Organic film forming material, organic film forming method, pattern forming method, and compound

Abstract

The present invention relates to an organic film forming material, an organic film forming method, a pattern forming method, and a compound. The present invention provides an organic film material for forming an organic film that takes into account high-level filling characteristics / high-level planarization characteristics / and excellent adhesion between substrates. An organic film forming material containing a compound represented by the following general formula (1) and an organic solvent is provided. In the general formula (1), X is an n1-valent organic group with a carbon number of 2 to 50, n1 represents an integer of 2 to 10, and R1 is at least one of the following formulas (2) to (4); in the general formula (3), l1 represents 0 or 1; in the general formula (4), l2 represents 0 or 1.

Description

Technical Field

[0001] The present invention relates to an organic film forming material, an organic film forming method, a pattern forming method, and a compound. Background Art

[0002] With the high integration and high speed of LSI, the miniaturization of pattern size has been progressing rapidly. With this miniaturization, photolithography technology has achieved the formation of fine patterns through the shortening of the wavelength of the light source and the appropriate selection of the corresponding resist composition. The center of this is the positive photoresist composition used in a single layer. This single-layer positive photoresist composition has a skeleton with etching resistance to dry etching using chlorine-based or fluorine-based gas plasma in the resist resin, and has a resist structure that dissolves the exposed part, thereby dissolving the exposed part to form a pattern, and using the remaining resist pattern as an etching mask, the substrate to be processed that has been coated with the resist composition is dry-etched.

[0003] However, if the thickness of the photoresist film used in this state is miniaturized, that is, when the pattern width is reduced, the resolution of the photoresist film will decrease, and if the photoresist film is to be patterned with a developer, the so-called aspect ratio will become too large, resulting in pattern collapse. Therefore, with miniaturization, the thickness of the photoresist film will become thinner and thinner.

[0004] On the other hand, in the processing of the substrate to be processed, a method of processing the substrate by dry etching is usually adopted, using a photoresist film with a pattern as an etching mask. However, in reality, there is no dry etching method that can obtain complete etching selectivity between the photoresist film and the substrate to be processed, so the resist film will also be damaged during the substrate processing, and the resist film collapse will occur during the substrate processing, and the resist pattern cannot be accurately transferred to the substrate to be processed. Therefore, with the miniaturization of the pattern, higher dry etching resistance is also required for the resist composition. In addition, due to the shortening of the exposure wavelength, the resin used in the photoresist composition needs to have no resin with low light absorption at the exposure wavelength. Therefore, in view of the transition to i-rays, KrF, and ArF, it gradually shifts to novolac resins, polyhydroxystyrene, and resins with aliphatic polycyclic skeletons. However, in reality, the etching speed becomes faster under the above-mentioned dry etching conditions, and the recent photoresist composition with high resolution tends to weaken the etching resistance.

[0005] Therefore, the substrate to be processed has to be dry-etched using a thinner photoresist film with weaker etching resistance, and securing materials and processing in this processing step becomes a top priority.

[0006] One method to solve such a problem is the multilayer resist method. This method is to insert an intermediate film having a different etching selectivity from the photoresist film (i.e., the resist upper film) between the resist upper film and the processed substrate, and after the resist upper film has a pattern, the resist upper film pattern is used as a dry etching mask to transfer the pattern to the intermediate film by dry etching, and then the intermediate film is used as a dry etching mask to transfer the pattern to the processed substrate by dry etching.

[0007] One of the multilayer resist methods is a three-layer resist method that can be implemented using a general resist composition used in the single-layer resist method. In this three-layer resist method, for example, an organic film obtained by novolac resin or the like is formed on a substrate to be processed as a resist lower film, a silicon-containing film is formed thereon as a resist intermediate film, and a normal organic photoresist film is formed thereon as a resist upper film. When dry etching is performed using fluorine-based gas plasma, the organic resist upper film can obtain a good etching selectivity ratio to the silicon-containing resist intermediate film, so the resist upper film pattern can be transferred to the silicon-containing resist intermediate film by dry etching using fluorine-based gas plasma. Furthermore, for etching using oxygen or hydrogen, the silicon-containing resist intermediate film obtains a good etching selectivity ratio to the organic lower film, so the silicon-containing intermediate film pattern can be transferred to the lower film by etching using oxygen or hydrogen. According to this method, even if a resist composition that is difficult to form a pattern with a sufficient film thickness for directly processing a substrate or a resist composition that does not have sufficient dry etching resistance for substrate processing is used, if the pattern can be transferred to a silicon-containing film (resist intermediate film), a pattern of an organic film (resist lower film) made of a phenolic varnish resin or the like that has sufficient dry etching resistance for substrate processing can be obtained.

[0008] As mentioned above, there are many technologies for the organic lower film that are known to the public (for example, Patent Document 1). However, in recent years, in addition to dry etching resistance, the need for excellent filling characteristics, flattening characteristics, or adhesion to the substrate has gradually increased. For example, when the substrate to be processed of the base has micro-pattern structures such as holes and trenches, it is necessary to have a filling characteristic that fills the pattern with a film without gaps. In addition, when the substrate to be processed of the base has a height difference, and when there are pattern-dense parts and pattern-free areas on the same wafer, it is necessary to use the lower film to flatten the film surface. By flattening the surface of the lower film, the thickness variation of the intermediate layer and photoresist formed thereon can be suppressed, and the focus tolerance of the lithography and the tolerance of the subsequent processing steps of the substrate to be processed can be expanded. Furthermore, when an inorganic hard mask is formed on the organic lower film, it is necessary to have a close fit with the substrate. By improving the adhesion, it is possible to prevent film peeling when an inorganic hard mask is formed directly on an organic film using a CVD method or an ALD method, and to form an organic film with an excellent process margin.

[0009] As for the method for improving the filling / planarization characteristics of the lower film material, it is proposed to add liquid additives such as polyether polyols (Patent Document 2). However, the organic film formed by this method contains a large amount of polyether polyol units with poor etching resistance, so the etching resistance will be greatly reduced, which is not suitable for use as a three-layer resist lower film. In addition, as for the method for improving the adhesion between the lower film material and the substrate, it is proposed to use a resist lower film material with a lactone ring structure as a constituent component (Patent Document 3). However, the resist lower film material has the problem that the adhesion to the substrate is difficult to meet the requirements of the most advanced devices. In this way, a resist lower film material that takes into account excellent filling / planarization characteristics / adhesion between the substrate and sufficient etching resistance, and a pattern forming method using this material are sought.

[0010] Furthermore, the use of organic film materials with excellent filling characteristics / planarization characteristics / adhesion to substrates is not limited to three-layer resist underlayer films, but can also be widely used as planarization materials for semiconductor device manufacturing, such as substrate planarization before patterning using nanostamping. Furthermore, overall planarization in the semiconductor device manufacturing process is currently generally performed by CMP processing, but CMP is a high-cost process, and it is expected that the present invention can be used as a material for overall planarization methods that replace it.

[0011] Prior art literature

[0012] Patent Literature

[0013] [Patent Document 1] Japanese Patent Application Publication No. 2004-205685

[0014] [Patent Document 2] Japanese Patent No. 4784784

[0015] [Patent Document 3] Japanese Patent No. 3985165 Summary of the invention

[0016] Problem that the invention aims to solve

[0017] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organic film material for forming an organic film that satisfies both high-level filling characteristics, high-level planarization characteristics, and excellent adhesion between substrates.

[0018] Solutions for solving problems

[0019] In order to solve the above-mentioned problems, the present invention provides an organic film-forming material comprising a compound represented by the following general formula (1) and an organic solvent.

[0020] [Chemistry 1]

[0021]

[0022] In the above general formula (1), X is an n1-valent organic group having 2 to 50 carbon atoms, n1 represents an integer of 2 to 10, and R1 is at least one of the following general formulae (2) to (4).

[0023] [Chemistry 2]

[0024]

[0025] In the above general formula (2), * (asterisk) represents the bonding site with the above organic group X, R a and R b represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R c represents a hydrogen atom, a methyl group or a phenyl group, m1 and m2 represent an integer of 0 or 1, n2 and n3 represent an integer of 1 to 7, satisfying the relationship of 1≤n2+n3≤7, and n4 represents an integer of 1 to 10;

[0026] [Chemistry 3]

[0027]

[0028] In the above general formula (3), * represents the bonding site to the above organic group X, R d and R e represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R f represents a hydrogen atom, a methyl group or a phenyl group, m3 and m4 represent integers of 0 or 1, n5 and n6 represent integers of 1 to 7, and satisfy the relationship of 1≤n5+n6≤7. l1 represents 0 or 1, when l1=1, the oxygen atom forms a bridging structure between aromatic rings as an ether bond, and when l1=0, there is no ether bond forming a bridging structure between aromatic rings.

[0029] [Chemistry 4]

[0030]

[0031] In the above general formula (4), * represents the bonding site to the above organic group X, R g and R h represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, m5 and m6 represent integers of 0 or 1, n7 and n8 represent integers of 1 to 7, and satisfy the relationship of 1≤n7+n8≤7. l2 represents 0 or 1, and when l2=1, the oxygen atom forms a bridging structure between aromatic rings as an ether bond, and when l2=0, there is no ether bond forming a bridging structure between aromatic rings.

[0032] If the organic film forming material contains a compound with a bisphenol derivative connected by such a soft chain as the terminal structure, it will become an organic film forming material that can form an organic film that can take into account high-level filling characteristics / high-level flattening characteristics, excellent adhesion between substrates, and good heat resistance and dry etching resistance.

[0033] The organic group X in the general formula (1) is preferably any of the following general formulas (5), (7), (8), (9), (10), (11), (12), (13), (14) and (15).

[0034] [Chemistry 5]

[0035]

[0036] In the above general formula (5), m7 and m8 each independently represent 0 or 1, W represents a single bond or any of the structures shown in the following (6), R1 is the aforementioned R1 group, n9 and n10 each independently represent an integer from 0 to 4, and n9+n10 is 1 or more and 8 or less.

[0037] [Chemistry 6]

[0038]

[0039] In the above general formula (6), n11 represents an integer from 0 to 3, Ri, Rj, Rk, Rl, Rm and Rn independently represent a hydrogen atom, or an alkyl group or phenyl group having 1 to 10 carbon atoms which may be substituted with fluorine, and Ri and Rj may also be bonded to form a cyclic compound.

[0040] [Chemistry 7]

[0041]

[0042] In the above general formula (7), R1 is the aforementioned R1 group, and Ro represents a hydrogen atom, a methyl group or a phenyl group.

[0043] [Chemistry 8]

[0044]

[0045] In the above general formulae (8) to (12), R1 is the aforementioned R1 group, and Rp, Rq, Rr, Rs, Rt, Ru, and Rv are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a benzyl group or a phenyl group which may have a substituent on the aromatic ring. Y represents the aforementioned R1 group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and at least two of the four Ys in formula (12) are the aforementioned R1 groups.

[0046] [Chemistry 9]

[0047] R1O-Rw-OR1 (13)

[0048]

[0049] Rw in the general formula (13) represents a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and Rx in the general formula (14) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R1 in the general formulas (13) to (15) is the aforementioned R1 group.

[0050] An organic film material using such an organic film-forming compound can form an organic film that has both high filling characteristics / high flattening characteristics and good adhesion to the substrate. In particular, by appropriately selecting the structure of the organic group X in accordance with the required performance, various physical properties such as etching resistance and optical constants (n / k) can also be controlled.

[0051] Furthermore, the R1 group in the above general formula is preferably composed of any one or more of the above general formulae (2) to (4) and any one or more of the following general formulae (16) and (17).

[0052] [Chemistry 10]

[0053]

[0054] In the above general formula (16), R2 represents a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and the methylene group constituting the R2 group may be substituted by an oxygen atom or a carbonyl group.

[0055] [Chemistry 11]

[0056]

[0057] In the above general formula (17), R3 represents a hydrogen atom, or a straight-chain or branched hydrocarbon group having 1 to 10 carbon atoms, R4 represents a straight-chain or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n11 represents 0 to 2, n12 and n13 represent the number of substituents on the aromatic ring, and n12 and n13 represent integers of 0 to 7, and satisfy the relationship that n12+n13 is greater than or equal to 0 and less than or equal to 7.

[0058] If the organic film forming material contains such a compound, by combining the use of aromatic rings or terminal groups with hydrocarbon structures, various physical properties such as heat resistance, etching resistance, filling characteristics / planarization characteristics, adhesion between substrates, control of optical constants (n / k) can be adjusted and / or improved according to the required performance.

[0059] Furthermore, the organic film-forming material preferably further contains one or more of a surfactant, a cross-linking agent, and a plasticizer.

[0060] The organic film-forming material of the present invention may contain one or more of the above-mentioned components depending on the purpose.

[0061] The organic solvent is more preferably a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

[0062] In such an organic film-forming composition, by adding a high-boiling-point solvent to the above-mentioned polymer to impart thermal fluidity to the film, it becomes an organic film-forming material that achieves both a higher degree of filling property and a higher degree of planarization property.

[0063] Thus, the organic film forming material of the present invention can provide a resist underlayer film material for forming a resist underlayer film having high dry etching resistance and having both high filling characteristics / high flattening characteristics / and excellent adhesion between substrates by using the formation of a multilayer resist film used in microfabrication in the manufacturing steps of semiconductor devices, etc. In addition, a planarizing material for semiconductor device manufacturing having excellent filling characteristics / excellent flattening characteristics / and excellent adhesion between substrates that can be used for planarization in the manufacturing steps of semiconductor devices other than multilayer resist processing can be provided.

[0064] Furthermore, the present invention provides a method for forming an organic film, which is a method for forming an organic film that functions as an organic flat film in a manufacturing step of a semiconductor device, wherein:

[0065] The organic film forming material is spin-coated on the substrate to be processed.

[0066] The substrate is heat-treated at a temperature of 100° C. to 600° C. for 10 seconds to 600 seconds to form a cured film.

[0067] Thus, by applying the aforementioned organic film forming material and heat treating the organic film material at a temperature of 100° C. to 600° C. for 10 to 600 seconds, the crosslinking reaction can be promoted and mixing with the upper film can be prevented.

[0068] Furthermore, the present invention provides an organic film forming method, which is a method for forming an organic film that acts as an organic flat film in the manufacturing steps of a semiconductor device, and is characterized in that: the above-mentioned organic film forming material is spin-coated on a processed substrate, and the substrate is heat-treated in a gas environment with an oxygen concentration of not less than 0.1% and not more than 21% to form a hardened film.

[0069] The organic film-forming material of the present invention can obtain a sufficiently hardened organic film by calcining in a gas atmosphere having such an oxygen concentration.

[0070] At this time, it is preferred that the substrate to be processed has a structure with a height of 30 nm or more or a height difference.

[0071] The organic film forming material of the present invention is excellent in filling property, planarizing property, and adhesion to a substrate, and is particularly useful for forming a flat organic film on a structure having a height of 30 nm or more or on a substrate having a height difference.

[0072] Furthermore, the present invention provides a pattern forming method, characterized in that:

[0073] Forming a resist underlayer film on a workpiece using the above-mentioned organic film forming material,

[0074] On the resist underlayer film, a resist intermediate layer film is formed using a resist intermediate layer film material containing silicon,

[0075] On the resist intermediate layer film, a resist upper layer film is formed using a resist upper layer film material containing a photoresist composition,

[0076] A circuit pattern is formed on the upper layer of the resist.

[0077] The resist upper layer film having the pattern is used as a mask to etch the resist intermediate layer film, thereby transferring the pattern to the resist intermediate layer.

[0078] Using the resist intermediate layer film to which the pattern has been transferred as a mask, the resist lower layer film is etched to transfer the pattern to the resist lower layer film.

[0079] Furthermore, the object to be processed is etched using the resist underlayer film to which the pattern has been transferred as a mask, thereby forming a pattern on the object to be processed.

[0080] In such a multilayer resist process, if the pattern forming method using the organic film forming material of the present invention is used, a fine pattern can be formed on the substrate to be processed with high precision.

[0081] At this time, the etching of the resist underlayer film is preferably performed using the resist intermediate layer film pattern obtained above as an etching mask, using an etching gas mainly composed of oxygen or hydrogen.

[0082] The resist interlayer film containing silicon atoms is resistant to etching by oxygen or hydrogen gas, so the etching of the resist underlayer film using the resist interlayer film as an etching mask can be performed using an etching gas mainly containing oxygen or hydrogen gas.

[0083] Furthermore, the present invention provides a pattern forming method, characterized in that:

[0084] Forming a resist underlayer film on a workpiece using the above-mentioned organic film forming material,

[0085] On the resist underlayer film, a resist intermediate layer film is formed using a resist intermediate layer film material containing silicon atoms,

[0086] forming an organic anti-reflective film (BARC) on the resist interlayer film,

[0087] A resist upper layer film material containing a photoresist composition is used on the organic anti-reflection film to form a resist upper layer film to form a 4-layer film structure.

[0088] A circuit pattern is formed on the upper layer of the resist.

[0089] The organic anti-reflection film and the resist intermediate film are etched using the patterned resist upper film as a mask, and the pattern is transferred to the organic anti-reflection film and the resist intermediate film.

[0090] The resist lower layer film is etched using the resist intermediate layer film to which the pattern has been transferred as a mask, thereby transferring the pattern to the resist lower layer film.

[0091] Furthermore, the object to be processed is etched using the resist underlayer film to which the pattern has been transferred as a mask, thereby forming a pattern on the object to be processed.

[0092] Furthermore, the present invention provides a pattern forming method, characterized in that:

[0093] Forming a resist underlayer film on a workpiece using the organic film-forming material of the present invention,

[0094] forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film and a silicon oxide nitride film on the resist underlayer film,

[0095] A resist upper layer film is formed on the inorganic hard mask intermediate film using a resist upper layer film material containing a photoresist composition,

[0096] A circuit pattern is formed on the upper layer of the resist.

[0097] The inorganic hard mask intermediate film is etched using the patterned resist upper film as a mask to transfer the pattern to the inorganic hard mask intermediate film.

[0098] The inorganic hard mask intermediate film having the pattern formed therein is used as a mask to etch the resist underlayer film, thereby transferring the pattern to the resist underlayer film.

[0099] Furthermore, the object to be processed is etched using the patterned resist underlayer film as a mask to form a pattern on the object to be processed.

[0100] In this way, a resist intermediate film may be formed on the resist lower film, but an inorganic hard mask intermediate film selected from any of a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film may be formed on the resist lower film. Furthermore, a photoresist film as a resist upper film may be formed on the inorganic hard mask intermediate film, but an organic anti-reflective film (BARC) may be formed by spin coating on the inorganic hard mask intermediate film and a photoresist film may be formed thereon. When a silicon oxide nitride film (SiON film) is used as an inorganic hard mask intermediate film, the two-layer anti-reflective film of the SiON film and the BARC can suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another advantage of forming the BARC is that it has the effect of reducing the tailing of the photoresist pattern directly on the SiON film.

[0101] Furthermore, in the pattern forming method of the present invention, the inorganic hard mask intermediate film may be formed by a CVD method or an ALD method.

[0102] In the pattern forming method of the present invention, an inorganic hard mask intermediate film formed by a CVD method or an ALD method and a resist underlayer film formed by a spin coating method may be combined.

[0103] The circuit pattern is preferably formed by photolithography using light with a wavelength of 10 nm to 300 nm, direct drawing using an electron beam, nano-molding, or a combination thereof.

[0104] Furthermore, the above-mentioned circuit pattern forming method of the resist upper layer film preferably includes alkali development or development using an organic solvent.

[0105] Furthermore, the aforementioned processed body is preferably a semiconductor device substrate, or 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 (for example, any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film is formed on the semiconductor device substrate).

[0106] Furthermore, the aforementioned processed object is preferably made of silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof.

[0107] According to the pattern forming method of the present invention, the above-mentioned workpiece can be processed to form a pattern.

[0108] Furthermore, the present invention provides a compound represented by the following general formula (1).

[0109] [Chemistry 12]

[0110]

[0111] In the above general formula (1), X is an n1-valent organic group having 2 to 50 carbon atoms, n1 represents an integer of 2 to 10, and R1 is at least one of the following general formulae (2) to (4).

[0112] [Chemistry 13]

[0113]

[0114] In the above general formula (2), * represents the bonding site to the above organic group X, R a and R b represents a hydrogen atom or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R c represents a hydrogen atom, a methyl group or a phenyl group, m1 and m2 represent an integer of 0 or 1, n2 and n3 represent an integer of 1 to 7, and satisfy the relationship of 1≤n2+n3≤7. n4 represents an integer of 1 to 10.

[0115] [Chemistry 14]

[0116]

[0117] In the above general formula (3), * represents the bonding site to the above organic group X, R d and R e represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R f represents a hydrogen atom, a methyl group or a phenyl group, m3 and m4 represent integers of 0 or 1, n5 and n6 represent integers of 1 to 7, and satisfy the relationship of 1≤n5+n6≤7. l1 represents 0 or 1, and when l1=1, the oxygen atom forms a bridging structure between aromatic rings as an ether bond, and when l1=0, there is no ether bond forming a bridging structure between aromatic rings.

[0118] [Chemistry 15]

[0119]

[0120] In the above general formula (4), * represents the bonding site to the above organic group X, R g and R h represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, m5 and m6 represent integers of 0 or 1, n7 and n8 represent integers of 1 to 7 and satisfy the relationship of 1≤n7+n8≤7. l2 represents 0 or 1, when l2=1, the oxygen atom forms a bridging structure between aromatic rings as an ether bond, and when l2=0, there is no ether bond forming a bridging structure between aromatic rings.

[0121] If the compound of the present invention has a bisphenol derivative linked by a soft chain at the terminal group, when used as a component of an organic film forming material, it will become an organic film material that can form an organic film that can impart high heat resistance, excellent filling characteristics / excellent planarization characteristics and excellent adhesion to the substrate.

[0122] In the compounds of the present invention, the organic group X in the above general formula (1) is preferably any of the following general formulas (5), (7), (8), (9), (10), (11), (12), (13), (14) and (15).

[0123] [Chemistry 16]

[0124]

[0125] In the above general formula (5), m7 and m8 each independently represent 0 or 1, W represents a single bond or any of the structures shown in the following (6), R1 is the aforementioned R1 group, n9 and n10 each independently represent an integer from 0 to 4, and n9+n10 is 1 or more and 8 or less.

[0126] [Chemistry 17]

[0127]

[0128] In the above general formula (6), n11 represents an integer from 0 to 3, Ri, Rj, Rk, Rl, Rm and Rn independently represent a hydrogen atom, or an alkyl group or phenyl group having 1 to 10 carbon atoms which may be substituted with fluorine, and Ri and Rj may be bonded to form a cyclic compound;

[0129] [Chemistry 18]

[0130]

[0131] In the above general formula (7), R1 is the aforementioned R1 group, and Ro represents a hydrogen atom, a methyl group or a phenyl group.

[0132] [Chemistry 19]

[0133]

[0134] In the above general formulae (8) to (12), R1 is the aforementioned R1 group, and Rp, Rq, Rr, Rs, Rt, Ru, and Rv each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a benzyl group or a phenyl group which may have a substituent on the aromatic ring. Y represents the aforementioned R1 group or a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and at least two of the four Ys in formula (12) are the aforementioned R1 groups.

[0135] [Chemistry 20]

[0136] R1O-Rw-OR1 (13)

[0137]

[0138] Rw in the general formula (13) represents a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and Rx in the general formula (14) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R1 in the general formulas (13) to (15) is the aforementioned R1 group.

[0139] If it is such a compound, by appropriately selecting the structure of the organic group X, various physical properties such as heat resistance, etching resistance, filling characteristics / planarization characteristics, adhesion between substrates, and control of optical constants (n / k) when used as a component of an organic film material can be adjusted according to the required performance.

[0140] It is preferred that R1 in the above general formula (1) is composed of at least one of the above general formulae (2) to (4) and at least one of the following general formulae (16) and (17).

[0141] [Chemistry 21]

[0142]

[0143] In the above general formula (16), R2 represents a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and the methylene group constituting the R2 group may be substituted by an oxygen atom or a carbonyl group.

[0144] [Chemistry 22]

[0145]

[0146] In the above general formula (17), R3 represents a hydrogen atom, or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R4 represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n11 represents 0 to 2, n12 and n13 represent the number of substituents on the aromatic ring, and n12 and n13 represent integers of 0 to 7, and n12+n13 satisfies the relationship of being greater than 0 and less than 7.

[0147] If it is such a compound, the aromatic ring structure and the hydrocarbon terminal group structure can be used in combination. When used as a component of an organic film forming material, various physical properties such as heat resistance, etching resistance, filling / planarization characteristics, adhesion between substrates, and control of optical constants (n / k) can be adjusted according to the required performance.

[0148] Effects of the Invention

[0149] As described above, the present invention can provide a compound useful as a component of an organic film forming material for forming an organic film that combines high-level embedding characteristics / high-level planarization characteristics / and excellent adhesion between substrates, and an organic film forming material containing the compound. In addition, the organic film material becomes an organic film forming material that has excellent embedding / excellent planarization characteristics / and adhesion between substrates without impairing other characteristics such as heat resistance and etching resistance, and is extremely useful as a resist lower film material in multi-layer resist processing such as two-layer resist processing, three-layer resist processing using a silicon-containing intermediate film, or four-layer resist processing using a silicon-containing intermediate film and an organic anti-reflection film, or a planarization material for semiconductor device manufacturing.

[0150] Furthermore, the organic film forming method of the present invention can form a sufficiently hardened and flat organic film on a substrate to be processed. Furthermore, the pattern forming method of the present invention can form a fine pattern on a substrate to be processed with high precision in a multilayer resist process. BRIEF DESCRIPTION OF THE DRAWINGS

[0151] Figure 1 (A) to (F) are explanatory diagrams showing an example of the pattern forming method using the three-layer resist process of the present invention.

[0152] Figure 2 (G) to (I) are explanatory diagrams showing the landfill property evaluation method of Examples and Comparative Examples.

[0153] Figure 3 (J) and (K) are explanatory diagrams showing the planarization characteristic evaluation method of Examples and Comparative Examples.

[0154] Figure 4Explanatory diagram showing the adhesion measurement method of Examples and Comparative Examples. DETAILED DESCRIPTION

[0155] The present invention relates to a resist underlayer film material used in a multilayer resist step used in microfabrication of a semiconductor device manufacturing step, etc., and an organic film forming material that is effective as a flattening material for semiconductor device manufacturing, etc., and an organic film forming method using the material, and a pattern forming method suitable for exposure to extreme ultraviolet rays, KrF excimer laser (248nm), ArF excimer laser (193nm), F2 laser (157nm), Kr2 laser (146nm), Ar2 laser (126nm), soft X-rays (EUV), electron beams (EB), ion beams, X-rays, etc. using the organic film forming material, and a compound that is useful as a component of the aforementioned organic film material.

[0156] As described above, an organic film forming material for forming an organic film that satisfies both high filling characteristics, high planarization characteristics, and excellent adhesion between substrates is desired.

[0157] The inventors of the present application have made intensive research on the above-mentioned subject and have found that an organic film forming material containing a compound represented by the following general formula (1) can form an organic film having both high filling characteristics / high flattening characteristics and excellent adhesion to the substrate, thereby completing the present invention.

[0158] That is, the present invention comprises an organic film material comprising a compound represented by the following general formula (1) and an organic solvent.

[0159] [Chemistry 23]

[0160]

[0161] In the above general formula (1), X is an n1-valent organic group having 2 to 50 carbon atoms, n1 represents an integer of 2 to 10, and R1 is at least one of the following general formulae (2) to (4).

[0162] [Chemistry 24]

[0163]

[0164] In the above general formula (2), * represents the bonding site to the above organic group X, R a and R b represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R c represents a hydrogen atom, a methyl group or a phenyl group, m1 and m2 represent an integer of 0 or 1, n2 and n3 represent integers of 1 to 7 and satisfy the relationship of 1≤n2+n3≤7, and n4 represents an integer of 1 to 10.

[0165] [Chemistry 25]

[0166]

[0167] In the above general formula (3), * represents the bonding site to the above organic group X, R d and R e represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R f represents a hydrogen atom, a methyl group or a phenyl group, m3 and m4 represent integers of 0 or 1, n5 and n6 represent integers of 1 to 7 and satisfy the relationship of 1≤n5+n6≤7. l1 represents 0 or 1, when l1=1, the oxygen atom forms a bridging structure between aromatic rings as an ether bond, and when l1=0, there is no ether bond forming a bridging structure between aromatic rings.

[0168] [Chemistry 26]

[0169]

[0170] In the above general formula (4), * represents the bonding site to the above organic group X, R g and R h represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, m5 and m6 represent integers of 0 or 1, n7 and n8 represent integers of 1 to 7 and satisfy the relationship of 1≤n7+n8≤7. l2 represents 0 or 1, when l2=1, the oxygen atom forms a bridging structure between aromatic rings as an ether bond, and when l2=0, there is no ether bond forming a bridging structure between aromatic rings.

[0171] Such an organic film forming material can form an organic film having excellent adhesion to a substrate while achieving heat resistance and high-level filling / planarization characteristics by virtue of the terminal group structure of the bisphenol derivative linked via a flexible chain. Such an organic film forming material can also exhibit high dry etching resistance.

[0172] The following describes embodiments of the present invention, but the present invention is not limited thereto.

[0173] <Organic film-forming compound>

[0174] The compound contained in the organic film-forming material of the present invention, that is, the compound for forming an organic film, is represented by the following general formula (1).

[0175] [Chemistry 27]

[0176]

[0177] In the above general formula (1), X is an n1-valent organic group having 2 to 50 carbon atoms, n1 represents an integer of 2 to 10, and R1 is at least one of the following general formulae (2) to (4).

[0178] [Chemistry 28]

[0179]

[0180] In the above general formula (2), * represents the bonding site to the above organic group X, R a and R b represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R c represents a hydrogen atom, a methyl group or a phenyl group, m1 and m2 represent an integer of 0 or 1, n2 and n3 represent integers of 1 to 7 and satisfy the relationship of 1≤n2+n3≤7, and n4 represents an integer of 1 to 10.

[0181] [Chemistry 29]

[0182]

[0183] In the above general formula (3), * represents the bonding site to the above organic group X, R d and R e represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R f represents a hydrogen atom, a methyl group or a phenyl group, m3 and m4 represent integers of 0 or 1, n5 and n6 represent integers of 1 to 7 and satisfy the relationship of 1≤n5+n6≤7. l1 represents 0 or 1, when l1=1, the oxygen atom forms a bridging structure between aromatic rings as an ether bond, and when l1=0, there is no ether bond forming a bridging structure between aromatic rings.

[0184] [Chemistry 30]

[0185]

[0186] In the above general formula (4), * represents the bonding site to the above organic group X, R g and R h represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, m5 and m6 represent integers of 0 or 1, n7 and n8 represent integers of 1 to 7 and satisfy the relationship of 1≤n7+n8≤7. l2 represents 0 or 1, when l2=1, the oxygen atom forms a bridging structure between aromatic rings as an ether bond, and when l2=0, there is no ether bond forming a bridging structure between aromatic rings.

[0187] Specific examples of the organic group X in the general formula (1) include the following: In the following formula, R1 is the aforementioned R1 group, n9 and n10 each independently represent an integer of 0 to 4, and n9+n10 is 1 to 8.

[0188] [Chemistry 31]

[0189]

[0190] [Chemistry 32]

[0191]

[0192] [Chemistry 33]

[0193]

[0194] [Chemistry 34]

[0195]

[0196] The organic group X in the general formula (1) is preferably any of the following general formulas (5), (7), (8), (9), (10), (11), (12), (13), (14) and (15).

[0197] [Chemistry 35]

[0198]

[0199] In the above general formula (5), m7 and m8 each independently represent 0 or 1, W is a single bond or any of the structures shown in the following (6), R1 is the aforementioned R1 group, n9 and n10 each independently represent an integer from 0 to 4, and n9+n10 is 1 or more and 8 or less.

[0200] [Chemistry 36]

[0201]

[0202] In the above general formula (6), n11 represents an integer from 0 to 3, Ri, Rj, Rk, Rl, Rm and Rn independently represent a hydrogen atom, or an alkyl group or phenyl group having 1 to 10 carbon atoms which may be substituted with fluorine, and Ri and Rj may be bonded to form a cyclic compound;

[0203] [Chemistry 37]

[0204]

[0205] In the above general formula (7), R1 is the aforementioned R1 group, and Ro represents a hydrogen atom, a methyl group or a phenyl group.

[0206] [Chemistry 38]

[0207]

[0208] In the above general formulae (8) to (12), R1 is the aforementioned R1 group, and Rp, Rq, Rr, Rs, Rt, Ru, and Rv each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a benzyl group or a phenyl group which may have a substituent on the aromatic ring. Y represents the aforementioned R1 group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and at least two of the four Ys in formula (12) are the aforementioned R1 groups.

[0209] [Chemistry 39]

[0210] R1O-Rw-OR1 (13)

[0211]

[0212] Rw in the above general formula (13) represents a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. Rx in the above general formula (14) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R1 in the above general formulas (13) to (15) is the aforementioned R1 group.

[0213] Among the organic groups X represented by the general formula (5), the following are particularly preferred from the viewpoint of heat resistance and etching resistance.

[0214] [Chemistry 40]

[0215]

[0216] Among the organic groups X represented by the general formula (7), the following are particularly preferable from the viewpoint of heat resistance, etching resistance and curability.

[0217] [Chemistry 41]

[0218]

[0219] In the present invention, among the organic groups X represented by any one of the general formulae (8) to (12), the following are particularly preferred from the viewpoints of etching resistance, optical properties, and adhesion.

[0220] [Chemistry 42]

[0221]

[0222] In the present invention, among the organic groups X represented by any one of the general formulae (13) to (15), the following are particularly preferable from the viewpoint of planarization / filling characteristics and adhesion.

[0223] [Chemistry 43]

[0224]

[0225] As for the R1 group, the following examples are mentioned in terms of the terminal group structure represented by the general formula (2): wherein m1=0, m2=0, n4=2 and R c A methyl group is particularly preferred from the viewpoint of easy availability of raw materials and planarization / filling properties.

[0226] [Chemistry 44]

[0227]

[0228] Examples of the terminal group structure represented by the general formula (3) include the following: wherein m3 = 0, m4 = 0, R f A hydrogen atom is particularly desirable from the viewpoint of raw material acquisition and planarization / filling characteristics.

[0229] [Chemistry 45]

[0230]

[0231] Examples of the terminal group structure represented by the general formula (4) include the following. Among the following, m5=0 and m6=0 are particularly preferred from the viewpoint of raw material availability and planarization / filling characteristics.

[0232] [Chemistry 46]

[0233]

[0234] [Chemistry 47]

[0235]

[0236] Furthermore, the R1 group in the above general formula may be composed of any one or more of the above general formulae (2) to (4) and any one or more of the following general formulae (16) and (17).

[0237] [Chemistry 48]

[0238]

[0239] R2 in the above general formula (16) represents a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and the methylene group constituting the R2 group may be substituted by an oxygen atom or a carbonyl group.

[0240] [Chemistry 49]

[0241]

[0242] In the general formula (17), R3 represents a hydrogen atom, or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R4 represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n11 represents 0 to 2, and n12 and n13 represent the number of substituents on the aromatic ring, and n12 and n13 represent integers of 0 to 7, and n12+n13 is in the range of 0 to 7.

[0243] Examples of the terminal group structure represented by the general formula (16) include the following: n14 in the following formula represents an integer of 0 to 30, and n15 represents an integer of 0 to 20.

[0244] [Chemistry 50]

[0245]

[0246] [Chemistry 51]

[0247]

[0248] [Chemistry 52]

[0249]

[0250] Examples of the terminal group structure represented by the general formula (17) include the following. n16 in the following formula represents an integer of 0-9.

[0251] [Chemistry 53]

[0252]

[0253] In the case of an organic film material containing these compounds, by combining the terminal group structures represented by the general formula (16) and / or (17), various physical properties such as heat resistance and etching resistance, filling characteristics / planarization characteristics, and adhesion between substrates can be adjusted according to the required performance. In addition, the optical constant (n / k) can be controlled, so that, especially during exposure of multi-layer ArF lithography, appropriate optical constants can be given, reflected light can be suppressed, and excellent resolution can be achieved.

[0254] In addition, the molecular weight of the organic film-forming compound of the present invention is preferably 2,500 or less. With such a molecular weight, the thermal fluidity of the organic film-forming compound is better, so when it is mixed with a composition, it can fill the fine structure formed on the substrate well, and it can also form an organic film with a flat substrate. In addition, by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, the weight average molecular weight (Mw) converted to polystyrene can be obtained as the molecular weight.

[0255] By using an organic film forming material containing such a compound as a resist underlayer film material used in forming a multilayer resist film used in microfabrication in a manufacturing step of a semiconductor device, etc., a resist underlayer film material, a resist underlayer film forming method, and a pattern forming method can be provided for forming a resist underlayer film that has both high filling characteristics / high flattening characteristics / and excellent adhesion to a substrate. In addition, in the present invention, a planarizing material for semiconductor device manufacturing that has excellent filling characteristics / excellent flattening characteristics / and excellent adhesion to a substrate and can be used for planarization in a semiconductor device manufacturing step other than multilayer resist processing can be provided.

[0256] [Method for producing compound]

[0257] The compound used in the organic film material of the present invention can be produced by selecting the most suitable method according to the structure. An example of a method for synthesizing the organic film forming compound represented by the above general formula (1) is described in detail below. The method for producing the organic film forming compound is not limited to this.

[0258] The above-mentioned organic film-forming compound can be synthesized, for example, by the addition reaction of an epoxy compound and a carboxylic acid compound as shown in the following (18) to (20). a ~R h , l1, l2 and X are the same as described above.

[0259] [Chemistry 54]

[0260]

[0261] [Chemistry 55]

[0262]

[0263] [Chemistry 56]

[0264]

[0265] The amount ratio of the epoxy compound to the carboxylic acid compound is preferably 0.3 to 2.0 moles, more preferably 0.5 to 1.5 moles, and even more preferably 0.75 to 1.25 moles of carboxyl groups in the carboxylic acid compound relative to 1 mole of epoxy groups in the epoxy compound. In this way, if the amount of carboxyl groups is appropriate relative to the amount of epoxy groups, there is no risk of unreacted epoxy groups remaining and damaging the storage stability of the organic film-forming composition, and it is possible to prevent unreacted carboxylic acid compounds from remaining and becoming a cause of dissipated gas.

[0266] Furthermore, in order to improve the required performance, such as optical constants (n / k), thermal fluidity, etching resistance, heat resistance, solvent solubility, adhesion, etc., a plurality of epoxy compounds or a plurality of carboxylic acid compounds may also be used in combination. In this case, the ratio of the amount of epoxy group to the amount of carboxyl group is preferably within the above range.

[0267] The organic film-forming compound of the present invention can be generally obtained by reacting the above-mentioned epoxy compound with a carboxylic acid compound in the absence of a solvent or in a solvent in the presence of a reaction catalyst at room temperature or under cooling or heating as required.

[0268] At this time, the solvent that can be used specifically includes alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, 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; chlorine-based 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; lactones such as γ-butyrolactone; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide. These solvents can be used alone or in combination of two or more. These solvents are preferably used in an amount within a range of 0 to 2,000 parts by mass based on 100 parts by mass of the reaction raw materials.

[0269] Specific examples of the reaction catalyst include: quaternary ammonium salts such as benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltrimethylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, trimethylbenzylammonium hydroxide, N-laurylpyridinium chloride, N-lauryl 4-picoline chloride, N-laurylpicoline chloride, trimethylphenylammonium bromide, and N-benzylpicoline chloride; quaternary phosphonium salts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, and tetraphenylphosphonium chloride; tertiary amines such as tri[2-(2-methoxyethoxy)ethyl]amine, tri(3,6-dioxaheptyl)amine, and tri(3,6-dioxaoctyl)amine, and the like. The amount of the catalyst used is preferably 0.001 to 100% by mass, more preferably 0.005 to 50% by mass, relative to the raw material. The reaction temperature is preferably -50°C to the boiling point of the solvent, more preferably room temperature to 150°C. The reaction time can be appropriately selected from the range of 0.1 to 100 hours.

[0270] Reaction method can be listed as follows: epoxy compound, carboxylic acid compound and catalyst are fed in batches, epoxy compound and carboxylic acid compound are dispersed or dissolved in solvent, catalyst batches are added or diluted with solvent and dripped, or catalyst is dispersed or dissolved in solvent, epoxy compound and carboxylic acid compound are added in batches or diluted with solvent and dripped. After reaction terminates, organic film can be directly used in the form of composition, or liquid separation can be cleaned and recovered after diluting with organic solvent in order to remove unreacted raw materials, catalysts, etc. present in the system.

[0271] The organic solvent used at this time is not particularly limited as long as it can dissolve the compound 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 ethyl cyclopentyl methyl ether; chlorine-based solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The washing water used at this time can be what is generally called deionized water or ultrapure water. The number of washing times can be more than one. Washing more than 10 times may not necessarily achieve the effect of the corresponding number of washing times, so it is preferably 1 to 5 times.

[0272] In order to remove the unreacted carboxylic acid compound or acidic component in the system during separation and washing, washing with an alkaline aqueous solution can also be performed. Specific examples of the base include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium.

[0273] In addition, in order to remove metal impurities or alkaline components in the system during liquid separation and cleaning, cleaning can also be performed with an acidic aqueous solution. Specifically, the acid includes inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids; and organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0274] The above-mentioned liquid separation and washing using alkaline aqueous solution and acidic aqueous solution may be performed alone or in combination. From the viewpoint of removing metal impurities, liquid separation and washing are preferably performed in the order of alkaline aqueous solution and acidic aqueous solution.

[0275] After the above-mentioned separation and washing using alkaline aqueous solution and acidic aqueous solution, it can be washed with neutral water. Neutral water can be the above-mentioned deionized water, ultrapure water, etc. The number of washing times can be more than one, but in order to fully remove the alkaline component and the acidic component, it is better to perform multiple washings. Washing more than 10 times may not necessarily obtain the effect of the corresponding number of washings, so it is preferably 1 to 5 times.

[0276] In addition, the reaction product after separation and washing can also be recovered in the form of powder by concentrating the solvent to dryness or performing crystallization operation under reduced pressure or normal pressure. In order to improve the operability when preparing the organic film forming material, it can also be made into a solution state of appropriate concentration in advance. At this time, the concentration is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass. If it is such a concentration, the viscosity is not easy to increase, so it can prevent damage to the operability, and the amount of solvent will not be too large, so it is economical.

[0277] The solvent used at this time 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; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate. These can be used alone or in combination of two or more.

[0278] When the compound used in the organic film forming material of the present invention is further manufactured, other carboxylic acid compounds different from epoxy compounds and carboxylic acid compounds may be appropriately combined in accordance with the required performance. Specifically, by combining a soft hydrocarbon structure that contributes to the improvement of the embedding / planarization characteristics, a rigid aromatic ring structure that contributes to the etching resistance and heat resistance, and a structure with a polar group for improving the adhesion in an arbitrary ratio to synthesize the organic film forming compound, the optical constant (n / k) can be controlled, and the embedding / planarization characteristics, heat resistance, and etching resistance can be taken into account in a high dimension.

[0279] The carboxylic acid component used at this time is preferably a combination of a carboxylic acid compound (21) and / or a carboxylic acid compound (22) represented by the following general formula. The following carboxylic acid compound (21) and a combination of multiple carboxylic acid compounds (22) may also be used. As for the feed amount when the carboxylic acid compound (21) and the carboxylic acid compound (22) are used in combination with the aforementioned carboxylic acid compounds, when the sum of the total carboxylic acid feed amount is set to 100 mol%, each can be adjusted within the range of 1 to 99 mol%. The feed amount will vary depending on the required performance, but considering the etching resistance, heat resistance, and fluidity, when the carboxylic acid compounds (21) and (22) are used in combination, it is preferably adjusted within the range of 10 to 50 mol%. n11, n12, n13, R2, R3 and R4 in the following formula are the same as described above.

[0280] [Chemistry 57]

[0281]

[0282] [Chemistry 58]

[0283]

[0284] The reaction and recovery methods when the above carboxylic acids (21) and (22) are used are the same as those when the above carboxylic acid compound is used as the compound to react with the epoxy compound.

[0285] Furthermore, another method for obtaining the compound used in the organic film material of the present invention, taking the compound having the terminal group structure represented by the above general formula (2) as an example, the intermediate can be obtained by reacting an epoxy compound with a carboxylic acid having a hydroxyl group as a substituent (STEP 1) as shown below, and then further converting the hydrogen atoms of the hydroxyl group into R a and R b The compound having the terminal structure of the above general formula (3) or (4) can also be obtained by the method based on the same reaction.

[0286] [Chemistry 59]

[0287]

Step 1

[0288]

[0289]

Step 2

[0290]

[0291] The reaction for introducing the above-mentioned substituents is not particularly limited, and examples thereof include substitution reactions using halides, toluenesulfonates, or mesylates with base catalysts, etc. In the following formula, Z represents a halogen, toluenesulfonyl, or mesylate, and R represents R a , R b , R d , R e , R g and R h Any of .

[0292] [Chemistry 60]

[0293]

[0294] Examples of the base catalyst used in the substitution reaction include inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, 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.

[0295] The solvent used at this time is not particularly limited as long as it is a solvent that is inactive to the above reaction, for example: ether solvents such as diethyl ether, tetrahydrofuran, dioxane, aromatic solvents such as benzene, toluene, xylene, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, water, etc., which can be used alone or in combination.

[0296] The reaction method and recovery method of the compound are the same as those when the aforementioned carboxylic acid compound is used as the compound to react with the epoxy compound.

[0297] In the preparation of the compound used in the organic film material obtained by this method, various halides, toluene sulfonates and mesylates can be used alone or in combination according to the required performance. For example, structures that contribute to the improvement of the filling property / planarization property, structures that improve the hardening property, etc. can be combined in any proportion.

[0298] As described above, the organic film-forming compound of the present invention can provide an organic film-forming composition having high filling / flattening properties, good adhesion to the substrate, good heat resistance, and dry etching resistance through the action of the terminal group structure of the bisphenol derivative linked by a soft chain.

[0299] [Organic film forming material]

[0300] The present invention also provides an organic film-forming material containing the organic film-forming compound of the present invention and an organic solvent. The organic film-forming material may also be referred to as an organic film-forming composition. In the organic film-forming material of the present invention, the organic film-forming compound of the present invention may be used alone or in combination of a plurality of them.

[0301] The organic film forming material of the present invention may be further blended with other polymers. The blending compound or the blending polymer, when mixed with the organic film forming material of the present invention, has the effect of improving the film forming property of spin coating and the filling property on a substrate with unevenness.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, phenol, 2-propylphenol, 3-propylphenol, 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'diallyl-4,4'-(9H-fluorene-9-ylidene) bisphenol, 2,2'difluoro-4,4'-(9H-fluorene-9-ylidene) bisphenol, 2,2'diphenyl-4,4'-(9H-fluorene-9-ylidene) bisphenol, 2,2'dimethoxy-4,4'-(9H-fluorene-9-ylidene) bisphenol, 2,3,2 ',3'-tetrahydro-(1,1')-spirobiindene-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 dihydroxynaphthalene such as 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene and 2,6-dihydroxynaphthalene, methyl 3-hydroxynaphthalene-2-carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, vinylnaphthalene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornene, 5-vinylnorbornene-2-ene, α-pinene, β-pinene, limonene and other novolac resins, polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyvinylnaphthalene, polynorbornene, polycyclodecene, polytetracyclododecene, polytricyclo[2.2.1.0(2,6)]heptane (poly-nortricyclene), poly(meth)acrylate and copolymers thereof.Furthermore, 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 phenol groups 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 adamantane phenol compounds described in Japanese Patent Application Laid-Open No. 2006-285095, bisnaphthol compounds and novolac resins thereof described in Japanese Patent Application Laid-Open No. 2010-122656, fullerene resin compounds described in Japanese Patent Application Laid-Open No. 2008-158002, and the like may be blended. The blending amount of the above-mentioned compound for doping or polymer for doping 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 organic film material of the present invention.

[0302] 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 aforementioned base polymer (organic film forming compound), acid generator, crosslinking agent, and other additives. Specifically, a solvent having a boiling point of less than 180° C. such as the solvents described in paragraphs (0091) to (0092) of Japanese Patent Publication No. 2007-199653 can be used. Among them, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and a mixture of two or more thereof are preferably used.

[0303] Such a material can be applied by spin coating, and contains the organic film-forming compound of the present invention as described above, so it can be an organic film-forming material having good dry etching resistance, heat resistance, and high filling / high planarization properties.

[0304] Furthermore, in the organic film composition of the present invention, in terms of the organic solvent, a 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 more than 180°C) may be added to the above-mentioned solvent having a boiling point of less than 180°C. The high boiling point organic solvent may be any solvent capable of dissolving the organic film forming compound, and is not limited to hydrocarbons, alcohols, ketones, esters, ethers, chlorine-based solvents, and the like. Specific examples include: 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol. , triethylene glycol, tripropylene glycol, 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 ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol monomethyl ether ethyl Acid esters, 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, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc., which can be used alone or in combination.

[0305] The boiling point of the high boiling point solvent can be appropriately selected in accordance with the temperature of the heat treatment of the organic film composition. The boiling point of the added high boiling point solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. If the boiling point is such, there is no risk of volatilization too fast during baking (heat treatment) due to the boiling point being too low, so sufficient thermal fluidity can be obtained. In addition, if the boiling point is such, the boiling point will not be too high, and it will not remain in the film after baking without volatilization, and will not have an adverse effect on the film properties such as etching resistance.

[0306] In the case of using a high boiling point solvent, the blending amount of the high boiling point solvent is preferably 1 to 30 parts by mass relative to 100 parts by mass of the solvent having a boiling point of less than 180° C. If the blending amount is such, there is no risk that the blending amount is too small and sufficient thermal fluidity cannot be imparted during baking, or that the blending amount is too large and the solvent remains in the film and the film properties such as etching resistance may be deteriorated.

[0307] The organic solvent is preferably a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

[0308] Such an organic film forming material (organic film forming composition) can be given thermal fluidity by adding a high boiling point solvent to the organic film forming compound, thereby achieving an organic film forming composition having both high filling characteristics and high planarizing characteristics.

[0309] In order to further promote the curing reaction, an acid generator may be added to the organic film forming material of the present invention. Acid generators may generate acid by thermal decomposition or by light irradiation, and both may be added. Specifically, materials described in paragraphs (0061) to (0085) of Japanese Patent Publication No. 2007-199653 may be added, but the present invention is not limited thereto.

[0310] The acid generator may be used alone or in combination of two or more thereof. The amount of the acid generator added is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, based on 100 parts of the organic film-forming compound.

[0311] A surfactant may be added to the organic film-forming material of the present invention to improve coating properties during spin coating. As the surfactant, for example, those described in (0142) to (0147) of JP-A-2009-269953 may be used.

[0312] In addition, in the organic film forming material of the present invention, a crosslinking agent may be added in order to improve the hardening property and further suppress the cross-mixing with the upper film. The crosslinking agent is not particularly limited, and various known crosslinking agents can be widely used. For example, hydroxymethyl or methoxymethyl type crosslinking agents of polynuclear phenols, melamine crosslinking agents, glycoluril crosslinking agents, benzoguanamine crosslinking agents, urea crosslinking agents, β-hydroxyalkylamide crosslinking agents, isocyanurate crosslinking agents, aziridine crosslinking agents, oxazoline crosslinking agents, and epoxy crosslinking agents can be cited.

[0313] Melamine-based crosslinking agents specifically include hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxyl substitutions, and their partial self-condensation products. Methoxymethyl-type crosslinking agents of polynuclear phenols include tetrahydroxymethylated and tetramethoxymethylated bisphenols such as bisphenol A and bisphenol F, trisphenol methane, trisphenol ethane, 1,1,1-tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and other trisphenols hexamethoxymethylated and their partial condensation products. Glycoluril-based crosslinking agents specifically include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, their alkoxy and / or hydroxyl substitutions, and their partial self-condensation products. Benzoguanamine-based crosslinking agents specifically include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxyl substitutions, and their partial self-condensation products. Urea crosslinking agents include, specifically, dimethoxymethylated dimethoxyethylene urea, alkoxy and / or hydroxyl substitution products thereof, and partial self-condensation products thereof. β-Hydroxyalkylamide crosslinking agents include, specifically, N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide. Isocyanurate crosslinking agents include, specifically, triglycidyl isocyanurate and triallyl isocyanurate. Aziridine crosslinking agents include, specifically, 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Specific examples of the oxazoline crosslinking agent include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-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.

[0314] Among the above crosslinking agents, methoxymethyl crosslinking agents of polynuclear phenols are more ideal, and hexamethoxymethylated forms of trisphenolmethane, trisphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are particularly ideal from the perspective of thermal curability. When using these crosslinking agents, it is better not to use an acid generator that acts as a curing reaction accelerator. Since the combination with a curing accelerator will cause the generation of acid by the action of heat or light, accompanied by a violent curing reaction, it will not benefit from the fluidity of the compound itself and will harden. Although the curability is improved, the filling characteristics / flatness characteristics will deteriorate, so it is not ideal to use it in combination with an acid generator.

[0315] In addition, in the organic film forming material of the present invention, a plasticizer can be added to make the planarization characteristic / landfilling characteristic better. The plasticizer is not particularly limited, and plasticizers of various known systems can be widely used. For 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 recorded in Japanese Patent Application Laid-Open No. 2013-253227 can be listed.

[0316] In the organic film forming material of the present invention, it is preferable to use an additive that imparts a filling property / planarization property like a plasticizer, for example, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a thermally decomposable polymer having a weight loss rate of 40% by mass or more between 30°C and 250°C and a weight average molecular weight of 300 to 200,000. The thermally decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formula (DP1) or (DP1a).

[0317] [Chemistry 61]

[0318]

[0319] In the formula, R6 represents a hydrogen atom or a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms which may be substituted. Y1 represents a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.

[0320] [Chemistry 62]

[0321]

[0322] In the formula, R 6a Y is an alkyl group having 1 to 4 carbon atoms. a It is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms, and may have an ether bond. n represents the average number of repeating units, and is 3 to 500.

[0323] The organic film-forming material of the present invention can be used alone or in combination of two or more thereof. The organic film-forming material can be used as a resist underlayer film material or a planarizing material for semiconductor device manufacturing.

[0324] In addition, the organic film forming material of the present invention is extremely useful as a resist underlayer film material for multilayer resist processing such as a two-layer resist processing, a three-layer resist processing using a silicon-containing intermediate film, and a four-layer resist processing using a silicon-containing inorganic hard mask intermediate film and an organic antireflective film.

[0325] [Substrates for semiconductor device manufacturing]

[0326] Furthermore, the present invention can provide a substrate for manufacturing a semiconductor device, wherein an organic film obtained by curing the organic film-forming material is formed on the substrate.

[0327] The organic film formed by curing the organic film forming material of the present invention has high filling characteristics, high flattening characteristics, and excellent adhesion between substrates, so that there are no microscopic voids due to poor filling, unevenness on the surface of the organic film due to insufficient flatness, and no film peeling when an inorganic hard mask is formed directly on the organic film. The substrate for semiconductor device manufacturing obtained by flattening the organic film has a wider processing margin during patterning, and semiconductor devices can be manufactured with good yield.

[0328] [Organic film formation method]

[0329] The present invention provides a method for forming an organic film that functions as a resist underlayer film of a multilayer resist film used for photolithography or a planarizing film (organic planarizing film) for semiconductor manufacturing using the above-mentioned organic film forming material.

[0330] The method for forming an organic film of the present invention is, for example, a method for forming an organic film that acts as an organic flat film in a manufacturing step of a semiconductor device, and is characterized in that: the organic film forming material of the present invention is spin-coated on a substrate to be processed, and the substrate is heat-treated at a temperature of 100° C. to 600° C. in a range of 10 seconds to 600 seconds to form a hardened film.

[0331] In the organic film forming method of the present invention, the above-mentioned organic film forming material is coated on 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 baking (heat treatment) is performed to prevent mixing with the resist upper film and the resist middle film and to promote the cross-linking reaction. The baking is preferably performed in the range of 100°C to 600°C for 10 to 600 seconds, and more preferably in the range of 200°C to 500°C for 10 to 300 seconds. If device damage and the influence on wafer deformation are taken into consideration, the upper limit of the photolithography heating temperature in wafer processing should be set to below 600°C, and more preferably below 500°C.

[0332] Furthermore, in the organic film forming method of the present invention, the organic film forming material of the present invention can also be coated on the processed substrate by spin coating (spin coating) in the same way as mentioned above, and the organic film forming material can be calcined and hardened in a gas environment with an oxygen concentration of not less than 0.1% and not more than 21% to form an organic film.

[0333] By calcining the organic film material of the present invention in such an oxygen atmosphere, a sufficiently hardened film can be obtained.

[0334] The gas environment for baking can be air, or an inert gas such as N2, Ar, or He can be sealed in. The baking temperature and the like can be the same as above.

[0335] The organic film forming method of the present invention can obtain a flat cured film regardless of the unevenness of the processed substrate due to its excellent filling / flattening characteristics, so it is very useful for forming a flat cured film on a processed substrate with a structure with a height of 30nm or more or a height difference.

[0336] [Pattern Formation Method]

[0337] The present invention provides a pattern forming method, which is a pattern forming method using a three-layer resist process using such an organic film forming material, comprising: forming a resist lower layer film on a workpiece using the organic film forming material of the present invention, forming a resist middle layer film on the resist lower layer film using a silicon-containing resist middle layer film material, forming a resist upper layer film on the resist middle layer film using a resist upper layer film material containing a photoresist composition, forming a circuit pattern on the resist upper layer film, etching the resist middle layer film using the patterned resist upper layer film as a mask, transferring the pattern to the resist middle layer film, etching the resist lower layer film using the pattern-transferred resist middle layer film as a mask, transferring the pattern to the resist lower layer film, and further etching the workpiece using the pattern-transferred resist lower layer film as a mask to form a pattern on the workpiece. This pattern forming method, for example: is a method for forming a pattern on a processed substrate, which at least includes: using the organic film forming material of the present invention to form a resist lower layer film on the processed substrate, using a resist intermediate layer film material containing silicon atoms on the resist lower layer film to form a resist intermediate layer film (silicon-containing resist intermediate layer film), using a resist upper layer film material containing a photoresist composition on the resist intermediate layer film to form a resist upper layer film to prepare a multi-layer resist film, after exposing the pattern circuit area of ​​the aforementioned resist upper layer film, developing with a developer to form a resist pattern on the aforementioned resist upper layer film, using the obtained resist pattern as an etching mask to etch the aforementioned resist intermediate layer film to form a resist intermediate layer film pattern, using the obtained resist intermediate layer film pattern as an etching mask to etch the aforementioned resist lower layer film to form a resist lower layer film pattern, and then using the obtained resist lower layer film pattern as an etching mask to etch the aforementioned processed substrate to form a pattern on the aforementioned processed substrate.

[0338] Since the silicon-containing resist intermediate layer film in the above-mentioned three-layer resist treatment shows resistance to etching using oxygen or hydrogen, the etching of the resist lower layer film using the resist intermediate layer film as a mask in the above-mentioned three-layer resist treatment is preferably carried out using an etching gas containing oxygen or hydrogen as the main component.

[0339] For the silicon-containing resist intermediate layer film of the above-mentioned three-layer resist treatment, it is also preferable to use a polysilsesquioxane-based intermediate layer film. This intermediate layer film can act as an organic antireflection film (BARC). By making the resist intermediate layer film have an antireflection effect, reflection can be suppressed. In particular, if a material containing a large amount of aromatic groups and having high substrate etching resistance is used as the resist lower layer film for 193nm exposure, the k value will become higher and the substrate reflection will increase, but the reflection can be suppressed by the resist intermediate layer film, and the substrate reflection can be reduced to less than 0.5%. For the resist intermediate layer film with antireflection effect, it is preferable to use anthracene as the pendant group for 248nm and 157nm exposure, and it is preferable to use phenyl or a light-absorbing group with a silicon-silicon bond as the pendant group for 193nm exposure, and it is more preferable to use a polysilsesquioxane cross-linked by acid or heat.

[0340] In this case, compared with the CVD method, the spin coating method is simpler and has a cost advantage when forming the silicon-containing resist intermediate layer film.

[0341] Or the resist treatment of the present invention can also form another organic anti-reflective film that is not a resist intermediate film on the resist intermediate film containing silicon, and form a four-layer film structure. That is, the present invention provides a pattern forming method, using the organic film forming material of the present invention to form a resist lower film on a workpiece, and using a resist intermediate film material containing silicon atoms to form a resist intermediate film on the resist lower film, forming an organic anti-reflective film on the resist intermediate film, using a resist upper film material containing a photoresist composition to form a resist upper film on the organic anti-reflective film, and forming a four-layer film structure, forming a circuit pattern on the resist upper film, and The patterned resist upper layer film is used as a mask to etch the organic anti-reflective film and the resist middle layer film, and the pattern is transferred to the organic anti-reflective film and the resist middle layer film, the resist middle layer film to which the pattern has been transferred is used as a mask to etch the resist lower layer film, and the pattern is transferred to the resist lower layer film, and further, the resist lower layer film to which the pattern has been transferred is used as a mask to etch the processed object, and a pattern is formed on the processed object.

[0342] Furthermore, an inorganic hard mask intermediate film may be formed as an intermediate film. In this case, the organic film material of the present invention may be used at least on a substrate to be processed to form a resist lower film, an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film may be formed on the resist lower film, a resist upper film material composed of a photoresist composition may be used on the inorganic hard mask intermediate film to form a resist upper film, and a pattern circuit region of the resist upper film may be exposed to light, and then the resist upper film may be exposed to light by developing the resist upper film. The resist is developed with a liquid to form a resist pattern on the resist upper film, the obtained resist pattern is used as an etching mask to etch the inorganic hard mask intermediate film to form an inorganic hard mask intermediate film pattern, and the obtained inorganic hard mask intermediate film pattern is used as an etching mask to etch the resist lower film to form a resist lower film pattern, and the obtained resist lower film pattern is used as an etching mask to etch the processed substrate to form a pattern on the processed substrate. That is, the present invention also provides a pattern forming method, which comprises forming a resist lower layer film on a workpiece using the organic film forming material of the present invention, forming an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film and silicon oxide nitride film on the resist lower layer film, forming a resist upper layer film on the inorganic hard mask intermediate film using a resist upper layer film material containing a photoresist composition, forming a circuit pattern on the resist upper layer film, etching the inorganic hard mask intermediate film with the pattern formed as a mask, transferring the pattern to the inorganic hard mask intermediate film, etching the resist lower layer film with the pattern formed as a mask, transferring the pattern to the resist lower layer film, and further etching the workpiece using the resist lower layer film with the pattern formed as a mask to form a pattern on the workpiece.

[0343] As described above, when an inorganic hard mask intermediate film is formed on the resist lower film, a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, the method for forming a silicon nitride film is described in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The film thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, and more preferably 10 to 100 nm. In addition, it is most preferable to use a SiON film that has a high effect as an anti-reflective film as the inorganic hard mask intermediate film. The substrate temperature when forming the SiON film becomes 300 to 500°C, so the lower film needs to be able to withstand a temperature of 300 to 500°C. The organic film forming material used in the present invention has high heat resistance and can withstand high temperatures of 300°C to 500°C, so it can be a combination of an inorganic hard mask intermediate film formed by CVD or ALD, and an anti-etching agent underlayer film formed by spin coating.

[0344] Furthermore, a four-layer resist process using an organic anti-reflection film is also ideal. In this case, the organic film forming material of the present invention can be used at least on the processed substrate to form a resist lower layer film, an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film is formed on the resist lower layer film, an organic anti-reflection film is formed on the inorganic hard mask intermediate film, and a resist upper layer film material of a photoresist composition is used on the organic anti-reflection film to form a resist upper layer film to prepare a multi-layer resist film, and for the pattern circuit area of ​​the aforementioned resist upper layer film After exposure, development is performed with a developer to form a resist pattern on the aforementioned resist upper film, the obtained resist pattern is used as an etching mask to etch the aforementioned organic anti-reflective film and the aforementioned inorganic hard mask intermediate film to form an inorganic hard mask intermediate film pattern, and the obtained inorganic hard mask intermediate film pattern is used as an etching mask to etch the aforementioned resist lower film to form a resist lower film pattern, and then the obtained resist lower film pattern is used as an etching mask to etch the aforementioned processed substrate to form a pattern on the aforementioned processed substrate. That is, the present invention provides a pattern forming method, which comprises forming a resist lower layer film on a workpiece using the organic film forming material of the present invention, forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film and a silicon oxide nitride film on the resist lower layer film, forming an organic anti-reflection film on the inorganic hard mask intermediate film, and forming a resist upper layer film using a resist upper layer film material containing a photoresist composition on the organic anti-reflection film to obtain a four-layer film structure, and forming an electroplating film on the resist upper layer film. The organic anti-reflective film and the inorganic hard mask intermediate film are etched using the patterned resist upper film as a mask, and the pattern is transferred to the organic anti-reflective film and the inorganic hard mask intermediate film, the inorganic hard mask having the pattern formed is used as a mask to etch the resist lower film, and the pattern is transferred to the resist lower film, and further, the resist lower film having the pattern formed is used as a mask to etch the aforementioned object to be processed, and a pattern is formed on the object to be processed.

[0345] As described above, a photoresist film may be formed on the inorganic hard mask interlayer as the resist upper film, but an organic antireflection film (BARC) may be formed on the inorganic hard mask interlayer by spin coating, and a photoresist film may be formed thereon. In particular, when a SiON film is used as the inorganic hard mask interlayer, the two-layer antireflection film of the SiON film and the BARC can suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another benefit of forming the BARC is that it has the effect of reducing the tailing of the photoresist pattern directly on the SiON film.

[0346] In the above-mentioned 3-layer and 4-layer resist treatment, the resist upper film can be positive or negative, and can use the same photoresist composition as commonly used. After the photoresist composition is spin-coated, it is pre-baked, preferably in the range of 60 to 180° C. and 10 to 300 seconds. Thereafter, exposure is performed according to the usual method, and then post-exposure baking (PEB) and development are performed to obtain a resist pattern. In addition, the thickness of the resist upper film is not particularly limited, and 30 to 500 nm is ideal, and 50 to 400 nm is particularly preferred.

[0347] A circuit pattern is formed on the resist upper film (resist upper film pattern). The circuit pattern is preferably formed by photolithography using light with a wavelength of 10 nm to 300 nm, direct drawing using an electron beam, nano-stamping, or a combination thereof.

[0348] In addition, the exposure light is a high-energy ray with a wavelength of less than 300nm, specifically, far ultraviolet light, KrF excimer laser (248nm), ArF excimer laser (193nm), F2 laser (157nm), Kr2 laser (146nm), Ar2 laser (126nm), 3 to 20nm soft X-ray (EUV), electron beam (EB), ion beam, X-ray, etc.

[0349] Furthermore, when forming the circuit pattern, it is preferred to develop the circuit pattern using an alkali developer or an organic solvent.

[0350] Then, the obtained resist pattern is used as a mask to perform etching. In the three-layer and four-layer resist processing, the etching of the resist intermediate layer film and the inorganic hard mask intermediate film is performed using a fluorine-based gas and the resist pattern as a mask. In this way, the resist intermediate layer film pattern and the inorganic hard mask intermediate film pattern are formed.

[0351] Next, the resist underlayer film is etched using the obtained resist intermediate layer film pattern, inorganic hard mask intermediate layer film pattern, and organic antireflection film pattern as masks.

[0352] The subsequent etching of the processed substrate can also be performed according to the usual method. For example, if the processed substrate is SiO2, SiN, or a silicon dioxide-based low dielectric constant insulating film, etching is performed mainly using a fluorine-based gas. If it is p-Si, Al, or W, etching is performed mainly using a chlorine-based or bromine-based gas. When the substrate is processed using fluorine-based gas etching, the silicon-containing intermediate film pattern in the 3-layer and 4-layer resist treatment is stripped while the substrate is being processed. When the substrate is etched using a chlorine-based or bromine-based gas, the stripping of the silicon-containing intermediate film pattern needs to be performed by dry etching stripping using a fluorine-based gas after the substrate is processed.

[0353] The resist underlayer film obtained by using the organic film material of the present invention has a characteristic of being excellent in etching resistance when etching these substrates to be processed.

[0354] Furthermore, the substrate to be processed is not particularly limited, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., and substrates on which the processed layer is formed, etc. can be used. The processed layer can be various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, and barrier films thereof, and can generally be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm. Furthermore, when the processed layer is formed, the substrate and the processed layer can be made of different materials.

[0355] In the pattern forming method of the present invention, the object to be processed is preferably 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 is formed. That is, the object to be processed is preferably a semiconductor device substrate, 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.

[0356] In addition, the workpiece preferably contains silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof.

[0357] For an example of 3-layer resist processing, use Figure 1 Specific examples are as follows.

[0358] When 3 layers of resist are processed, such as Figure 1 (A) After forming a resist lower layer film 3 using the organic film material of the present invention on the processing layer 2 stacked on the substrate 1, a resist intermediate layer film 4 is formed, and a resist upper layer film 5 is formed thereon.

[0359] Secondly, if Figure 1 (B), a specific portion 6 of the resist upper layer film is exposed, PEB and development are performed to form a resist pattern 5a ( Figure 1 (C)). Using the obtained resist pattern 5a as a mask, the resist intermediate layer film 4 is etched using a CF-based gas to form a resist intermediate layer film pattern 4a ( Figure 1 (D)). After removing the resist pattern 5a, the obtained resist intermediate film pattern 4a is used as a mask to perform oxygen plasma etching on the resist lower film 3 to form a resist lower film pattern 3a ( Figure 1(E)). After removing the resist intermediate film pattern 4a, the resist lower film pattern 3a is used as a mask to perform etching on the processed layer 2 to form a pattern 2a ( Figure 1 (F)).

[0360] When an inorganic hard mask interlayer film is used, the resist interlayer film 4 is an inorganic hard mask interlayer film, and when an organic anti-reflection film (BARC) is applied, a BARC layer is provided between the resist interlayer film 4 and the resist upper film 5. The etching of the BARC may be performed continuously before the etching of the resist interlayer film 4, or only the etching of the BARC layer may be performed, and then the etching of the resist interlayer film 4 may be performed after changing the etching device.

[0361] Thus, 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.

[0362] [Example]

[0363] The following synthesis examples, comparative synthesis examples, embodiments, and comparative examples are provided to more specifically describe the present invention, but the present invention is not limited thereto. In addition, the molecular weight and the dispersity are obtained by using gel permeation chromatography (GPC) using tetrahydrofuran as an eluent to obtain the weight average molecular weight (Mw) and number average molecular weight (Mn) converted to polystyrene, and the dispersity (Mw / Mn) is obtained.

[0364] Synthesis Example Synthesis of Compounds for Organic Film Forming Materials

[0365] The following epoxy compounds (compound group B: (B1) to (B14)) and carboxylic acid compounds (compound group C: (C1) to (C9)) were used to synthesize the polymers (A1) to (A29) for organic film forming materials.

[0366] Compound Group B:

[0367] [Chemistry 63]

[0368]

[0369] Commercially available reagents other than those listed above were used.

[0370] (B1) EXA-850CRP (manufactured by DIC Corporation) Epoxy equivalent: 172

[0371] (B2) HP-4700 (manufactured by DIC Corporation) Epoxy equivalent: 165

[0372] (B3) HP-4770 (manufactured by DIC Corporation) Epoxy equivalent: 205

[0373] (B5) 1032H60 (Mitsubishi Chemical Co., Ltd.) Epoxy equivalent: 167

[0374] (B10) DAG-G (manufactured by Shikoku Chemical Industry Co., Ltd.) Epoxy equivalent: 168

[0375] (B11) TG-G (manufactured by Shikoku Chemical Industry Co., Ltd.) Epoxy equivalent: 92

[0376] (B13) EPOLIGHT MF (manufactured by Kyoei Chemical Industry Co., Ltd.) Epoxy equivalent: 140

[0377] (B14) PETG (Showa Denko Co., Ltd.) Epoxy equivalent: 90

[0378] Compound Group C:

[0379] [Chemistry 64]

[0380]

[0381] [Synthesis Example 1] Synthesis of Compound (A1)

[0382] [Chemistry 65]

[0383]

[0384] 15.0 g of epoxy compound (B1), 25.0 g of carboxylic acid compound (C1), and 200 g of 2-methoxy-1-propanol were made into a uniform solution under nitrogen atmosphere at an internal temperature of 100°C, and then 1.00 g of benzyltriethylammonium chloride was added and stirred at an internal temperature of 120°C for 12 hours. After cooling to room temperature, 300 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 100 g of 2% NaHCO3 aqueous solution and 100 g of 3% nitric acid aqueous solution, and washed 5 times with 100 g of ultrapure water. The organic layer was dried under reduced pressure to obtain compound (A1). The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were obtained by GPC, and the results were Mw=920 and Mw / Mn=1.04.

[0385] [Synthesis Examples 2 to 27] Synthesis of Compounds (A2) to (A27)

[0386] The same reaction conditions as in Synthesis Example 1 except that the epoxy compound and carboxylic acid compound shown in Table 1 were used to obtain compounds (A2) to (A27) shown in Tables 2 to 7 as products. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of these compounds were calculated and are shown in Tables 2 to 7.

[0387] [Table 1]

[0388]

[0389] [Table 2]

[0390]

[0391] [Table 3]

[0392]

[0393] [Table 4]

[0394]

[0395] [Table 5]

[0396]

[0397] [Table 6]

[0398]

[0399] [Table 7]

[0400]

[0401] [Synthesis Example 28] Synthesis of Compound (A28)

[0402] [Chemistry 66]

[0403]

[0404] 20.0 g of the compound (A2) synthesized in Synthesis Example 2, 13.5 g of potassium carbonate and 100 g of dimethylformamide were prepared into a uniform dispersion under a nitrogen atmosphere at an internal temperature of 50°C, and then 12.8 g of propargyl bromide was added and reacted at an internal temperature of 50°C for 24 hours. After cooling to room temperature, 300 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 100 g of ultrapure water, twice with 100 g of a 3% nitric acid aqueous solution, and five times with 100 g of ultrapure water in that order. The organic layer was dried under reduced pressure to obtain a compound (A28). The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were obtained by GPC, and the results were Mw=2230 and Mw / Mn=1.38.

[0405] [Synthesis Example 29] Synthesis of Compound (A29)

[0406] [Chemistry 67]

[0407]

[0408] 20.0 g of the compound (A4) synthesized in Synthesis Example 4, 11.6 g of potassium carbonate and 100 g of dimethylformamide were added to obtain a uniform dispersion at an internal temperature of 50°C under a nitrogen atmosphere, and then 11.0 g of propargyl bromide was added to react at an internal temperature of 50°C for 24 hours. After cooling to room temperature, 300 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 100 g of ultrapure water, twice with 100 g of a 3% nitric acid aqueous solution, and five times with 100 g of ultrapure water in that order. The organic layer was dried under reduced pressure to obtain a compound (A29). The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were Mw=1310 and Mw / Mn=1.28.

[0409] [Comparative Synthesis Example 1] Synthesis of Comparative Compound (R1)

[0410] 20.0 g of epoxy compound (B2), 23.3 g of butoxybenzoic acid, and 200 g of 2-methoxy-1-propanol were mixed under nitrogen atmosphere at an internal temperature of 100°C to obtain a uniform solution, and then 1.00 g of benzyltriethylammonium chloride was added and stirred at an internal temperature of 120°C for 12 hours. After cooling to room temperature, 300 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 100 g of 2% NaHCO3 aqueous solution and 100 g of 3% nitric acid aqueous solution, and washed five times with 100 g of ultrapure water. The organic layer was dried under reduced pressure to obtain compound (R1). The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were obtained by GPC, and the results were Mw=1930 and Mw / Mn=1.32.

[0411] [Chemistry 68]

[0412]

[0413] [Comparative Synthesis Example 2] Synthesis of Comparative Compound (R2)

[0414] 20.0 g of epoxy compound (B2), 16.7 g of 4-hydroxybenzoic acid, and 200 g of 2-methoxy-1-propanol were mixed under nitrogen atmosphere at an internal temperature of 100°C to obtain a uniform solution, and then 1.00 g of benzyltriethylammonium chloride was added and stirred at an internal temperature of 120°C for 12 hours. After cooling to room temperature, 300 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 100 g of 2% NaHCO3 aqueous solution and 100 g of 3% nitric acid aqueous solution, and washed five times with 100 g of ultrapure water. The organic layer was dried under reduced pressure to obtain compound (R2). The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were obtained by GPC, and the results were Mw=1610 and Mw / Mn=1.35.

[0415] [Chemistry 69]

[0416]

[0417] Preparation of organic film-forming materials (UDL-1 to 31, comparative examples UDL-1 to 2)

[0418] The above-mentioned compounds (A-1) to (A-29) and comparative compounds (R-1) to (R-2) and (S1) 1,6-diacetoxyhexane as a high boiling point solvent: boiling point 260°C, (S2) tripropylene glycol monomethyl ether: boiling point 242°C, XL1 and XL2 as crosslinking agents, AG1 as a thermal acid generator, propylene glycol monomethyl ether acetate (PGMEA) or 2-methoxy-1-propanol (PGME) containing 0.1% by mass of PF636 (manufactured by OMNOVA) were used, and after dissolving in the proportions shown in Table 8, the mixture was filtered with a 0.1μm fluororesin filter to prepare organic film-forming compositions (UDL-1 to 31, comparative examples UDL-1 to 2).

[0419] [Table 8]

[0420]

[0421] The structural formulas of the cross-linking agents (XL1 and XL2) and the thermal acid generator (AG1) used in the above-mentioned ULD and comparative example UDL are shown below.

[0422] [Chemistry 70]

[0423]

[0424] Example 1 Evaluation of Adhesion and Landfill Characteristics (Examples 1-1 to 1-31, Comparative Examples 1-1 to 1-2)

[0425] like Figure 2 The organic film forming materials (UDL-1 to 31, comparative examples UDL-1 to 2) were coated on a SiO2 wafer substrate treated with hexamethyldisilazane (HMDS) and having a dense hole pattern (hole diameter 0.16 μm, hole depth 2.0 μm, distance between the centers of two adjacent holes 0.32 μm), and calcined in the atmosphere using a hot plate under the conditions shown in Table 9 to form an organic film 8. The substrate used was Figure 2 (G) (bird's-eye view) and (H) (cross-sectional view) show a base substrate 7 (SiO2 wafer substrate) with a dense hole pattern. The cross-sectional shape of each wafer substrate obtained was observed using a scanning electron microscope (SEM) to confirm whether there were no pores (voids) inside the holes and whether they were filled with an organic film. The results are shown in Table 9. When an organic film forming material with poor filling characteristics is used, pores will occur inside the holes in this evaluation. In addition, when the adhesion is insufficient, peeling from the substrate will be confirmed in the cross section. When an organic film forming material with good adhesion and filling characteristics is used, in this evaluation, if Figure 2 As shown in (I), the interior of the pores is filled with an organic film without any voids.

[0426] [Table 9]

[0427]

[0428]

[0429] As shown in Table 9, Examples 1-1 to 1-31 using the organic film forming material (UDL1 to UDL-31) of the present invention can fill the hole pattern without peeling and voids, and it is confirmed that they have good adhesion to the substrate and excellent filling characteristics. On the other hand, Comparative Example 1-1 using Comparative Example UDL1 containing Comparative Compound R1 which does not have a bisphenol derivative linked by a flexible chain as an end structure has insufficient adhesion and peeling on the pattern substrate is observed. Moreover, Comparative Example 1-2 using Comparative Example UDL2 containing Comparative Compound R2 which does not have a bisphenol derivative linked by a flexible chain as an end structure does not observe peeling due to insufficient adhesion, but voids are observed due to insufficient filling characteristics. From these results, it can be seen that the organic film forming compound of the present invention can achieve better adhesion to the substrate and excellent filling characteristics than the compound without such an end structure by having a bisphenol derivative linked by a flexible chain as an end structure.

[0430] Example 2 Evaluation of planarization characteristics (Examples 2-1 to 2-31, Comparative Examples 2-1 to 2-2)

[0431] The organic film forming materials (UDL-1 to 31, comparative examples UDL-1 to 2) were coated on the surfaces having the giant isolated trench pattern ( Figure 3 The organic film 10 was calcined in the atmosphere using a hot plate according to the conditions shown in Table 10, and then the height difference between the organic film 10 in the groove part and the non-groove part was observed using an NX10 atomic force microscope (AFM) manufactured by Park Systems. Figure 3 (k) in delta10). The results are shown in Table 10. In this evaluation, the smaller the height difference, the better the planarization characteristics. In this evaluation, the trench pattern with a depth of 0.10 μm was planarized using an organic film material with a normal film thickness of 200 nm, and strict evaluation conditions were used to evaluate the quality of the planarization characteristics.

[0432] [Table 10]

[0433]

[0434]

[0435] As shown in Table 10, it is confirmed that in Examples 2-1 to 2-31 using the organic film forming material of the present invention, the height difference of the organic film between the trench part and the non-ditch part is small and the planarization characteristics are excellent compared with Comparative Examples 2-1 to 2-2. As mentioned above, Comparative Examples 2-1 and 2-2 are examples of using materials containing compounds containing bisphenol derivatives that do not have a flexible chain-linked terminal structure instead of the organic film forming material of the present invention. From this result, it can be seen that the organic film forming compound of the present invention can achieve excellent planarization characteristics by having a bisphenol derivative linked by a flexible chain as a terminal structure compared with a compound that does not have this terminal structure. In addition, it can be confirmed that if Examples 2-30 and 2-31 to which a high boiling point solvent is added are compared with Examples 2-28 and 2-29 to which a high boiling point solvent is not added, the addition of a high boiling point solvent can further improve the planarity. In particular, it is found that in Comparative Examples 2-1 and 2-2, a crosslinking agent and an acid generator are used in combination, and acid generation due to heat causes rapid hardening, thereby hindering fluidity and deteriorating flatness.

[0436] Example 3 Adhesion Test (Examples 3-1 to 3-31, Comparative Examples 3-1 to 3-2)

[0437] The above-mentioned organic film forming materials (UDL-1~31, comparative examples UDL-1~2) are coated on a SiO2 wafer substrate and calcined in the atmosphere using a hot plate according to the conditions shown in Table 11 to form an organic film with a thickness of 200nm. The wafer with the organic film is cut into 1×1cm squares, and aluminum pins with epoxy adhesive are installed on the cut wafer using a special fixture. Then, an oven is used to heat at 150°C for 1 hour to bond the aluminum pins to the substrate. After cooling to room temperature, a thin film adhesion strength measuring device (Sebastian Five-A) is used to evaluate the initial adhesion by resistance.

[0438] Figure 4 An explanatory diagram showing a method for measuring adhesion is shown. Figure 4 11 represents the silicon wafer (substrate), 12 represents the hardened film, 13 represents the aluminum pin with adhesive, 14 represents the support table, 15 represents the gripping part, and 16 represents the stretching direction. The adhesion is the average value of the 12-point measurement, and the higher the value, the higher the adhesion of the organic film to the substrate. The adhesion is evaluated by comparing the obtained values. The results are shown in Table 11.

[0439] [Table 11]

[0440]

[0441]

[0442] As shown in Table 11, it can be seen that Examples 3-1 to 3-31 using the organic film forming material of the present invention have better adhesion than Comparative Example 3-1 using Comparative Example UDL-1 which exhibited peeling in the adhesion and embedding characteristic evaluation test. In addition, it can be seen that Examples 3-1 to 3-31 have better adhesion than Comparative Example 3-2 using Comparative Example UDL-2. Comparative Examples UDL-1 and 2, as described above, are examples of using materials containing compounds that do not have a bisphenol derivative linked by a soft chain as an end structure. From these results, it can be seen that the organic film forming compound of the present invention can achieve better adhesion to the substrate by having a bisphenol derivative linked by a soft chain as an end structure than a compound that does not have such an end structure.

[0443] Example 4 Pattern Etching Test (Examples 4-1 to 4-31, Comparative Examples 4-1 to 4-2)

[0444] The organic film forming materials (UDL-1 to 31, comparative examples UDL-1 to 2) prepared above were coated on a SiO2 substrate with a groove pattern (groove width 10 μm, groove depth 0.10 μm) formed on a SiO2 film with a film thickness of 200 nm treated with HMDS, and calcined in the atmosphere according to the conditions shown in Table 10 to form a resist lower layer film with a film thickness of 200 nm on the bare Si substrate. A silicon-containing resist intermediate layer material (SOG-1) was coated thereon, and baked at 220°C for 60 seconds to form a resist intermediate layer film with a film thickness of 35 nm, and a resist upper layer film material (SL resist for ArF) was coated thereon, and baked at 105°C for 60 seconds to form a resist upper layer film with a film thickness of 100 nm. A wet protection film (TC-1) was coated on the resist upper layer film, and baked at 90°C for 60 seconds to form a protective film with a film thickness of 50 nm.

[0445] 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 mass% of FC-430 (manufactured by Sumitomo 3M Co., Ltd.) according to the proportions shown in Table 12, and filtered with a 0.1 μm fluororesin filter to prepare the material.

[0446] [Table 12]

[0447]

[0448] The structural formulas of the polymer (RP1), the acid generator (PAG1), and the basic compound (Amine1) used are shown below.

[0449] [Chemistry 71]

[0450]

[0451] The wet protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent at the ratio shown in Table 13, and filtering the solution with a 0.1 μm fluororesin filter.

[0452] [Table 13]

[0453]

[0454] The structural formula of the polymer (PP1) used is shown below.

[0455] [Chemistry 72]

[0456]

[0457] As for the silicon-containing anti-etching intermediate layer material (SOG-1), a polymer represented by the ArF silicon-containing intermediate film polymer (SiP1) and a cross-linking catalyst (CAT1) are dissolved in an organic solvent containing 0.1 mass % FC-4430 (produced by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 14, and filtered with a fluororesin filter with a pore size of 0.1 μm to prepare a silicon-containing anti-etching intermediate layer material (SOG-1).

[0458] [Table 14]

[0459]

[0460] The structural formulas of the ArF silicon-containing intermediate film polymer (SiP1) and the crosslinking catalyst (CAT1) used are shown below.

[0461] [Chemistry 73]

[0462]

[0463] Secondly, the film was exposed with an ArF immersion exposure device (manufactured by Nikon Co., Ltd.; NSR-S610C, NA1.30, σ0.98 / 0.65, 35 degree dipole s-polarized illumination, 6% half-step phase shift mask) while changing the exposure amount, baked (PEB) at 100°C for 60 seconds, and developed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a positive line and space pattern with a pitch of 100nm and a resist line width of 50nm to 30nm.

[0464] Next, the etching device Telius manufactured by Tokyo Electron was used to process the silicon-containing intermediate layer film using the resist pattern obtained by dry etching as a mask, and the lower layer film was processed using the silicon-containing intermediate layer film as a mask, and the SiO2 film was processed using the lower layer film as a mask.

[0465] The etching conditions were as follows.

[0466] Transfer conditions of the resist pattern to the SOG film.

[0467]

[0468] Transfer conditions of SOG film to underlying film.

[0469]

[0470] Transfer conditions to SiO2 film.

[0471]

[0472] The pattern cross-section was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the shapes were compared and summarized in Table 15.

[0473] [Table 15]

[0474]

[0475]

[0476] As shown in Table 15, the results of the organic film forming material of the present invention (Examples 4-1 to 4-31) all show that the resist upper film pattern is finally well transferred to the substrate, confirming that the organic film forming material of the present invention is suitable for use in fine processing using a multilayer resist method. On the other hand, in Comparative Examples 4-1 to 4-2, since the results of the adhesion and embedding property evaluation tests of Comparative Examples UDL-1 and Comparative Examples UDL-2 used in them show that the embedding property and adhesion are insufficient, the pattern collapse occurs during pattern processing and the pattern cannot be formed. Again, Comparative Examples UDL-1 and 2, as mentioned above, are examples of using a material containing a compound having no bisphenol derivative linked by a flexible chain as a terminal structure. From this result, it can be seen that the organic film forming compound of the present invention, by having a bisphenol derivative linked by a flexible chain as a terminal structure, can achieve a fine pattern with higher precision than a compound having no such terminal structure.

[0477] From the above, it can be seen that: if the organic film forming material of the present invention has a high degree of filling characteristics / a high degree of flattening characteristics / and excellent adhesion between substrates, it is extremely useful as an organic film material used in a multilayer resist method, and if the pattern forming method of the present invention uses it, even if the processed body is a substrate with height differences, a fine pattern can still be formed with high precision.

[0478] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are illustrative, and those having substantially the same configuration and exhibiting the same functions and effects as the technical concept described in the claims of the present invention are all included in the technical scope of the present invention.

[0479] Description of Reference Numerals

[0480] 1:Substrate

[0481] 2: Processing layer

[0482] 2a: Pattern (pattern formed on the processed layer)

[0483] 3: Organic film (resist lower layer film)

[0484] 3a: Resist lower film pattern

[0485] 4: Silicon-containing resist interlayer film

[0486] 4a: Silicon-containing resist interlayer film pattern

[0487] 5: Resist upper film

[0488] 5a: Resist upper film pattern (resist pattern)

[0489] 6: Exposure part

[0490] 7: Base substrate with dense hole pattern

[0491] 8: Organic film

[0492] 9: Base substrate with large isolated trench patterns

[0493] 10: Organic film

[0494] delta10: height difference between the organic film 10 in the trench part and the non-ditch part

[0495] 11: Silicon Wafer

[0496] 12: Hardening film

[0497] 13: Aluminum pin with adhesive

[0498] 14: Support Desk

[0499] 15: Grip

[0500] 16: stretching direction

Claims

1. A resist underlayer film of a multilayer resist film used in photolithography or an organic flat film for semiconductor manufacturing, characterized in that Formed from an organic film-forming material comprising a compound represented by the following general formula (1) and an organic solvent; In the general formula (1), X is an n1-valent organic group having 2 to 50 carbon atoms, n1 represents an integer of 2 to 10, and R1 is at least one of the following general formulae (2) to (4); In the general formula (2), * represents the bonding site to the organic group X, R a and R b represents a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R c represents a hydrogen atom, a methyl group or a phenyl group, m1 and m2 represent an integer of 0 or 1, n2 and n3 represent an integer of 1 to 7, satisfying the relationship of 1≤n2+n3≤7, and n4 represents an integer of 1 to 10; In the general formula (3), * represents the bonding site to the organic group X, R d and R e represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R f represents a hydrogen atom, a methyl group or a phenyl group, m3 and m4 represent integers of 0 or 1, n5 and n6 represent integers of 1 to 7, and meet the relationship of 1≤n5+n6≤7; l1 represents 1, and the oxygen atom serves as an ether bond to form a bridging structure between aromatic rings; In the general formula (4), * represents the bonding site to the organic group X, R g and R h represents a hydrogen atom, or a straight-chain or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, m5 and m6 represent integers of 0 or 1, n7 and n8 represent integers of 1 to 7 and satisfy the relationship of 1≤n7+n8≤7; l2 represents 0 or 1, when l2=1, the oxygen atom acts as an ether bond to form a bridging structure between aromatic rings, and when l2=0, there is no ether bond to form a bridging structure between aromatic rings.

2. The resist underlayer film of a multilayer resist film used for lithography or the organic flattening film for semiconductor manufacturing according to claim 1, wherein The general formula (1) is any of the following general formulas (5), (7), (8), (9), (10), (11), (12), (13), (14) and (15); In the general formula (5), m7 and m8 each independently represent 0 or 1, W is a single bond or any of the structures shown in the following (6); R1 is the aforementioned R1 group, and n9 and n10 each independently represent an integer from 0 to 4, and n9+n10 is 1 or more and 8 or less; In the general formula (6), n11 represents an integer from 0 to 3, Ri, Rj, Rk, Rl, Rm and Rn independently represent a hydrogen atom, or an alkyl group or phenyl group having 1 to 10 carbon atoms which may be substituted with fluorine, and Ri and Rj may be bonded to form a cyclic compound; In the general formula (7), R1 is the aforementioned R1 group, and Ro represents a hydrogen atom, a methyl group or a phenyl group; In the general formulae (8) to (12), R1 is the aforementioned R1 group; Rp, Rq, Rr, Rs, Rt, Ru and Rv each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a benzyl group or a phenyl group which may have a substituent on the aromatic ring; Y represents the aforementioned R1 group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and at least two of the four Ys in formula (12) are the aforementioned R1 groups; R1O-Rw-OR1 (13) Rw in the general formula (13) represents a straight-chain, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and Rx in the general formula (14) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R1 in the general formulas (13) to (15) is the aforementioned R1 group.

3. The resist underlayer film of a multilayer resist film used for lithography or the organic flattening film for semiconductor manufacturing according to claim 1 or 2, wherein The R1 group in the general formula (1) is composed of any one or more of the general formulas (2) to (4) and any one or more of the following general formulas (16) and (17); In the general formula (16), R2 represents a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and the methylene group constituting the R2 group may be substituted by an oxygen atom or a carbonyl group; In the general formula (17), R3 represents a hydrogen atom, or a straight-chain or branched hydrocarbon group having 1 to 10 carbon atoms, R4 represents a straight-chain or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms; n11 represents 0 to 2, n12 and n13 represent the number of substituents on the aromatic ring, n12 and n13 represent integers from 0 to 7, and satisfy the relationship that n12+n13 is greater than 0 and less than 7.

4. The resist underlayer film of a multilayer resist film used for lithography or the organic flattening film for semiconductor manufacturing according to claim 1 or 2, wherein The organic film-forming material further contains one or more of a surfactant, a cross-linking agent, and a plasticizer.

5. The resist underlayer film of a multilayer resist film used for lithography or the organic flattening film for semiconductor manufacturing 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° C. and one or more organic solvents having a boiling point of 180° C. or higher.

6. The method for forming an organic flat film for semiconductor manufacturing according to any one of claims 1 to 5, characterized in that : The organic film forming material is spin-coated on the processed substrate, The substrate is heat-treated at a temperature of 100° C. to 600° C. for 10 seconds to 600 seconds to form a cured film.

7. The method for forming an organic flat film for semiconductor manufacturing according to any one of claims 1 to 5, characterized in that : The organic film forming material is spin-coated on the processed substrate, The substrate is heat treated in a gas atmosphere having an oxygen concentration of 0.1% to 21% to form a cured film.

8. The method for forming an organic flat film for semiconductor manufacturing according to claim 6 or 7, wherein a substrate to be processed having a structure or a height difference of 30 nm or more is used as the substrate to be processed.

9. A pattern forming method, characterized in that: forming the resist underlayer film according to any one of claims 1 to 5 on a workpiece, On the resist underlayer film, a resist intermediate layer film is formed using a resist intermediate layer film material containing silicon, On the resist intermediate layer film, a resist upper layer film is formed using a resist upper layer film material containing a photoresist composition, A circuit pattern is formed on the upper layer of the resist. The resist upper layer film having the pattern is used as a mask to etch the resist intermediate layer film, thereby transferring the pattern to the resist intermediate layer film. Using the resist intermediate layer film with the transferred pattern as a mask, the resist lower layer film is etched to transfer the pattern to the resist lower layer film. Furthermore, the object to be processed is etched using the resist underlayer film to which the pattern has been transferred as a mask, thereby forming a pattern on the object to be processed.

10. A pattern forming method, characterized in that: forming the resist underlayer film according to any one of claims 1 to 5 on a workpiece, On the resist underlayer film, a resist intermediate layer film is formed using a resist intermediate layer film material containing silicon atoms, forming an organic anti-reflection film on the resist intermediate layer film, A resist upper layer film material containing a photoresist composition is used on the organic anti-reflection film to form a resist upper layer film to form a 4-layer film structure. A circuit pattern is formed on the upper layer of the resist. The organic anti-reflection film and the resist intermediate film are etched using the patterned resist upper film as a mask, and the pattern is transferred to the organic anti-reflection film and the resist intermediate film. The resist intermediate layer film to which the pattern has been transferred is used as a mask to etch the resist lower layer film, thereby transferring the pattern to the resist lower layer film. Furthermore, the object to be processed is etched using the resist underlayer film to which the pattern has been transferred as a mask, thereby forming a pattern on the object to be processed.

11. A pattern forming method, characterized in that: forming the resist underlayer film according to any one of claims 1 to 5 on a workpiece, forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film and a silicon oxide nitride film on the resist underlayer film, A resist upper layer film is formed on the inorganic hard mask intermediate film using a resist upper layer film material containing a photoresist composition, A circuit pattern is formed on the upper layer of the resist. The inorganic hard mask intermediate film is etched using the patterned resist upper film as a mask to transfer the pattern to the inorganic hard mask intermediate film. The inorganic hard mask intermediate film having the pattern formed therein is used as a mask to etch the resist underlayer film, thereby transferring the pattern to the resist underlayer film. Furthermore, the object to be processed is etched using the patterned resist underlayer film as a mask to form a pattern on the object to be processed.

12. A pattern forming method, characterized in that: forming the resist underlayer film according to any one of claims 1 to 5 on a workpiece, forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film and a silicon oxide nitride film on the resist underlayer film, forming an organic anti-reflection film on the inorganic hard mask intermediate film, A resist upper layer film material containing a photoresist composition is used on the organic antireflection film to form a resist upper layer film to form a four-layer film structure. A circuit pattern is formed on the upper layer of the resist. The patterned resist upper film is used as a mask to etch the organic anti-reflection film and the inorganic hard mask intermediate film, thereby transferring the pattern to the organic anti-reflection film and the inorganic hard mask intermediate film. The patterned inorganic hard mask intermediate film is used as a mask to etch the resist underlayer film, thereby transferring the pattern to the resist underlayer film. Furthermore, the object to be processed is etched using the patterned resist underlayer film as a mask to form a pattern on the object to be processed.

13. The pattern forming method according to claim 11 or 12, wherein: The inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

14. The pattern forming method according to any one of claims 9 to 12, wherein: The pattern forming method of the resist upper layer film forms a pattern by optical lithography using light with a wavelength of 10 nm to 300 nm, direct drawing using an electron beam, nano-stamping, or a combination thereof.

15. The pattern forming method according to any one of claims 9 to 12, wherein: The patterning method of the resist upper layer film includes alkali development or development using an organic solvent.

16. The pattern forming method according to any one of claims 9 to 12, wherein: The object to be processed is a semiconductor device substrate, 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.

17. The pattern forming method according to any one of claims 9 to 12, wherein: The processed object includes silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum or an alloy thereof.

18. Use of a compound represented by the following general formula (1) for forming a resist underlayer film of a multilayer resist film used in photolithography or an organic flat film for semiconductor manufacturing; In the general formula (1), X is an n1-valent organic group having 2 to 50 carbon atoms, n1 represents an integer of 2 to 10, and R1 is at least one of the following general formulae (2) to (4); In the general formula (2), * represents the bonding site to the organic group X, R a and R b represents a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R c represents a hydrogen atom, a methyl group or a phenyl group, m1 and m2 represent an integer of 0 or 1, n2 and n3 represent an integer of 1 to 7 and satisfy the relationship of 1≤n2+n3≤7, and n4 represents an integer of 1 to 10; In the general formula (3), * represents the bonding site to the organic group X, R d and R e represents a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, R f represents a hydrogen atom, a methyl group or a phenyl group, m3 and m4 represent integers of 0 or 1, n5 and n6 represent integers of 1 to 7, and satisfy the relationship of 1≤n5+n6≤7; l1 represents 1, and the oxygen atom serves as an ether bond to form a bridging structure between aromatic rings; In the general formula (4), * represents the bonding site to the organic group X, R g and R h represents a hydrogen atom, or a straight-chain or branched saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, m5 and m6 represent integers of 0 or 1, n7 and n8 represent integers of 1 to 7 and satisfy the relationship of 1≤n7+n8≤7; l2 represents 0 or 1, when l2=1, the oxygen atom acts as an ether bond to form a bridging structure between aromatic rings, and when l2=0, there is no ether bond to form a bridging structure between aromatic rings.

19. The use according to claim 18, wherein The general formula (1) is any of the following general formulas (5), (7), (8), (9), (10), (11), (12), (13), (14) and (15); In the general formula (5), m7 and m8 each independently represent 0 or 1, W is a single bond or any of the structures shown in the following (6); R1 is the aforementioned R1 group, n9 and n10 each independently represent an integer from 0 to 4, and n9+n10 is 1 or more and 8 or less; In the general formula (6), n11 represents an integer from 0 to 3, Ri, Rj, Rk, Rl, Rm and Rn independently represent a hydrogen atom, or an alkyl group or phenyl group having 1 to 10 carbon atoms which may be substituted with fluorine, and Ri and Rj may be bonded to form a cyclic compound; In the general formula (7), R1 is the aforementioned R1 group, and Ro represents a hydrogen atom, a methyl group or a phenyl group; In the general formulae (8) to (12), R1 is the aforementioned R1 group; Rp, Rq, Rr, Rs, Rt, Ru and Rv each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a benzyl group or a phenyl group which may have a substituent on the aromatic ring; Y represents the aforementioned R1 group or a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and at least two of the four Ys in formula (12) are the aforementioned R1 groups; R1O-Rw-OR1 (13) Rw in the general formula (13) represents a straight-chain, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and Rx in the general formula (14) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R1 in the general formulas (13) to (15) is the aforementioned R1 group.

20. The use according to claim 18 or 19, wherein R1 in the general formula (1) is composed of any one or more of the general formulae (2) to (4) and any one or more of the following general formulae (16) and (17); In the general formula (16), R2 represents a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and the methylene group constituting the R2 group may be substituted by an oxygen atom or a carbonyl group; In the general formula (17), R3 represents a hydrogen atom, or a straight-chain or branched hydrocarbon group having 1 to 10 carbon atoms, R4 represents a straight-chain or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms; n11 represents 0 to 2, n12 and n13 represent the number of substituents on the aromatic ring, n12 and n13 represent integers from 0 to 7, and satisfy the relationship that n12+n13 is greater than 0 and less than 7.

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