] The dehydration condensation reaction (STEP 1) and the replacement reaction (STEP 2) can be carried out by the reaction method and recovery method described in the method for producing the compound of the general formula (1), respectively.

[0165] In the preparation of compounds used in the organic film-forming material obtained by this method, various halides, toluenesulfonates, and mesylates can be used individually or in combination to match the required performance. For example, compounds having side chain structures that contribute to improved planarization properties, or rigid aromatic ring structures that contribute to etch resistance and heat resistance, can be combined in any ratio. As a result, organic film-forming materials using these compounds not only exhibit improved filling / planarization properties and film-forming properties, but also possess higher levels of etch resistance and optical properties.

[0166] As described above, the compound for an organic film-forming material of the present invention can provide an organic film-forming material exhibiting excellent filling / planarization characteristics and film-forming properties.

[0167] <Organic film-forming material>

[0168] The present invention also provides an organic film-forming material comprising the compound for use as an organic film-forming material according to the present invention and an organic solvent. The compound according to the present invention can be used alone or in combination of two or more.

[0169] [Organic solvents]

[0170] The organic solvent that can be used in the organic film-forming material of the present invention is not particularly limited as long as it can dissolve the above-mentioned compounds and, if contained, the surfactants, plasticizers, acid generators, crosslinking agents, and other additives described below. Specifically, solvents having a boiling point of less than 180°C, such as the solvents described in paragraphs

[0091] to

[0092] of Japanese Patent Application Laid-Open No. 2007-199653, can be used. Among them, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and mixtures of two or more thereof are preferably used. The amount of the above-mentioned organic solvent blended is preferably 200 to 10,000 parts by mass, more preferably 300 to 5,000 parts by mass, relative to 100 parts by mass of the above-mentioned compounds.

[0171] Such an organic film forming material can be applied by spin coating, and because it contains the compound for an organic film forming material of the present invention as described above, it is an organic film forming material having both heat resistance and high filling and planarizing properties.

[0172] In the organic film forming material of the present invention, as an organic solvent, an organic solvent having a boiling point of 180° C. or higher (high boiling point solvent) (a mixture of a solvent having a boiling point of less than 180° C. and a solvent having a boiling point of 180° C. or higher) may be added to the solvent having a boiling point of less than 180° C. As the high boiling point organic solvent, there are no particular restrictions as long as it can dissolve the compound for the organic film forming material, and hydrocarbons, alcohols, ketones, esters, ethers, chlorine-based solvents, etc. are included. Specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 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, and dipropylene glycol. 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 monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl triethylene glycol ether, triethylene glycol n-butyl ether, triethylene glycol butyl methyl ether, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene ...methyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monomethyl Acetate, 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, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc., which can be used alone or in combination.

[0173] The boiling point of the high-boiling-point solvent can be appropriately selected based on the temperature at which the organic film-forming material is heat-treated. The boiling point of the added high-boiling-point solvent is preferably 180°C to 300°C, more preferably 200°C to 300°C. This boiling point prevents the risk of excessively rapid volatilization during baking (heat treatment) due to a low boiling point, thereby achieving sufficient thermal fluidity. Furthermore, this boiling point is not too high, preventing the solvent from remaining in the film after baking without volatilization, thereby minimizing the risk of adversely affecting film properties such as etching resistance.

[0174] When a high-boiling-point solvent is used, the amount of the high-boiling-point solvent blended is preferably 1 to 30 parts by mass relative to 100 parts by mass of the solvent having a boiling point below 180° C. This blending amount provides sufficient thermal fluidity during baking and prevents the solvent from remaining in the film and deteriorating film properties such as etching resistance.

[0175] If such an organic film forming material is provided with thermal fluidity by adding a high-boiling-point solvent to the organic film forming material, it can be an organic film forming material having both high filling and planarizing properties.

[0176] [Acid generator]

[0177] An acid generator may be added to the organic film-forming material of the present invention to further promote the curing reaction. Such acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation; either type can be added. Specifically, the materials described in paragraphs

[0061] to

[0085] of JP-A-2007-199653 may be added, but are not limited to these.

[0178] The acid generators may be used alone or in combination of two or more. The amount of the acid generator 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 compound.

[0179] [Surfactant]

[0180] The organic film forming material of the present invention may be added with a surfactant to improve the coating properties during spin coating. Examples of the surfactant include those described in

[0142] to

[0147] of Japanese Patent Application Laid-Open No. 2009-269953. The amount of the surfactant 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 compound.

[0181] [Crosslinking agent]

[0182] In addition, in the organic film forming material of the present invention, in order to improve the hardening property and suppress the intermixing with the upper film of the resist, a crosslinking agent may also be added. As the above-mentioned crosslinking agent, there is no particular limitation, and crosslinking agents of various known systems can be widely used. As an example, hydroxymethyl or alkoxymethyl type crosslinking agents of polynuclear phenols, melamine-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, and epoxy-based crosslinking agents can be exemplified. The addition amount when adding the above-mentioned crosslinking agent is preferably 1 to 100 parts by mass relative to 100 parts by mass of the above-mentioned compound, and more preferably 5 to 50 parts by mass.

[0183] As melamine-based crosslinking agents, specifically, hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxyl substitutions, and their partial self-condensation products can be exemplified. As glycoluril-based crosslinking agents, specifically, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, their alkoxy and / or hydroxyl substitutions, and their partial self-condensation products can be exemplified. As benzoguanamine-based crosslinking agents, specifically, tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxyl substitutions, and their partial self-condensation products can be exemplified. As urea-based crosslinking agents, specifically, dimethoxymethylated dimethoxyethylene urea, its alkoxy and / or hydroxyl substitutions, and their partial self-condensation products can be exemplified. As β-hydroxyalkylamide-based crosslinking agents, specifically, N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide can be exemplified. Specific examples of isocyanurate-based crosslinking agents include triglycidyl isocyanurate and triallyl isocyanurate. Specific examples of aziridine-based crosslinking agents include 4,4′-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Specific examples of the oxazoline-based crosslinking agent include 2,2'-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), and 2-isopropenyloxazoline copolymers. Specific examples of the epoxy crosslinking agent include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0184] Specific examples of the polynuclear phenol-based crosslinking agent (a polynuclear phenol-based hydroxymethyl or alkoxymethyl type crosslinking agent) include compounds represented by the following general formula (6).

[0185] [Chemistry 19]

[0186]

[0187] (In the formula, Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. R3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. q is an integer of 1 to 5.)

[0188] Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. q is an integer of 1 to 5, more preferably 2 or 3. Specific examples of Q include groups obtained by removing q hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosane, preferably a hydrogen atom or a methyl group.

[0189] Specific examples of the compound represented by the general formula (6) include the following compounds. Among these, trisphenolmethane, trisphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and hexamethoxymethylated tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the perspective of improving the curability and film thickness uniformity of the organic film. R3 is the same as described above.

[0190] [Chemistry 20]

[0191]

[0192] [Chemistry 21]

[0193]

[0194] [Plasticizer]

[0195] In addition, in order to further improve the flattening / burying characteristics, a plasticizer may be added to the organic film forming material of the present invention. There is no particular limitation on the plasticizer, and plasticizers of various known systems can be widely used. As an example, low molecular weight compounds such as phthalates, adipic acid esters, phosphates, trimellitic acid esters, and citrates, polyethers, polyesters, and polymers such as polyacetal polymers described in Japanese Patent Application Laid-Open No. 2013-253227 can be exemplified. The amount of the plasticizer added is preferably 1 to 100 parts by mass, more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the above-mentioned compound.

[0196] Furthermore, in the organic film-forming material of the present invention, as an additive for imparting filling / planarizing properties similar to a plasticizer, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a pyrolyzable polymer having a weight loss rate of 40% by mass or greater between 30°C and 250°C and a weight-average molecular weight of 300 to 200,000 is preferably used. The pyrolyzable polymer preferably contains repeating units having an acetal structure represented by the following general formulas (DP1) and (DP1a).

[0197] [Chemistry 22]

[0198]

[0199] (In the formula, R4 is a hydrogen atom or an optionally substituted saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. Y is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.)

[0200] [Chemistry 23]

[0201]

[0202] (In the formula, R5 is an alkyl group having 1 to 4 carbon atoms. Z is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms, which may have an ether bond. j represents the average number of repeating units and is 3 to 500.)

[0203] [Other ingredients]

[0204] The organic film forming material of the present invention may also be blended with other compounds or polymers. The blending compound or polymer mixed with the organic film forming material of the present invention has the function of improving the film forming properties of spin coating and improving the filling characteristics of substrates with uneven surfaces.

[0205] Examples of such materials include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-tert-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, phenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, gallol, thymol, isothymol, 4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-dimethyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'-dimethyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, -4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'difluoro-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'diphenyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'dimethoxy-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,3,2',3'-tetrahydro-(1,1')-spiro- Indene-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 2,3,2',3'-tetrahydro-(1 ,1')-spirobiindene-5,5'-diol, 5,5'-dimethyl-3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol and 1,5-dihydroxynaphthalene, Dihydroxynaphthalenes such as 1,7-dihydroxynaphthalene and 2,6-dihydroxynaphthalene, methyl 3-hydroxynaphthalene-2-carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, vinylnaphthalene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene, and novolac resins such as limonene, polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyvinylnaphthalene, polynorbornene, polycyclodecene, polytetracyclododecene, polytricyclo[2.2.1.0(2,6)]heptane (poly-nortricyclene), poly(meth)acrylates, and copolymers thereof.In addition, naphthol dicyclopentadiene copolymers described in Japanese Patent Application Laid-Open No. 2004-205685, fluorene bisphenol novolac resins described in Japanese Patent Application Laid-Open No. 2005-128509, ethylene naphthalene copolymers described in Japanese Patent Application Laid-Open No. 2005-250434, fullerenes having a phenolic group described in Japanese Patent Application Laid-Open No. 2006-227391, bisphenol compounds and novolac resins thereof described in Japanese Patent Application Laid-Open No. 2006-293298, novolac resins of adamantaneol compounds described in Japanese Patent Application Laid-Open No. 2006-285095, bisnaphthol compounds and novolac resins described in Japanese Patent Application Laid-Open No. 2010-122656, and fullerene resin compounds described in Japanese Patent Application Laid-Open No. 2008-158002 may also be blended.

[0206] The amount of the compound for blending or the polymer for blending is preferably 0 to 1,000 parts by mass, more preferably 0 to 500 parts by mass, based on 100 parts by mass of the compound.

[0207] The organic film-forming material containing these components can be used as an organic film material or a planarization material for manufacturing semiconductor devices.

[0208] Furthermore, the organic film forming material of the present invention is extremely useful as an organic film material for multilayer resist processing, such as two-layer resist processing, three-layer resist processing using a silicon-containing intermediate film, and four-layer resist processing using a silicon-containing inorganic hard mask or intermediate film and an organic antireflective film.

[0209] (Organic film formation method)

[0210] The present invention provides a method for forming an organic film that functions as an organic film of a multilayer resist film used in photolithography or a planarizing film for semiconductor manufacturing, using the above-mentioned organic film-forming material.

[0211] The method for forming an organic film using the organic film forming material of the present invention is to apply the above-mentioned organic film forming material to the processed substrate by spin coating or the like. By using the spin coating method or the like, good filling characteristics can be obtained. After spin coating, the solvent is evaporated, and in order to prevent mixing with the resist upper film and the resist intermediate film, baking (heat treatment) is performed to promote the cross-linking reaction. The baking is preferably carried out at a temperature of 100°C to 600°C for 10 to 600 seconds, more preferably at a temperature of 200°C to 500°C for 10 to 300 seconds. Considering the influence on device damage and wafer deformation, the upper limit of the heating temperature in the wafer processing of photolithography is preferably 600°C or less, more preferably 500°C or less.

[0212] In addition, in an organic film forming method using the organic film forming material of the present invention, the organic film forming material of the present invention is coated on a processed substrate by the same spin coating method as mentioned above, and the above-mentioned organic film forming material is calcined in an environment with an oxygen concentration of not less than 0.1 volume % and not more than 21 volume % to harden it, thereby also forming an organic film.

[0213] By calcining the organic film forming material of the present invention in such an oxygen environment, a fully hardened film can be obtained. As the environment in the baking, it is also fine in air. In order to reduce oxygen, inert gases such as N , Ar, He are enclosed, which is preferable for preventing the oxidation of the organic film. In order to prevent oxidation, the oxygen concentration needs to be controlled, which should be below 1000ppm, more preferably below 100ppm (volume basis). If the oxidation of the organic film in the baking is prevented, absorption will not increase or etching tolerance will not reduce, so it is preferable.

[0214] The organic film formation method using the organic film formation material of the present invention can obtain a flat cured film regardless of the unevenness of the processed substrate due to its excellent filling / planarization properties. Therefore, it is extremely useful for forming a flat cured film on a processed substrate having a structure with a height of 30 nm or more or a height difference.

[0215] The thickness of the organic film or the organic film such as the planarization film for manufacturing a semiconductor device is appropriately selected and is preferably 30 to 20,000 nm, particularly preferably 50 to 15,000 nm.

[0216] (Pattern Formation Method)

[0217] The present invention provides a pattern forming method using such an organic film forming material and utilizing a three-layer resist process, wherein the method is a method for forming a pattern on a substrate to be processed, comprising at least the following steps:

[0218] An organic film is formed on a workpiece (substrate to be worked) using the organic film forming material of the present invention.

[0219] A silicon-containing resist interlayer film is formed on the organic film using a silicon-containing resist interlayer material.

[0220] A photoresist composition is used to form a resist upper layer film on the silicon-containing resist intermediate film to form a multilayer resist film.

[0221] After the pattern circuit area of ​​the resist upper layer film is exposed, the resist upper layer film is developed with a developer to form a circuit pattern (resist pattern).

[0222] The patterned resist upper layer film is used as an etching mask to transfer the pattern to the silicon-containing resist intermediate film by etching.

[0223] The pattern is transferred to the organic film by etching using the silicon-containing resist intermediate film having the transferred pattern as an etching mask.

[0224] Furthermore, the object to be processed is etched using the organic film to which the pattern has been transferred as an etching mask to form a pattern on the object to be processed.

[0225] In order for the silicon-containing resist intermediate film in the above three-layer resist treatment to exhibit etching resistance using oxygen or hydrogen, it is preferable that the dry etching of the organic film in the above three-layer resist treatment is performed using the silicon-containing resist intermediate film as a mask using an etching gas mainly containing oxygen or hydrogen.

[0226] A polysiloxane-based interlayer is preferably used as the silicon-containing resist interlayer for the three-layer resist treatment. By providing the silicon-containing resist interlayer with an antireflection effect, reflection can be suppressed. Especially for 193nm exposure, using an organic film made of a material containing a large number of aromatic groups and having high etching selectivity with the substrate results in a high k value and increased substrate reflection. However, by providing the silicon-containing resist interlayer with an absorption function that achieves an appropriate k value, reflection can be suppressed, reducing substrate reflection to less than 0.5%. Silicon-containing resist interlayers with an antireflection effect are preferably polysiloxanes with pendant anthracene-based light-absorbing groups for 248nm and 157nm exposure, and pendant phenyl-based or silicon-silicon-based light-absorbing groups for 193nm exposure. These polysiloxanes are crosslinked with acid or heat.

[0227] Furthermore, it is also suitable for a four-layer resist process using an organic antireflective film, in which case the process comprises at least the following steps:

[0228] An organic film is formed on a workpiece (substrate to be worked) using the organic film forming material of the present invention.

[0229] A silicon-containing resist interlayer film is formed on the organic film using a silicon-containing resist interlayer material.

[0230] forming an organic anti-reflective film (BARC) on the silicon-containing resist intermediate film,

[0231] A photoresist composition is used to form a resist upper layer film on the BARC to form a four-layer film structure (multi-layer resist film).

[0232] After exposing the pattern circuit area of ​​the resist upper layer film, the resist upper layer film is developed with a developer to form a circuit pattern (resist pattern).

[0233] The patterned resist upper layer film is used as an etching mask to transfer the pattern to the BARC film and the silicon-containing resist intermediate film by etching.

[0234] The pattern is transferred to the organic film by etching using the silicon-containing resist intermediate film having the transferred pattern as an etching mask.

[0235] Furthermore, the organic film having the transferred pattern is used as an etching mask to etch the workpiece to form a pattern on the workpiece.

[0236] Thereby, a semiconductor device circuit pattern can be formed on the substrate.

[0237] Alternatively, an inorganic hard mask may be formed instead of the silicon-containing resist interlayer. In this case, a semiconductor device circuit pattern can be formed on the substrate by at least the following steps:

[0238] An organic film is formed on a workpiece (substrate to be worked) using the organic film forming material of the present invention.

[0239] forming an inorganic hard mask film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film;

[0240] Using a photoresist composition to form a resist upper layer film on the inorganic hard mask,

[0241] After exposing the pattern circuit area of ​​the resist upper layer film, the resist upper layer film is developed with a developer to form a circuit pattern (resist pattern).

[0242] The patterned resist upper layer film is used as an etching mask to etch the inorganic hard mask to transfer the pattern.

[0243] The patterned inorganic hard mask is used as an etching mask to etch the organic film to transfer the pattern.

[0244] Furthermore, the object to be processed is etched using the patterned organic film as an etching mask to form a pattern on the object to be processed.

[0245] As described above, when forming an inorganic hard mask on an organic film, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) can be formed by CVD, ALD, or the like. For example, methods for forming a silicon nitride film are described in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The inorganic hard mask preferably has a thickness of 5 to 200 nm, more preferably 10 to 100 nm. Furthermore, SiON film, which is highly effective as an antireflective film, is most preferably used as the inorganic hard mask. The substrate temperature during SiON film formation is 300 to 500°C, so the organic film must be able to withstand temperatures of 300 to 500°C. The organic film-forming material used in the present invention has high heat resistance and can withstand temperatures of 300 to 500°C, making it possible to combine an inorganic hard mask formed by CVD or ALD with an organic film formed by spin coating.

[0246] Furthermore, the present invention is also suitable for a four-layer resist process using an organic antireflection film. In this case, a semiconductor device circuit pattern can be formed on a substrate by at least comprising the following steps:

[0247] An organic film is formed on a workpiece (substrate to be worked) using the organic film forming material of the present invention.

[0248] forming an inorganic hard mask film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film;

[0249] forming an organic anti-reflective film (BARC) on the inorganic hard mask,

[0250] A photoresist composition is used to form a resist upper layer film on the BARC to form a four-layer film structure (multi-layer resist film).

[0251] After exposing the pattern circuit area of ​​the resist upper layer film, the resist upper layer film is developed with a developer to form a circuit pattern (resist pattern).

[0252] The patterned resist upper layer film is used as an etching mask to etch the BARC film and the inorganic hard mask to transfer the pattern.

[0253] The patterned inorganic hard mask is used as an etching mask to etch the organic film to transfer the pattern.

[0254] Furthermore, the object to be processed is etched using the patterned organic film as an etching mask to form a pattern on the object to be processed.

[0255] As described above, a photoresist film can be formed as a resist upper layer on a silicon-containing resist interlayer and an inorganic hard mask. Alternatively, an organic antireflective coating (BARC) can be formed on the silicon-containing resist interlayer and the inorganic hard mask by spin coating, and a photoresist film can be formed thereon. In particular, when a SiON film is used as the inorganic hard mask, the dual antireflective coating of the SiON film and the BARC can suppress reflection even during immersion exposure with a high NA exceeding 1.0. Another advantage of forming a BARC is that it reduces the tailing of the photoresist pattern directly above the SiON film.

[0256] The resist top layer in the three-layer resist process can be either positive or negative, and the same photoresist composition as commonly used can be used. After spin coating the photoresist composition, a pre-bake is performed, preferably at 60-180°C for 10-300 seconds. Exposure is then performed according to conventional methods, followed by a post-exposure bake (PEB) and development to obtain a resist pattern. The thickness of the resist top layer is not particularly limited, but is preferably 30-500 nm, particularly 50-400 nm.

[0257] The exposure light is high-energy radiation having a wavelength of 300 nm or less, and specifically includes excimer lasers of 248 nm, 193 nm, and 157 nm, soft X-rays of 3 to 20 nm, electron beams, and X-rays.

[0258] As a method for forming a pattern of the resist upper layer film, optical lithography with a wavelength of 10 nm to 300 nm, direct writing using an electron beam, nanoimprinting, or a combination thereof is preferably used.

[0259] Furthermore, the development method in the above-mentioned pattern forming method is preferably alkali development or development using an organic solvent.

[0260] Then, etching is performed using the resulting resist pattern as a mask. Etching of the silicon-containing resist interlayer and the inorganic hard mask in the three-layer resist process is performed using a fluorocarbon-based gas and the upper resist pattern as a mask. This forms a silicon-containing resist interlayer pattern and an inorganic hard mask pattern.

[0261] Then, the organic film is etched using the obtained silicon-containing resist intermediate film pattern and the inorganic hard mask pattern as masks.

[0262] Subsequent etching of the substrate can also be performed using conventional methods. For example, if the substrate is SiO2, SiN, or a silicon dioxide-based low-k dielectric film, etching is performed primarily using chlorofluorocarbon-based gases; if it is p-Si, Al, or W, etching is performed primarily using chlorine-based or bromine-based gases. When etching the substrate using chlorofluorocarbon-based gases, the silicon-containing resist interlayer pattern in the three-layer resist process is stripped simultaneously with substrate processing. When etching the substrate using chlorine-based or bromine-based gases, stripping the silicon-containing resist interlayer pattern requires a separate dry etching stripping process using chlorofluorocarbon-based gases after substrate processing.

[0263] The organic film obtained by using the organic film-forming material of the present invention is characterized by excellent etching resistance when etching these substrates to be processed.

[0264] Furthermore, the substrate to be processed is not particularly limited, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, as well as substrates formed with a processed layer on such substrates, can be used. The processed layer can be formed using various low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, as well as their barrier films. Typically, a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm, can be achieved. Furthermore, when forming the processed layer, the substrate and the processed layer can be made of different materials.

[0265] As the processed substrate (processed body), it is preferable to use a semiconductor device substrate, or a semiconductor device substrate on which a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film are formed. More specifically, Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al and other substrates can be used, and the above-mentioned metal films can be formed on the substrate as the processed layer.

[0266] In addition, the metal constituting the processed substrate is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, cobalt, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, manganese, molybdenum, ruthenium or an alloy thereof.

[0267] Furthermore, as the substrate to be processed, it is preferable to use a substrate to be processed having a structure or a height difference of 30 nm or more.

[0268] Regarding an example of a 3-layer resist process, if you use Figure 1 The specific display is as follows. When the 3-layer resist is processed, Figure 1As shown in (A), an organic film 3 is formed on a workpiece layer 2 laminated on a substrate 1 using the organic film forming material of the present invention, and then a silicon-containing resist intermediate film 4 is formed, and a resist upper film 5 is formed thereon.

[0269] Then, if Figure 1 In the manner shown in (B), the portion 6 of the resist upper layer film 5 is exposed, and PEB and development are performed to form a resist upper layer film pattern 5a ( Figure 1 (C)). The obtained resist upper film pattern 5a is used as a mask, and the silicon-containing resist intermediate film 4 is etched using CF-based gas to form a silicon-containing resist intermediate film pattern 4a ( Figure 1 After removing the resist upper film pattern 5a, the obtained silicon-containing resist intermediate film pattern 4a is used as a mask to perform oxygen plasma etching on the organic film 3 to form an organic film pattern 3a ( Figure 1 (E)). Further, after removing the silicon-containing resist intermediate film pattern 4a, the processed layer 2 is etched using the organic film pattern 3a as a mask to form a pattern 2a formed on the processed layer ( Figure 1 (F)).

[0270] When an inorganic hard mask is used, the silicon-containing resist interlayer film 4 serves as the inorganic hard mask, and when applying BARC, a BARC layer is provided between the silicon-containing resist interlayer film 4 and the resist upper layer film 5. BARC etching may be performed continuously before etching the silicon-containing resist interlayer film 4. Alternatively, etching of the silicon-containing resist interlayer film 4 may be performed after etching the BARC alone, and then etching of the silicon-containing resist interlayer film 4 may be performed by changing the etching equipment.

[0271] As described above, according to the pattern forming method of the present invention, a fine pattern can be formed on a substrate to be processed with high precision in a multilayer resist process.

[0272] [Example]

[0273] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. Furthermore, as molecular weight and dispersity, the polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent, and the dispersity (Mw / Mn) was determined.

[0274] Synthesis Example Synthesis of Compounds for Organic Film-Forming Materials

[0275] In the synthesis of compounds (A1) to (A9) for organic film-forming materials, the following anilines or aminonaphthalenes (B1) to (B5) and bis(indole-2,3-dione) compounds (C1) to (C3) were used. Furthermore, in the comparative examples, raw materials (D1) to (D4) were used as compounds (R1) to (R3). Furthermore, a 37% aqueous solution of (D4) was used.

[0276] Anilines or aminonaphthalenes:

[0277] [Chemistry 24]

[0278]

[0279] Bis(indole-2,3-diones):

[0280] [Chemistry 25]

[0281]

[0282] Comparative Example Compound Raw Materials:

[0283] [Chemistry 26]

[0284]

[0285] The bis(indole-2,3-diones) shown above were synthesized as follows.

[0286] (Synthesis example 1)

[0287] Synthesis of compound (C1)

[0288] [Chemistry 27]

[0289]

[0290] Under a nitrogen environment, 73.6 g of indole-2,3-dione, 207.3 g of potassium carbonate, and 900 g of DMF (dimethylformamide) were added to form a uniform dispersion at an internal temperature of 50°C. 205.1 g of 1,4-dibromobutane was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. After the reaction was completed, the reaction solution was added to 5000 ml of pure water to precipitate crystals. The settled crystals were separated by filtration, washed 3 times with 1000 ml of pure water, and then washed twice with 1000 ml of methanol and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (C1).

[0291] (Synthesis example 2)

[0292] Synthesis of compound (C2)

[0293] [Chemistry 28]

[0294]

[0295] Under a nitrogen environment, add 73.6 g of indole-2,3-dione, 207.3 g of potassium carbonate, and 900 g of DMF to form a uniform dispersion at an internal temperature of 50°C. Slowly add it to a mixed solution of 250.8 g of 1,4-bis(bromomethyl)benzene previously dissolved in 500 g of DMF, and react at an internal temperature of 50°C for 24 hours. After the reaction is completed, add the reaction solution to 6000 ml of pure water to precipitate crystals. The settled crystals are separated by filtration, washed 3 times with 1000 ml of pure water, and then washed twice with 1000 ml of methanol and recovered. The recovered crystals are vacuum dried at 70°C to obtain compound (C2).

[0296] (Synthesis example 3)

[0297] Synthesis of compound (C3)

[0298] [Chemistry 29]

[0299]

[0300] Under a nitrogen environment, 107.6 g of 7-(trifluoromethyl)indole-2,3-dione, 207.3 g of potassium carbonate, and 900 g of DMF were added to form a uniform dispersion at an internal temperature of 50°C. 231.8 g of 1,6-dibromohexane was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. After the reaction was completed, the reaction solution was added to 6000 ml of pure water to precipitate crystals. The settled crystals were separated by filtration, washed 3 times with 1000 ml of pure water, then washed twice with 1000 ml of methanol and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (C3).

[0301] Synthesis of Compounds (A1) to (A9) and Comparative Example Compounds (R1) to (R3)

[0302] (Synthesis Example 4)

[0303] Synthesis of compound (A1)

[0304] [Chemistry 30]

[0305]

[0306] Under a nitrogen atmosphere, 9.3 g of compound (B1), 10.0 g of compound (C1), and 120 g of PGME (propylene glycol monomethyl ether) were added, and a uniform solution was prepared at 100° C. 2.0 g of acetic acid was slowly added dropwise, and the mixture was reacted at 100° C. for 8 hours. After the reaction was completed, the mixture was cooled in an ice bath to precipitate crystals. 200 g of MeOH (methanol) was added and stirred to disperse the mixture, and the settled crystals were separated by filtration, washed three times with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70° C. to obtain compound (A1).

[0307] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0308] (A1): Mw=640, Mw / Mn=1.01

[0309] (Synthesis Example 5)

[0310] Synthesis of compound (A2)

[0311] [Chemistry 31]

[0312]

[0313] Under a nitrogen atmosphere, 12.5 g of compound (B2), 10.0 g of compound (C1), and 120 g of PGME (propylene glycol monomethyl ether) were added, and a uniform solution was prepared at 100 ° C. Then, 2.0 g of acetic acid was slowly added dropwise, and the reaction was carried out at 100 ° C for 8 hours. After the reaction was completed, the mixture was cooled in an ice bath to precipitate crystals. After adding 200 g of MeOH and stirring to disperse it, the settled crystals were separated by filtration, washed 3 times with 100 g of MeOH, and recovered. Compound (A2) was obtained by vacuum drying the recovered crystals at 70 ° C.

[0314] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0315] (A2): Mw=740, Mw / Mn=1.03

[0316] (Synthesis Example 6)

[0317] Synthesis of compound (A3)

[0318] [Chemistry 32]

[0319]

[0320] Under a nitrogen atmosphere, 7.4 g of compound (B3), 10.0 g of compound (C1), and 120 g of PGME (propylene glycol monomethyl ether) were added, and a uniform solution was prepared at 100 ° C. Then, 2.0 g of acetic acid was slowly added dropwise, and the reaction was carried out at 100 ° C for 8 hours. After the reaction was completed, the mixture was cooled in an ice bath to precipitate crystals. After adding 200 g of MeOH and stirring to disperse it, the settled crystals were separated by filtration, washed 3 times with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70 ° C to obtain compound (A3).

[0321] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0322] (A3): Mw=590, Mw / Mn=1.01

[0323] (Synthesis Example 7)

[0324] Synthesis of compound (A4)

[0325] [Chemistry 33]

[0326]

[0327] Under a nitrogen atmosphere, 8.2 g of compound (B1), 10.0 g of compound (C2), and 120 g of PGME (propylene glycol monomethyl ether) were added, and a uniform solution was prepared at 100 ° C. Then, 2.0 g of acetic acid was slowly added dropwise, and the reaction was carried out at 100 ° C for 8 hours. After the reaction was completed, the mixture was cooled in an ice bath to precipitate crystals. After adding 200 g of MeOH and stirring to disperse it, the settled crystals were separated by filtration, washed three times with 100 g of MeOH, and recovered. Compound (A4) was obtained by vacuum drying the recovered crystals at 70 ° C.

[0328] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0329] (A4): Mw=690, Mw / Mn=1.02

[0330] (Synthesis Example 8)

[0331] Synthesis of compound (A5)

[0332] [Chemistry 34]

[0333]

[0334] Under a nitrogen atmosphere, 6.5 g of compound (B3), 10.0 g of compound (C2), and 120 g of PGME (propylene glycol monomethyl ether) were added, and a uniform solution was prepared at 100 ° C. Then, 2.0 g of acetic acid was slowly added dropwise, and the reaction was carried out at 100 ° C for 8 hours. After the reaction was completed, the mixture was cooled in an ice bath to precipitate crystals. After adding 200 g of MeOH and stirring to disperse it, the settled crystals were separated by filtration, washed 3 times with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70 ° C to obtain compound (A5).

[0335] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0336] (A5): Mw=630, Mw / Mn=1.02

[0337] (Synthesis Example 9)

[0338] Synthesis of compound (A6)

[0339] [Chemistry 35]

[0340]

[0341] Under a nitrogen atmosphere, 7.3 g of compound (B4), 10.0 g of compound (C2), and 120 g of PGME (propylene glycol monomethyl ether) were added, and a uniform solution was prepared at 100 ° C. Then, 2.0 g of acetic acid was slowly added dropwise, and the reaction was carried out at 100 ° C for 8 hours. After the reaction was completed, the mixture was cooled in an ice bath to precipitate crystals. After adding 200 g of MeOH and stirring to disperse it, the settled crystals were separated by filtration, washed three times with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70 ° C to obtain compound (A6).

[0342] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0343] (A6): Mw=660, Mw / Mn=1.03

[0344] (Synthesis Example 10)

[0345] Synthesis of compound (A7)

[0346] [Chemistry 36]

[0347]

[0348] Under a nitrogen atmosphere, 8.5 g of compound (B2), 10.0 g of compound (C3), and 120 g of PGME (propylene glycol monomethyl ether) were added, and a uniform solution was prepared at 100 ° C. Then, 2.0 g of acetic acid was slowly added dropwise, and the reaction was carried out at 100 ° C for 8 hours. After the reaction was completed, the mixture was cooled in an ice bath to precipitate crystals. After adding 200 g of MeOH and stirring to disperse it, the settled crystals were separated by filtration, washed three times with 100 g of MeOH, and recovered. Compound (A7) was obtained by vacuum drying the recovered crystals at 70 ° C.

[0349] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0350] (A7): Mw=890, Mw / Mn=1.04

[0351] (Synthesis Example 11)

[0352] Synthesis of compound (A8)

[0353] [Chemistry 37]

[0354]

[0355] Under a nitrogen atmosphere, 5.0 g of compound (B3), 10.0 g of compound (C3), and 120 g of PGME (propylene glycol monomethyl ether) were added, and a uniform solution was prepared at 100 ° C. Then, 2.0 g of acetic acid was slowly added dropwise, and the reaction was carried out at 100 ° C for 8 hours. After the reaction was completed, the mixture was cooled in an ice bath to precipitate crystals. After adding 200 g of MeOH and stirring to disperse it, the settled crystals were separated by filtration, washed three times with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70 ° C to obtain compound (A8).

[0356] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0357] (A8): Mw=720, Mw / Mn=1.02

[0358] (Synthesis Example 12)

[0359] Synthesis of compound (A9)

[0360] [Chemistry 38]

[0361]

[0362] Under a nitrogen atmosphere, 8.3 g of compound (B5), 10.0 g of compound (C3), and 120 g of PGME (propylene glycol monomethyl ether) were added, and a uniform solution was prepared at 100 ° C. Then, 2.0 g of acetic acid was slowly added dropwise, and the reaction was carried out at 100 ° C for 8 hours. After the reaction was completed, the mixture was cooled in an ice bath to precipitate crystals. After adding 200 g of MeOH and stirring to disperse it, the settled crystals were separated by filtration, washed three times with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70 ° C to obtain compound (A9).

[0363] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0364] (A9): Mw=890, Mw / Mn=1.03

[0365] (Synthesis Example 13)

[0366] Synthesis of Compound (R1) for Comparative Example

[0367] [Chemistry 39]

[0368]

[0369] Under a nitrogen atmosphere, 31.8 g of compound (D1), 4.9 g of compound (D4), 5.0 g of oxalic acid, and 50 g of dioxane were added, and the mixture was reacted at an internal temperature of 100°C for 24 hours. After the reaction, the mixture was cooled to room temperature, 500 ml of MIBK (methyl isobutyl ketone) was added, and the mixture was washed six times with 100 ml of pure water. The organic layer was recovered, and water and solvent were removed under reduced pressure at an internal temperature of 150°C and a pressure of 2 mmHg to obtain a comparative example compound (polymer) (R1).

[0370] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0371] (R1): Mw=3200, Mw / Mn=4.88

[0372] (Synthesis Example 14)

[0373] Synthesis of Compound (R2) for Comparative Example

[0374] [Chemistry 40]

[0375]

[0376] Under a nitrogen atmosphere, 42.3 g of compound (D2), 5.7 g of compound (D4), 5.0 g of oxalic acid, and 60 g of dioxane were added, and the mixture was reacted at an internal temperature of 100°C for 24 hours. After the reaction, the mixture was cooled to room temperature, 500 ml of MIBK was added, and the mixture was washed six times with 100 ml of pure water. The organic layer was recovered, and the water and solvent were removed under reduced pressure at an internal temperature of 150°C and a pressure of 2 mmHg to obtain a comparative example compound (polymer) (R2).

[0377] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0378] (R2): Mw=2600, Mw / Mn=3.55

[0379] (Synthesis Example 15)

[0380] Synthesis of Compound (R3) for Comparative Example

[0381] [Chemistry 41]

[0382]

[0383] Under nitrogen environment, add indole-2,3-dione 3.1g, compound (D3) 10.0g, methanesulfonic acid 3.0g, propylene glycol monomethyl ether 16.1g, 3-mercaptopropionic acid 3.4g, heat to 140 ° C and react under reflux for 4 hours. After the reaction is completed, the reaction solution is added dropwise to methanol / pure water = 1 / 1 (weight ratio) 200g to precipitate crystals. The settled crystals are separated by filtration, washed twice with 100g of pure water and recovered. The recovered crystals are vacuum dried at 60 ° C to obtain a comparative example compound (polymer) (R3).

[0384] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0385] (R3): Mw=8500, Mw / Mn=2.30

[0386] Tables 1 to 3 list the results of Mw and Mw / Mn of compounds (A1) to (A9) and comparative example compounds (R1) to (R3) used in the examples.

[0387] [Table 1]

[0388]

[0389] [Table 2]

[0390]

[0391] [Table 3]

[0392]

[0393] [Preparation of Organic Film-Forming Materials (UDL-1 to 13, Comparative UDL-1 to 9)]

[0394] The above-mentioned compounds (A1) to (A9), the comparative example compounds (R1) to (R3), the raw materials (D1) and (D2) described in the above-mentioned synthesis examples, a crosslinking agent (XL), a thermal acid generator (TAG), 1,6-diacetoxyhexane (S1) with a boiling point of 260°C and tripropylene glycol monomethyl ether (S2) with a boiling point of 242°C as high boiling point solvents, and cyclohexanone (CyHO) containing 0.1% by mass of PF-6320 (manufactured by OMNOVA) were dissolved in the proportions shown in Table 4, and filtered through a 0.1 μm fluororesin filter to prepare organic film-forming materials (UDL-1 to 13, comparative UDL-1 to 9).

[0395] The structural formulas of the compounds, crosslinking agents, and thermal acid generators used in the organic film-forming material are shown below.

[0396] (Compound)

[0397] [Chemistry 42]

[0398]

[0399] (cross-linking agent)

[0400] [Chemistry 43]

[0401]

[0402] (Thermal Acid Generator)

[0403] [Chemistry 44]

[0404]

[0405] [Table 4]

[0406]

[0407] [Example 1 Solvent Resistance Measurement (Examples 1-1 to 1-13, Comparative Examples 1-1 to 1-9)]

[0408] UDLs 1 to 13 and comparative UDLs 1 to 9 prepared above were coated on silicon substrates and baked in air at the temperatures shown in Table 5 for 60 seconds. The film thickness was then measured. A PGMEA solvent was dispensed onto the substrates, left to stand for 30 seconds, and then spin-dried. The coatings were then baked at 100°C for 60 seconds to evaporate the PGMEA. The film thickness before and after the PGMEA treatment was measured. The residual film rate was calculated using the film thickness after deposition and the film thickness after the PGMEA treatment. The results are shown in Table 5.

[0409] [Table 5]

[0410]

[0411] As shown in Table 5, the organic films (Examples 1-1 to 1-13) using the compounds of the present invention exhibited a residual film rate of 99.5% or higher after PGMEA treatment, demonstrating sufficient solvent resistance through crosslinking reactions caused by heat treatment. Comparing Examples 1-1 to 13 with Comparative Examples 1-7 to 9, the compounds of the present invention exhibited sufficient curability regardless of the individual molecules. However, Comparative Examples 1-7 and 1-8, which used only monomolecular compounds other than the compounds of the present invention, exhibited insufficient curability, insufficient heat resistance, or low molecular weight, failing to achieve solvent resistance due to factors such as sublimation. As in Comparative Example 1-9, the addition of a crosslinker was required to ensure solvent resistance. Furthermore, in Comparative Examples 1-5 and 1-6, the polymers alone did not exhibit curability regardless of the polymers used, requiring the addition of a crosslinker and a thermal acid generator to ensure solvent resistance. Furthermore, Comparative Examples 1-2 and 4, which contained monomolecular compounds other than the compounds of the present invention and had low polymer content, did not exhibit sufficient solvent resistance.

[0412] [Example 2 Evaluation of Heat Resistance Characteristics (Examples 2-1 to 2-13, Comparative Examples 2-1 to 2-9)]

[0413] The above-described organic film-forming materials (UDL-1 to 13, comparative UDL-1 to 9) were each applied onto a silicon substrate and baked in air at the temperature listed in Table 6 for 60 seconds to form a coating film having a thickness of approximately 200 nm. The film thickness A was then measured. The substrate was further calcined at 400°C for 20 minutes under a nitrogen flow with an oxygen concentration controlled to 0.2% by volume or less, and the film thickness B was measured. These results are shown in Table 6.

[0414] [Table 6]

[0415]

[0416] As shown in Table 6, the organic films (Examples 2-1 to 2-13) formed by the organic film forming material of the present invention did not reduce in thickness by 2% even after long-term baking at 400°C, indicating that the organic film forming material of the present invention has excellent heat resistance. In particular, the compounds in which propargyloxy and ethynyl groups were introduced as substituents maintained a residual film rate of more than 99%, indicating that the heat resistance was particularly excellent. On the other hand, the residual film rates of Comparative Examples 2-1 to 2-9 were all low, and among them, the residual film rates of the samples that could not obtain solvent resistance compared to the results of Comparative Example 1 were significantly low. In particular, in Comparative Examples 2-7 and 2-8, which used monomolecular compounds other than the compounds of the present invention, almost no organic film remained. Even in Comparative Examples 2-1, 2-3, 2-6, and 2-9, which ensured solvent resistance by adding a crosslinking agent or using a polymer, the residual film rates were still low compared to the examples of the present invention, indicating that the organic films using the compounds of the present invention have excellent heat resistance.

[0417] [Example 3 Evaluation of Film Formability (Examples 3-1 to 3-13, Comparative Examples 3-1 to 3-9)]

[0418] The organic film-forming materials (UDL-1 to 13, comparative UDL-1 to 9) prepared above were coated onto bare-Si substrates, substrates treated with hexamethyldisilazane (HMDS), and substrates treated with SiON, as shown in Table 7. These were then baked in air at the temperatures listed in Table 7 for 60 seconds to form organic films with a thickness of 100 nm. The formed organic films were then observed using an optical microscope (ECLIPSE L200, manufactured by Nikon Corporation) for the presence of coating abnormalities. In this evaluation, the film thickness was reduced to assess coating properties, creating stringent evaluation conditions that are prone to film formation abnormalities.

[0419] [Table 7]

[0420]

[0421] As shown in Table 7, it can be seen that the organic films (Examples 3-1 to 3-13) formed by the organic film-forming material of the present invention have no substrate dependence and can ensure film-forming properties. In contrast, in Comparative Examples 3-7 and 3-8, as in Comparative Examples 1 and 2, film-forming properties cannot be ensured due to insufficient hardening and heat resistance of the monomolecular compound and the generation of sublimates. In addition, as in Comparative Examples 3-1 to 3-4 and 3-9, regardless of the addition of a crosslinker, a polymer, or a single polymer, film-forming properties cannot be ensured due to the substrate. From the comparison of these results, it can be inferred that the compound of the present invention contributes to the improvement of film-forming properties by the cyclic amide structure functioning as an adhesion group. In terms of the same tendency, it can also be inferred that in Comparative Example 3-5 using a polymer having a cyclic amide structure, the single polymer having no hardening properties and poor heat resistance cannot ensure film-forming properties, while Comparative Example 3-6, which adds a crosslinker to form a cured film, improves film-forming properties.

[0422] [Example 4 Evaluation of Landfill Characteristics (Examples 4-1 to 4-13, Comparative Examples 4-1 to 4-9)]

[0423] The organic film forming materials (UDL-1 to 13, comparative UDL-1 to 9) prepared above were coated on SiO2 wafer substrates with dense hole patterns (hole diameter 0.16 μm, hole depth 0.50 μm, distance between the centers of two adjacent holes 0.32 μm), and calcined in air at the temperature listed in Table 8 for 60 seconds to form organic films. The substrate used was as follows Figure 2 The base substrate 7 (SiO2 wafer substrate) with a dense hole pattern shown in (G) (top view) and (H) (cross-sectional view). The cross-sectional shape of each wafer substrate obtained was observed using a scanning electron microscope (SEM) to confirm whether the inside of the hole was filled with the organic film 8 without gaps. The results are shown in Table 8. When an organic film forming material with poor filling characteristics is used, gaps will be generated inside the hole in this evaluation. When an organic film forming material with good filling characteristics is used, in this evaluation, as shown in FIG. Figure 2 As shown in (I), the organic film is filled inside the pores without any gaps.

[0424] [Table 8]

[0425]

[0426] As shown in Examples 4-1 to 4-13 in Table 8, it can be seen that when the compounds of the present invention are used, the hole pattern can be filled without voids regardless of the organic film material, and the filling characteristics are excellent. On the other hand, in Comparative Examples 4-1 to 4-5, 4-7, and 4-8, as in the results of Comparative Examples 1 and 2, it is believed that due to insufficient heat resistance, voids are generated due to thermal decomposition, resulting in poor filling. In addition, in Comparative Example 4-6, it is believed that the use of a polymer to ensure solvent resistance and heat resistance has poor thermal fluidity compared to a single molecule, and the rapid hardening reaction caused by the action of the thermal acid generator has led to insufficient thermal fluidity and poor filling, resulting in voids. On the other hand, in Comparative Example 4-9, it can be seen that a single compound is used, so although a cross-linking agent is used, the contribution of thermal fluidity can ensure filling properties.

[0427] [Evaluation of Flattening Characteristics of Example 5 (Examples 5-1 to 5-13, Comparative Examples 5-1 to 5-9)]

[0428] The organic film forming materials (UDL-1 to 13, comparative UDL-1 to 9) prepared above were coated on the surfaces of the substrates having large isolated trench patterns ( Figure 3 The organic film 10 was baked in the atmosphere at the temperature described in Table 9 for 60 seconds, and the height difference between the organic film 10 in the trench portion and the non-trench portion (the difference in film thickness of the resist underlayer film in the trench portion and the non-trench portion) was observed using an NX10 atomic force microscope (AFM) manufactured by Park Systems. Figure 3 The results are shown in Table 9. In this evaluation, smaller height differences indicate better planarization characteristics. Furthermore, this evaluation used a 0.10μm deep trench pattern planarized using an organic film material with a typical film thickness of approximately 0.2μm, a strict evaluation condition for evaluating the quality of planarization characteristics.

[0429] [Table 9]

[0430]

[0431] As shown in Examples 5-1 to 5-13 in Table 9, when the compounds of the present invention were used, the height difference between the organic film in the trench portion and the non-trench portion was smaller in all organic film materials compared to Comparative Examples 5-1 to 5-9, resulting in better planarization properties. It can be seen that the examples using propargyloxy and ethynyl groups in the compounds in particular achieved excellent planarization results. The results of the heat resistance test in Example 2 suggest that this is due to excellent heat resistance, which suppresses film shrinkage during baking. In contrast, Comparative Examples 5-1 to 5-5, 5-7, and 5-8, as in the results of the heat resistance test in Comparative Example 2, are believed to have insufficient heat resistance and significant film shrinkage during baking, resulting in a film thickness with a height difference and deteriorating planarization properties. In Comparative Examples 5-6 and 5-9, it is believed that the use of a crosslinker to ensure solvent resistance resulted in a rapid curing reaction, preventing the benefits of thermal fluidity and failing to achieve good planarization properties. Furthermore, Comparative Example 5-6, which uses a polymer and inherently lacks thermal fluidity, demonstrates deteriorated planarization properties compared to Comparative Example 5-9, which uses a single, non-polymeric molecule. Furthermore, a comparison of Examples 5-10 to 5-13, which added a high-boiling-point solvent, with Examples 5-1, 5-3, 5-4, and 5-5, which did not, also reveals that the addition of a high-boiling-point solvent further improved planarization.

[0432] [Example 6 Adhesion Test (Examples 6-1 to 6-13, Comparative Examples 6-1 to 6-4)]

[0433] The organic film-forming materials (UDL-1 to 13, comparative UDL-1, 3, 6, and 9) were applied to a SiO2 wafer substrate and baked in air using a hot plate for 60 seconds at the temperature listed in Table 10 to form an organic film with a thickness of 200 nm. The wafer with the organic film was cut into 1×1 cm squares, and aluminum pins with epoxy adhesive were attached to the cut wafers using a specialized jig. The wafers were then heated in an oven at 150°C for 1 hour to bond the aluminum pins to the substrate. After cooling to room temperature, initial adhesion was evaluated by resistance using a thin film adhesion strength tester (Sebastian Five-A). Furthermore, since comparative UDL-2, 4, 5, 7, and 8 in Comparative Example 1 could not ensure solvent resistance, adhesion testing could not be performed.

[0434] Figure 4 This figure shows an explanatory diagram illustrating the adhesion measurement method. Figure 4 11 represents the silicon wafer (substrate), 12 represents the hardened film, 14 represents the aluminum pin with adhesive, 13 represents the support, 15 represents the clamp, and 16 represents the direction of tension. Adhesion strength is the average value of measurements taken at 12 points. A higher value indicates greater adhesion to the substrate. Adhesion was evaluated by comparing the obtained values. The results are shown in Table 10.

[0435] [Table 10]

[0436]

[0437] As shown in Examples 6-1 to 6-13 in Table 10, organic film materials using the compounds of the present invention exhibit higher adhesion than those of Comparative Examples 6-1, 6-2, and 6-4. Furthermore, Comparative Example 6-3 exhibits high adhesion due to its similar cyclic amide structure. These results also suggest that the cyclic amide structure introduced into the compounds and polymers of the present invention improves adhesion, demonstrating excellent film-forming properties, as demonstrated in Example 3.

[0438] [Example 7 Pattern Formation Test (Examples 7-1 to 7-13, Comparative Examples 7-1 to 7-4)]

[0439] The organic film-forming materials (UDL-1 to 13, comparative UDL-1, 3, 6, and 9) were applied to a bare Si substrate with a 200 nm thick SiO2 film and a trench pattern (10 μm trench width, 0.10 μm trench depth) formed thereon, which had been treated with HMDS. The organic film (resist underlayer film) was then calcined in air under the conditions shown in Table 14 to achieve a 200 nm film thickness on the bare Si substrate. A silicon-containing resist interlayer material (SOG-1) was then applied thereto and baked at 220°C for 60 seconds to form a 35 nm thick resist interlayer film. A resist upper layer material (SL resist for ArF) was then applied thereto and baked at 105°C for 60 seconds to form a 100 nm thick resist upper layer film. A wet resist film (TC-1) was applied to the resist upper layer film and baked at 90°C for 60 seconds to form a 50 nm thick protective film. Furthermore, in Comparative Example 1, the comparative UDL-2, 4, 5, 7, and 8, which could not ensure solvent resistance, could not form a silicon-containing resist interlayer film, and thus the pattern formation test could not be performed.

[0440] As an anti-etching agent upper layer film material (SL anti-etching agent for ArF), a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) are dissolved in a solvent containing 0.1% by mass of FC-430 (produced by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 11, and the mixture is filtered through a 0.1 μm fluororesin filter to prepare the material.

[0441] [Table 11]

[0442]

[0443] The structural formulas of the polymer (RP1), acid generator (PAG1), and basic compound (Amine1) used are shown below.

[0444] [Chemistry 45]

[0445]

[0446] As the wet protective film material (TC-1), the protective film polymer (PP1) was dissolved in an organic solvent at the ratio shown in Table 12, and the solution was filtered through a 0.1 μm fluororesin filter to prepare the wet protective film material (TC-1).

[0447] [Table 12]

[0448]

[0449] The structural formula of the polymer (PP1) used is shown below.

[0450] [Chemistry 46]

[0451]

[0452] As a silicon-containing anti-etching intermediate film material (SOG-1), a polymer represented by ArF silicon-containing intermediate film polymer (SiP1) and a cross-linking catalyst (CAT1) were dissolved in an organic solvent containing 0.1% by mass of FC-4430 (produced by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 13, and filtered through a fluororesin filter with a pore size of 0.1 μm to prepare a silicon-containing anti-etching intermediate film material (SOG-1).

[0453] [Table 13]

[0454]

[0455] The structural formulas of the ArF silicon-containing interlayer polymer (SiP1) and the crosslinking catalyst (CAT1) used are shown below.

[0456] [Chemistry 47]

[0457]

[0458] Then, exposure was performed while changing the exposure amount using an ArF immersion exposure device (manufactured by Nikon Corporation; NSR-S610C, NA1.30, σ0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% half-step phase shift mask), baked (PEB) at 100°C for 60 seconds, and developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a positive line and space pattern with a pitch of 100 nm and a resist line width ranging from 50 nm to 30 nm.

[0459] Then, dry etching was performed using a Telius etching apparatus manufactured by Tokyo Electron Corporation to process the silicon-containing interlayer film using the resist pattern as a mask, process the organic film using the silicon-containing interlayer film as a mask, and process the SiO2 film using the organic film as a mask.

[0460] The etching conditions are as follows.

[0461] Transfer conditions of the resist pattern to the SOG film.

[0462]

[0463] Transfer conditions of SOG film to organic film.

[0464]

[0465] Transfer conditions for SiO2 films.

[0466]

[0467] The pattern cross-sections were observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the shapes were compared. The results are summarized in Table 14.

[0468] [Table 14]

[0469]

[0470] As shown in Table 14, similar to the results for the organic film-forming materials of the present invention (Examples 7-1 to 7-13), the resist upper layer pattern was successfully transferred to the substrate in all cases, confirming that the organic film-forming materials of the present invention are suitable for microfabrication using the multilayer resist method. On the other hand, in Comparative Examples 7-1, 7-2, and 7-3, pinholes generated during film formation caused pattern collapse during pattern processing, resulting in failure to form a pattern. In Comparative Example 7-4, pinholes generated during film formation also caused pattern collapse during pattern processing, resulting in failure to form a pattern.

[0471] Based on the above facts, it is clear that if it is the organic film forming material of the present invention, it has good film-forming properties and adhesion, and excellent filling / planarization characteristics, so it is extremely useful as an organic film material (resist underlayer film) used in the multilayer resist method. In addition, if it is the pattern forming method of the present invention using the organic film forming material of the present invention, even if the processed body is a substrate with height differences, a fine pattern can be formed with high precision.

[0472] The present invention is not limited to the above-described embodiments, which are merely illustrative, and any technology having substantially the same configuration and exhibiting the same effects as those described in the claims of the present invention is encompassed within the technical scope of the present invention.

[0473] Description of Reference Numerals

[0474] 1:Substrate

[0475] 2: Processed layer

[0476] 2a: Pattern formed on the processed layer

[0477] 3: Organic film

[0478] 3a: Organic film pattern

[0479] 4: Silicon-containing resist interlayer

[0480] 4a: Silicon-containing resist interlayer pattern

[0481] 5: Resist upper film

[0482] 5a: Resist upper film pattern

[0483] 6: Used part (exposed part)

[0484] 7: Base substrate with dense hole pattern

[0485] 8: Organic film

[0486] 9: Base substrate with large isolated trench patterns

[0487] 10: Organic film

[0488] delta 10: Difference in thickness of the resist underlayer film between the trench portion and the non-trench portion

[0489] 11: Silicon wafer

[0490] 12: Hardened film

[0491] 13: Support Desk

[0492] 14: Aluminum pin with adhesive

[0493] 15: Fixture

[0494] 16: stretching direction

Claims

1. An organic film-forming material, characterized in that: Contains a compound represented by the following general formula (1) and an organic solvent: In the general formula (1), R1 is any one of the following formulas (2); R2 represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; n represents 0 or 1, m represents an integer of 1 to 3, p represents 0 or 1, and l represents an integer of 0 to 2; and W represents any one of the following structures:

2. The organic film-forming material according to claim 1, wherein The compound represented by the general formula (1) is a compound represented by the following general formula (3); In the general formula (3), R1, R2, W, l, and p are the same as described above; and m' represents an integer of 1 or 2.

3. The organic film-forming material according to claim 1 or 2, wherein The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the compound as measured by gel permeation chromatography in terms of polystyrene is 1.00≦Mw / Mn≦1.

10.

4. The organic film-forming material according to claim 1 or 2, wherein The organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180 degrees and one or more organic solvents having a boiling point of 180 degrees or higher.

5. The organic film-forming material according to claim 1 or 2, wherein It further contains one or more of an acid generator, a cross-linking agent, a surfactant, and a plasticizer.

6. A pattern forming method comprising the following steps: forming an organic film on a workpiece using the organic film-forming material according to any one of claims 1 to 5; forming a silicon-containing resist interlayer film on the organic film using a silicon-containing resist interlayer material; forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition; forming a circuit pattern on the upper layer of the resist; Using the patterned resist upper layer film as a mask, the pattern is transferred to the silicon-containing resist intermediate film by etching; Using the transferred patterned silicon-containing resist intermediate film as a mask, the pattern is transferred to the organic film by etching; Furthermore, the object to be processed is etched using the organic film to which the pattern has been transferred as a mask to form a pattern on the object to be processed.

7. A pattern forming method comprising the following steps: forming an organic film on a workpiece using the organic film-forming material according to any one of claims 1 to 5; forming a silicon-containing resist interlayer film on the organic film using a silicon-containing resist interlayer material; forming an organic anti-reflective film (BARC) on the silicon-containing resist intermediate film; A photoresist composition is used to form a resist upper layer film on the BARC to form a four-layer film structure; forming a circuit pattern on the upper layer of the resist; Using the patterned resist upper layer film as a mask, transferring the pattern to the BARC film and the silicon-containing resist intermediate film by etching; Using the transferred patterned silicon-containing resist intermediate film as a mask, the pattern is transferred to the organic film by etching; Furthermore, the object to be processed is etched using the organic film to which the pattern has been transferred as a mask to form a pattern on the object to be processed.

8. A pattern forming method comprising the following steps: forming an organic film on a workpiece using the organic film-forming material according to any one of claims 1 to 5; forming an inorganic hard mask film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a photoresist composition; forming a circuit pattern on the upper layer of the resist; Using the patterned resist upper layer film as a mask, the inorganic hard mask is etched to transfer the pattern; Using the patterned inorganic hard mask as a mask, the organic film is etched to transfer the pattern; Furthermore, the object to be processed is etched using the patterned organic film as a mask to form a pattern on the object to be processed.

9. A pattern forming method comprising the following steps: forming an organic film on a workpiece using the organic film-forming material according to any one of claims 1 to 5; forming an inorganic hard mask film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film; forming an organic anti-reflective film (BARC) on the inorganic hard mask; Using a photoresist composition, a resist upper layer film is formed on the BARC to form a four-layer film structure; forming a circuit pattern on the upper layer of the resist; Using the patterned resist upper layer film as a mask, the BARC film and the inorganic hard mask are etched to transfer the pattern; Using the patterned inorganic hard mask as a mask, the organic film is etched to transfer the pattern; Furthermore, the object to be processed is etched using the patterned organic film as a mask to form a pattern on the object to be processed.

10. The pattern forming method according to claim 8 or 9, wherein The inorganic hard mask is formed by a CVD method or an ALD method.

11. The pattern forming method according to any one of claims 6 to 9, wherein The patterning method of the resist upper layer film is optical lithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

12. The pattern forming method according to any one of claims 6 to 9, wherein In this pattern forming method, after exposing the pattern circuit region of the resist upper layer film, the resist upper layer film is developed with a developer to form a circuit pattern. The developing method is alkali development or development with an organic solvent.

13. The pattern forming method according to any one of claims 6 to 9, wherein The workpiece is a semiconductor device substrate, or a semiconductor device substrate on which a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film is formed.

14. The pattern forming method according to claim 13, wherein The metal is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, cobalt, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, manganese, molybdenum, ruthenium, or an alloy thereof.

15. A compound characterized by being represented by the following general formula (1): In the general formula (1), R1 is any one of the following formulas (2); R2 represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; n represents 0 or 1, m represents an integer of 1 to 3, p represents 0 or 1, and l represents an integer of 0 to 2; and W represents any one of the following structures:

16. The compound according to claim 15, wherein The compound represented by the general formula (1) is a compound represented by the following general formula (3): In the general formula (3), R1, R2, W, l, and p are the same as those described above, and m' represents an integer of 1 or 2.

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