Composition for forming organic films, method for forming organic films, and method for forming patterns

Abstract

To provide a composition for forming an organic film that has excellent film-formability on a substrate and filling characteristics, and that inhibits humps in EBR process; and a method for forming an organic film and a patterning process, each using this composition.SOLUTION: The present invention provides a composition comprising: a resin for forming an organic film; a polymer having a structural unit represented by the formula (I) and a structural unit represented by the formula (II); and a solvent. The structural units of the formulae (I) and (II) form a random copolymer, and the polymer has a fluorine content of 5 mass% to 16 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an organic film forming composition for forming an organic film for multilayer resists for microfabrication in the manufacture of semiconductor devices and the like, and an organic film for planarization in the manufacture of semiconductor devices and the like, an organic film forming method using the composition, and a pattern forming method using the composition. [Background technology]

[0002] In recent years, with the increasing integration and speed of semiconductor devices, there has been a demand for miniaturization of pattern rules. In lithography, which uses light exposure and is currently used as a general-purpose technology, various technological developments are being carried out to determine how to process patterns more finely and with higher precision using the light source.

[0003] For lithography light sources used in resist pattern formation, light exposure using mercury lamps with g-line (436nm) or i-line (365nm) wavelengths is widely used in areas with low integration density. On the other hand, in areas with high integration density and requiring miniaturization, lithography using shorter wavelength KrF excimer lasers (248nm) and ArF excimer lasers (193nm) has also been put into practical use, and in the cutting edge generation requiring even greater miniaturization, lithography using extreme ultraviolet (EUV, 13.5nm) is also approaching practical application.

[0004] As resist patterns become thinner, the ratio of the pattern height to the pattern line width (aspect ratio) increases in the single-layer resist method, which is a typical resist pattern formation method. It is well known that the pattern collapses during development due to the surface tension of the developer. Therefore, it is known that multilayer resist methods, which form patterns by stacking films with different dry etching properties, are superior for forming high-aspect-ratio patterns on stepped substrates. Two-layer resist methods have been developed, such as a two-layer resist method (Patent Document 1) that combines a photoresist layer made of a silicon-containing photosensitive polymer with a lower layer made of an organic polymer whose main constituent elements are carbon, hydrogen, and oxygen, such as a novolac polymer, and a three-layer resist method (Patent Document 2) that combines a photoresist layer made of an organic photosensitive polymer used in the single-layer resist method with an intermediate layer made of a silicon-based polymer or silicon-based CVD film and a lower layer made of an organic polymer.

[0005] In this three-layer resist method, for example, an organic film such as novolac is uniformly deposited on the substrate to be processed as the resist underlayer, a silicon-containing film is deposited on top of it as the resist interlayer, and a normal organic photoresist film is formed on top of that as the resist upper layer. For dry etching with a fluorine-based gas plasma, the organic resist upper layer has a good etching selectivity ratio compared to the silicon-containing resist interlayer, so the resist pattern is transferred to the silicon-containing resist interlayer by dry etching with a fluorine-based gas plasma. With this method, even if a resist composition that is difficult to form a pattern with sufficient thickness for direct processing of the substrate or a resist composition that does not have sufficient dry etching resistance for processing the substrate is used, the pattern can be transferred to the silicon-containing film, and then by performing pattern transfer using dry etching with an oxygen-based gas plasma, a novolac film pattern with sufficient dry etching resistance for processing can be obtained.

[0006] While numerous technologies for organic underlayer films as described above are already publicly known (e.g., Patent Document 3), with the recent advancements in miniaturization, there is a growing need for excellent embedding properties in addition to dry etching properties. There is a need for an organic underlayer film material that can uniformly form a film even on substrates with complex shapes or materials, and that has embedding properties that can completely fill the required pattern without any voids.

[0007] The organic underlayer films described above are formed using a coater / developer capable of performing processes such as spin coating, EBR, and firing when manufacturing semiconductor substrates. The EBR (Edge Bead Removal) process is a process in which, after forming a film on the substrate (wafer) by spin coating, the film at the edges of the substrate is removed with a removal solution to prevent contamination of the substrate transport arm of the coater / developer. The removal solution used in the EBR process is a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30% by mass:70% by mass), and is widely used in the EBR process of resist films, silicon-containing interlayer films, and organic underlayer films.

[0008] Due to the effects of the removal agent in the EBR process, the outer edges of the organic underlayer film may develop thicker layers (humps). In the dry etching process during substrate processing described above, these humps can cause defects, so there is a need for organic underlayer films that suppress hump formation. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 6-118651 [Patent Document 2] Patent No. 4355943 [Patent Document 3] Japanese Patent Publication No. 2004-205685 [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] The present invention has been made in view of the above circumstances, and aims to provide an organic film formation composition that is excellent in film formation properties (in-plane uniformity) and embedding characteristics on a substrate (wafer), and that suppresses hump formation during the EBR process, an organic film formation method using this composition, and a pattern formation method. [Means for solving the problem]

[0011] To achieve the above objectives, the present invention provides an organic film-forming composition comprising an organic film-forming resin, a polymer containing a structural unit represented by the following general formula (I), a structural unit represented by the following general formula (II), and a structural unit represented by the following general formula (III), and a solvent, wherein the structural unit represented by the following general formula (I), the structural unit represented by the following general formula (II), and the structural unit represented by the following general formula (III) form a random copolymer, and the fluorine content of the polymer is 5% to 16% by mass. [ka] (In the formula, R 1 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 2 This refers to an organic group containing a fluorine atom, with 1 to 20 carbon atoms, and that does not contain a sulfonyl group or an amino group. [ka] (In the formula, R 3 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 4 and R 5 Each of these is a divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched, R 6 (where m1 is a hydrogen atom or an alkyl group or phenyl group having 1 to 4 carbon atoms, m1 is 0 to 23, n1 is 0 to 23, and 23 ≥ m1 + n1 ≥ 2.) [ka] (In the formula, R 7and R 8 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R 9 and R 10 each represents a divalent alkylene group having 1 to 4 carbon atoms which may be linear or branched, m2 is 0 to 23, n2 is 0 to 23, and 23 ≥ m2 + n2 ≥ 2.)

[0012] For such a composition for forming an organic film, it is possible to form an organic film excellent in in-plane uniformity and embedding characteristics and suppressing the formation of humps due to the influence of the remover in the EBR process.<00002??4>

[0013] Further, it is preferable that the R of the structural unit represented by the general formula (I) of the polymer is an organic film-forming composition containing a structure represented by the following general formula (IV) or (V). 2 [Chemical formula] <00??231>(In the formula, * indicates the bonding position.)

[0014] For an organic film-forming composition containing such a polymer, it is preferable because the in-plane uniformity of the formed organic film is more excellent.

[0015] ?Further, it is preferable that the composition for forming an organic film is a composition for forming an organic film in which the resin for forming an organic film is a resin having an aromatic skeleton.

[0016] For a resin having such an aromatic skeleton, it is preferable because etching resistance, optical properties, heat resistance, etc. are more excellent.

[0017] Further, it is preferable that the composition for forming an organic film is a composition for forming an organic film in which the content of the polymer is 0.01 parts by mass to 5 parts by mass with 100 parts by mass of the resin for forming an organic film.

[0018] For an organic film-forming composition containing the polymer having such a content, it is preferable because the in-plane uniformity of the formed organic film is more excellent.

[0019] It should be noted that there are some question marks in the original text (such as <00002??4> and ?>) which might be errors in the original. I've translated them as accurately as possible while keeping the original format.Furthermore, it is preferable that the organic film-forming composition contains 10 to 40 parts by mass of the organic film-forming resin, with 100 parts by mass of the organic film-forming composition.

[0020] When the content of the organic film-forming resin is such that the organic film-forming composition can have excellent in-plane uniformity and embedding properties, it can be used suitably.

[0021] The effects of the present invention can be fully demonstrated with organic film-forming compositions as described above.

[0022] Furthermore, the present invention provides a method for forming an organic film used in the manufacturing process of a semiconductor device, comprising: rotatingly coating a substrate to be processed with the above-mentioned organic film forming composition; and heat-treating the substrate coated with the organic film forming composition at a temperature of 100°C to 600°C for a period of 10 to 600 seconds to form a cured film.

[0023] According to the organic film formation method of the present invention, the above-mentioned organic film forming composition can be used to fill complex patterns on a workpiece substrate by rotary coating, and an organic film with excellent in-plane uniformity can be formed. The organic film obtained by the above method is preferable because it allows for the removal of the organic film at the edges while suppressing hump formation during the EBR process.

[0024] Furthermore, the present invention provides a pattern formation method comprising: forming an organic film on a workpiece using the above-mentioned organic film forming composition; forming a resist interlayer on the organic film using a resist interlayer material containing silicon atoms; forming a resist upper layer on the resist interlayer using a resist upper layer material made of a photoresist composition; forming a circuit pattern on the resist upper layer; transferring the pattern to the resist interlayer by etching using the resist upper layer on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the resist interlayer on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0025] Thus, the present invention provides a pattern formation method using a three-layer resist process with an organic film-forming composition, a silicon-containing resist interlayer, and a resist upper layer. With this pattern formation method of the present invention, the circuit pattern of the resist upper layer can be transferred and formed on the workpiece with high precision.

[0026] Furthermore, the present invention provides a pattern formation method comprising: forming an organic film on a workpiece using the above-mentioned organic film forming composition; forming a resist interlayer on the organic film using a resist interlayer material containing silicon atoms; forming an organic anti-reflective film or adhesion film on the resist interlayer; forming a resist upper layer on the organic anti-reflective film or adhesion film using a resist upper layer material made of a photoresist composition; forming a circuit pattern on the resist upper layer; transferring the pattern to the organic anti-reflective film or adhesion film and the resist interlayer by etching using the resist upper layer on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the resist interlayer on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0027] Thus, the present invention provides a pattern formation method using a four-layer resist process with an organic film-forming composition, a silicon-containing resist interlayer, an organic anti-reflective film or adhesion film, and a resist top layer film. With this pattern formation method of the present invention, the circuit pattern of the resist top layer film can be transferred and formed on the workpiece with high precision.

[0028] Furthermore, the present invention provides a pattern formation method comprising: forming an organic film on a workpiece using the above-mentioned organic film forming composition; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a resist upper film on the inorganic hard mask using a resist upper film material made of a photoresist composition; forming a circuit pattern on the resist upper film; transferring the pattern to the inorganic hard mask by etching using the resist upper film on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0029] Thus, the present invention provides a pattern formation method using a three-layer resist process with an organic film formation composition, an inorganic hard mask, and a resist upper layer film. With this pattern formation method of the present invention, the circuit pattern of the resist upper layer film can be transferred and formed on the workpiece with high precision.

[0030] Furthermore, the present invention provides a pattern formation method comprising: forming an organic film on a workpiece using the above-mentioned organic film forming composition; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming an organic anti-reflective film or an adhesion film on the inorganic hard mask; forming a resist upper film on the organic anti-reflective film or adhesion film using a resist upper film material made of a photoresist composition; forming a circuit pattern on the resist upper film; transferring the pattern to the organic anti-reflective film or adhesion film and the inorganic hard mask by etching using the resist upper film on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0031] Thus, the present invention provides a pattern formation method using a four-layer resist process with an organic film forming composition, an inorganic hard mask, an organic anti-reflective film or adhesion film, and a resist top layer film. With this pattern formation method of the present invention, the circuit pattern of the resist top layer film can be transferred and formed on the workpiece with high precision.

[0032] Furthermore, it is preferable to form the inorganic hard mask by CVD or ALD.

[0033] In the pattern formation method of the present invention, an inorganic hard mask can be formed by, for example, the method described above.

[0034] Furthermore, in forming the circuit pattern, it is preferable to form the circuit pattern by lithography using light with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0035] Furthermore, in forming the circuit pattern, it is preferable to develop the circuit pattern using alkaline development or an organic solvent.

[0036] In the pattern formation method of the present invention, such circuit pattern formation means and developing means can be suitably used.

[0037] Furthermore, it is preferable that the workpiece is a semiconductor device substrate, or a semiconductor device substrate on which any of the following films are formed: a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film.

[0038] Furthermore, it is preferable that the metal constituting the workpiece is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0039] With the pattern forming method of the present invention, patterns can be formed by processing the workpiece as described above. [Effects of the Invention]

[0040] As described above, the present invention provides an organic film formation composition that exhibits excellent film-forming properties (in-plane uniformity) and embedding characteristics on a substrate (wafer), and suppresses hump formation during the EBR process. Furthermore, because such an organic film formation composition of the present invention is excellent in film-forming properties, embedding characteristics, and suppression of hump formation during the EBR process, it is extremely useful as an organic film material used in multilayer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing resist interlayer or inorganic hard mask, or a four-layer resist process using a silicon-containing resist interlayer or inorganic hard mask and an organic anti-reflective film or adhesion film, or as an organic film formation material for semiconductor device manufacturing. Moreover, since the organic film formation method of the present invention can form an organic film with suppressed hump formation, semiconductor devices and the like can be manufactured efficiently. [Brief explanation of the drawing]

[0041] [Figure 1] This graph shows the hump height measured using a contact profiler in an example of a comparative example (Comparative UDL-1) of the organic film-forming composition of the present invention. [Figure 2] This graph shows the height of a hump measured using a contact profiler in an example of the organic film-forming composition of the present invention (UDL-4). [Figure 3] This is an explanatory diagram illustrating an example of a pattern formation method using the three-layer resist process of the present invention. [Figure 4] This is an explanatory diagram of the embedding characteristics evaluation method in the example. [Modes for carrying out the invention]

[0042] As described above, there was a need for the development of an organic film formation composition that exhibits excellent film-forming properties (in-plane uniformity) and embedding characteristics on a substrate (wafer), and that suppresses hump formation during the EBR process.

[0043] Typically, when forming an organic film, an organic film-forming resin and additives are dissolved in an organic solvent to form a composition. This composition is then applied to a substrate on which structures and wiring are formed using a coater / developer. The composition is spread by rotating the substrate, the composition at the edges is removed in an EBR process, and then the film is formed by firing. If the fluidity of the above composition is insufficient, voids will be generated when filling holes or trenches with a very high aspect ratio. Furthermore, if the organic film-forming resin or additives have poor solubility in the removal agent used in the EBR process, it is thought that humps will be generated on the outer periphery of the organic film.

[0044] The inventors have conducted further intensive studies and have found that by incorporating into the organic film-forming composition an organic film-forming composition comprising an organic film-forming resin, a polymer containing a structural unit represented by the following general formula (I), a structural unit represented by the following general formula (II), and a structural unit represented by the following general formula (III), and a solvent, the structural unit represented by the following general formula (I), the structural unit represented by the following general formula (II), and the structural unit represented by the following general formula (III) form a random copolymer, and the fluorine content of the polymer is 5% to 16% by mass, an organic film-forming composition with excellent film-forming properties, high embedding characteristics, and hump suppression during the EBR process is obtained, thus completing the present invention. [ka] (In the formula, R 1 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 2 This refers to an organic group containing a fluorine atom, with 1 to 20 carbon atoms, and that does not contain a sulfonyl group or an amino group. [ka] (In the formula, R3 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 4 and R 5 Each of these is a divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched, R 6 (where m1 is a hydrogen atom or an alkyl group or phenyl group having 1 to 4 carbon atoms, m1 is 0 to 23, n1 is 0 to 23, and 23 ≥ m1 + n1 ≥ 2.) [ka] (In the formula, R 7 and R 8 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 9 and R 10 Each of these groups is a divalent alkylene group with 1 to 4 carbon atoms, which can be either linear or branched. m2 has 0 to 23 carbon atoms, n2 has 0 to 23 carbon atoms, and 23 ≥ m2 + n2 ≥ 2.

[0045] In other words, the present invention relates to an organic film-forming composition comprising an organic film-forming resin, a polymer containing a structural unit represented by the following general formula (I), a structural unit represented by the following general formula (II), and a structural unit represented by the following general formula (III), and a solvent, wherein the structural unit represented by the following general formula (I), the structural unit represented by the following general formula (II), and the structural unit represented by the following general formula (III) form a random copolymer, and the fluorine content of the polymer is 5% to 16% by mass. [ka] (In the formula, R 1 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 2 This refers to an organic group containing a fluorine atom, with 1 to 20 carbon atoms, and that does not contain a sulfonyl group or an amino group. [ka] (In the formula, R 3 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 4 and R 5Each of these is a divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched, R 6 (where m1 is a hydrogen atom or an alkyl group or phenyl group having 1 to 4 carbon atoms, m1 is 0 to 23, n1 is 0 to 23, and 23 ≥ m1 + n1 ≥ 2.) [ka] (In the formula, R 7 and R 8 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 9 and R 10 Each of these groups is a divalent alkylene group with 1 to 4 carbon atoms, which can be either linear or branched. m2 has 0 to 23 carbon atoms, n2 has 0 to 23 carbon atoms, and 23 ≥ m2 + n2 ≥ 2. The fluorine content of the polymer used in this invention was calculated from the mass ratio of fluorine atoms to the total amount of the raw material monomers used.

[0046] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0047] [Composition for organic film formation] The present invention relates to an organic film-forming composition comprising an organic film-forming resin, a polymer containing a structural unit represented by the following general formula (I), a structural unit represented by the following general formula (II), and a structural unit represented by the following general formula (III), and a solvent, wherein the structural unit represented by the following general formula (I), the structural unit represented by the following general formula (II), and the structural unit represented by the following general formula (III) form a random copolymer, and the fluorine content of the polymer is 5% to 16% by mass. [ka] (In the formula, R 1 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 2 This refers to an organic group containing a fluorine atom, with 1 to 20 carbon atoms, and that does not contain a sulfonyl group or an amino group. [ka] (In the formula, R 3 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 4 and R 5 Each of these is a divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched, R 6 (where m1 is a hydrogen atom or an alkyl group or phenyl group having 1 to 4 carbon atoms, m1 is 0 to 23, n1 is 0 to 23, and 23 ≥ m1 + n1 ≥ 2.) [ka] (In the formula, R 7 and R 8 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 9 and R 10 Each of these groups is a divalent alkylene group with 1 to 4 carbon atoms, which can be either linear or branched. m2 has 0 to 23 carbon atoms, n2 has 0 to 23 carbon atoms, and 23 ≥ m2 + n2 ≥ 2.

[0048] In the organic film-forming composition of the present invention, the organic film-forming resin, the polymer, and the solvent can each be used individually or in combination of two or more types.

[0049] [A polymer comprising a structural unit represented by general formula (I), at least one of the structural units represented by general formula (II) and general formula (III), wherein the structural unit represented by general formula (I), at least one of the structural units represented by general formula (II) and general formula (III) form a random copolymer, and the fluorine content of the polymer is 5% to 16% by mass.] The present invention provides an organic film-forming composition comprising a structural unit represented by general formula (I), at least one of the structural units represented by general formula (II) and general formula (III), wherein the structural unit represented by general formula (I), at least one of the structural units represented by general formula (II) and general formula (III) form a random copolymer, and the polymer has a fluorine content of 5% to 16% by mass. These structural units are polymerized to form a random copolymer because of their excellent compatibility with organic film-forming resins and solvents. This polymer contains oxyalkylene groups, resulting in excellent flexibility, and by controlling the aggregation state of the polymer within an appropriate fluorine content range, the fluidity of the organic film-forming composition is improved, resulting in excellent embedding properties. Furthermore, this polymer has excellent solubility in the removal solution of the EBR process, which suppresses hump formation. In addition, the inclusion of fluorine reduces surface tension, improving the in-plane uniformity of the organic film-forming composition. The upper limit of the fluorine content is 16% by mass, with 14% by mass being preferred from the viewpoint of hump suppression, and 12% by mass being most preferred from the viewpoint of embedding characteristics. From the viewpoint of in-plane uniformity, the lower limit of the fluorine content is 5% by mass, and 7% by mass is preferred.

[0050] The above R 1 The group represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, and decyl groups. Among these, hydrogen atoms and methyl groups are more preferred.

[0051] The above R 2 This refers to an organic group containing a fluorine atom, having 1 to 20 carbon atoms, and not containing a sulfonyl group or an amino group. Here, in the present invention, "organic group" means a group containing at least one carbon atom, and may further contain hydrogen, as well as nitrogen, oxygen, sulfur, silicon, halogen atoms, etc. Organic groups having 1 to 20 carbon atoms and containing a fluorine atom are preferred, and organic groups having 1 to 20 carbon atoms in which the substituent containing a fluorine atom is represented by the following general formula (IV) or (V) are more preferred. [ka] (In the formula, * indicates a bonding position.) R 2 The reason why sulfonyl and amino groups are not included is that these structures increase polarity, limiting the types of solvents that can be used. Because the polymer contains such a structure, the surface tension of the organic film-forming composition is reduced, and the polymer also gains excellent compatibility with solvents. As a result, it becomes possible to form an organic film with superior in-plane uniformity by spin coating.

[0052] More specifically, the following are examples of structural units represented by the above general formula (I), but are not limited to these. As stated above, among these, those having a perfluoroalkyl group with 3 or 4 carbon atoms are preferred. [ka]

[0053] The above R 3 The group represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, and decyl groups. Among these, hydrogen atoms and methyl groups are more preferred.

[0054] The above R 4 and R 5Each represents a divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched. Specific examples of divalent alkylene groups having 1 to 4 carbon atoms, which may be linear or branched, include methylene, ethylene, propylene, butylene, trimethylene, and tetramethylene groups. Among these, the ethylene group is more preferred from the viewpoint of embedding properties. (R 4 O) and (R 5 The array in O) can be random, blocky, or multiblocky.

[0055] The above R 6 The group represents a hydrogen atom, a C1-C4 alkyl group, or a phenyl group. Specific examples of C1-C4 alkyl groups include methyl, ethyl, propyl, isopropyl, allyl, n-butyl, s-butyl, t-butyl, and isobutyl groups. Among these, a hydrogen atom, a methyl or ethyl group, or a phenyl group are more preferred.

[0056] In the above, m1 is between 0 and 23, n1 is between 0 and 23, and 23 ≥ m1 + n1 ≥ 2. Here, m1 and n1 represent the average number of repetitions. The upper limit of m1 + n2 is 23, and from the viewpoint of low-temperature storage stability, 13 is more preferable.

[0057] The following are some more specific examples of structural units represented by the general formula (II) above, but are not limited to these. [ka]

[0058] [ka]

[0059] The above R 7 and R 8The group represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, and decyl groups. Among these, hydrogen atoms and methyl groups are more preferred.

[0060] The above R 9 and R 10 Each represents a divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched. Specific examples of divalent alkylene groups having 1 to 4 carbon atoms, which may be linear or branched, include methylene, ethylene, propylene, butylene, trimethylene, and tetramethylene groups. Among these, the ethylene group is more preferred. (R 9 O) and (R 10 The array in O) can be random or blocky.

[0061] In the above, m2 is between 0 and 23, n2 is between 0 and 23, and 23 ≥ m2 + n2 ≥ 2. Here, m2 and n2 represent the average number of repetitions. The upper limit of m2 + n2 is 23, and 13 is more preferable from the viewpoint of low-temperature storage stability.

[0062] The following are some more specific examples of structural units represented by the general formula (III) above, but are not limited to these. [ka]

[0063] The polymer can be synthesized by polymerizing a monomer that gives a structural unit represented by general formula (I), and at least one monomer from among those that give a structural unit represented by general formula (II) and those that give a structural unit represented by general formula (III), in a blending ratio that is determined to be a predetermined content ratio according to the structure of each polymer, using a known method.

[0064] Furthermore, the polymer can be made by using one or more monomers from among the monomers that give structural units represented by general formula (I), the monomers that give structural units represented by general formula (II), and the monomers that give structural units represented by general formula (III).

[0065] By combining multiple structural units, the structure becomes more complex, which suppresses aggregation of the polymer and allows for appropriate adjustment of solvent solubility.

[0066] The polymer can be obtained by polymerizing polymerizable monomers using known methods, wherein the polymerization is carried out such that a structural unit represented by general formula (I) and at least one of the structural units represented by general formula (II) and general formula (III) form a random copolymer. When obtaining the polymer, it is also possible to synthesize the polymer by polymerizing each monomer protected with a protecting group as needed, and then performing a deprotection reaction as needed. The reaction method for obtaining the polymer is not particularly limited, but methods such as radical polymerization and cationic polymerization can be appropriately selected according to the reactivity of the monomers.

[0067] When using radical polymerization, monomers having polymerizable unsaturated bonds are mixed, and a radical initiator is added to a solvent and heated to perform polymerization, thereby obtaining a polymer. Polymerization conditions can be selected in various ways depending on the monomers used, the target molecular weight, etc. Specific examples of solvents used during polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, 2-butanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, cyclohexanone, γ-butyrolactone, ethyl acetate, and butyl acetate. Examples of polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. Additionally, thiols such as octanthiol and 2-mercaptoethanol may be added as chain transfer agents during polymerization. The polymerization reaction can preferably be carried out by heating to 40°C or the boiling point of the reaction solvent. The reaction time is 0.5 to 100 hours, preferably 1 to 48 hours.

[0068] When using cationic polymerization, monomers having polymerizable unsaturated bonds are mixed, and polymerization is carried out by adding a cationic polymerization initiator, thereby obtaining a polymer. Polymerization conditions can be selected in various ways depending on the monomers used, the target molecular weight, etc. Specific examples of solvents used during polymerization include hexane, heptane, octane, toluene, methylene chloride, 1,2-dichloroethane, ethyl ether, and butyl ether. Catalysts used as cationic polymerization initiators include acids, for example, Sulfuric acid, perchloric acid, trifluoroacetic acid, methanesulfonic acid, Riff Protonic acids such as chloromethanesulfonic acid, chlorosulfonic acid, and fluorosulfonic acid ,three Boron fluoride, aluminum chloride, titanium tetrachloride, tinnic chloride, ferric chloride, etc. Louis Lewis acids can be used. When using a Lewis acid as a catalyst, use approximately the same amount as the catalyst. AcidThe presence of a proton source such as water or alcohol can improve cationic polymerization activity and may therefore be added. The polymerization reaction is not particularly limited as long as the reaction proceeds at a temperature, but it is preferably carried out by heating from -10°C to the boiling point of the reaction solvent. The reaction time is 0.5 to 100 hours, preferably 1 to 48 hours.

[0069] The polymer preferably has a weight-average molecular weight (Mw) of 1,000 to 30,000, more preferably 2,000 to 20,000, and even more preferably 3,000 to 15,000. If Mw is 1,000 or higher, it exhibits excellent in-plane uniformity. On the other hand, if Mw is 30,000 or lower, coating defects due to insufficient solubility in the solvent can be suppressed. Furthermore, the molecular weight distribution (Mw / Mn) is preferably 1.0 to 3.0, and more preferably 1.0 to 2.0. In this invention, Mw and molecular weight distribution are polystyrene-converted values ​​measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the solvent.

[0070] The amount of polymer added is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and particularly preferably 0.5 to 2 parts by mass, per 100 parts by mass of the organic film-forming resin. If the amount of polymer added is 0.01 parts by mass or more, the blending effect can be sufficiently obtained. In addition, the polymer decomposes due to the heat during firing, which deteriorates the in-plane uniformity and embedding characteristics, but it can be suitably used if the amount is in the range of 5 parts by mass or less.

[0071] [Organic film forming resin] The organic film-forming resin usable in the organic film composition of the present invention is not particularly limited as long as it is a compound containing a resin that satisfies the film-forming and curing properties of spin coating, but from the viewpoint of etching resistance, optical properties, heat resistance, etc., a compound containing an aromatic skeleton is more preferred.

[0072] Examples of the aromatic skeletons mentioned above include benzene, naphthalene, anthracene, pyrene, indene, fluorene, furan, pyrrole, thiophene, phosphole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, and carbazole. Among these, benzene, naphthalene, fluorene, and carbazole are particularly preferred.

[0073] Examples of organic film-forming resins applicable to the present invention include resins containing the following structures described in Japanese Patent Publication No. 2012-1687 and Japanese Patent Publication No. 2012-77295. [ka] (In formula (1), the ring structures Ar1 and Ar2 represent benzene rings or naphthalene rings. X represents a single bond or an alkylene group with 1 to 20 carbon atoms. m represents 0 or 1. n represents any natural number such that the molecular weight is 100,000 or less. Note that the symbols in the formula are applied only within this formula.)

[0074] [ka] (In formula (2), the ring structures Ar1 and Ar2 represent benzene rings or naphthalene rings. n represents any natural number such that the polystyrene-based weight-average molecular weight determined by gel permeation chromatography is 100,000 or less. Note that the symbols in the formula are applied only within this formula.)

[0075] Examples of organic film-forming resins applicable to the present invention include resins containing the following structures described in Japanese Patent Publication No. 2004-264710, Japanese Patent Publication No. 2005-043471, Japanese Patent Publication No. 2005-250434, Japanese Patent Publication No. 2007-293294, and Japanese Patent Publication No. 2008-65303. [ka] (In equations (3) and (4), R 1 and R 2R represents a hydrogen atom or an alkyl group or aryl group having 1 to 3 carbon atoms. 3 The '' represents an alkyl group, vinyl group, allyl group, or optionally substituted aryl group having 1 to 3 carbon atoms, where n is 0 or 1 and m is 0, 1, or 2. Note that the symbols in the formula are only applicable within this formula.

[0076] [ka] (In equation (5), R1 is a monovalent atom or group other than a hydrogen atom, and n is an integer from 0 to 4. However, when n is from 2 to 4, multiple R1s may be the same or different. R2 and R3 are independently monovalent atoms or groups. X is a divalent group. Note that the symbols in the equation are applied only within this equation.)

[0077] [ka] (In formula (6), R1 is a hydrogen atom or a methyl group. R2 is a single bond, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may have any of the following characteristics: ether, ester, lactone, or amide. 3 , R 4 Each of these is either a hydrogen atom or a glycidyl group. X represents a polymer of a hydrocarbon containing an indene skeleton, a cycloolefin having 3 to 10 carbon atoms, or a maleimide, and may have one of the following: an ether, ester, lactone, or carboxylic acid anhydride. 5 , R 6 Each of these is either a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 7 is one of the following: a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or an alkoxycarbonyl group. p and q are integers from 1 to 4. r is an integer from 0 to 4. a, b, and c are within the ranges of 0.5 ≤ a + b + c ≤ 1, 0 ≤ a ≤ 0.8, 0 ≤ b ≤ 0.8, 0.1 ≤ a + b ≤ 0.8, and 0.1 ≤ c ≤ 0.8, respectively. Note that the symbols used in the formula are only applicable within this formula.

[0078] [ka] (In formula (7), R1 represents a hydrogen atom or a monovalent organic group, and R2 and R3 independently represent a monovalent atom or a monovalent organic group. The symbols in the formula are applied only within this formula.)

[0079] Examples of organic film-forming resins applicable to the present invention include resins containing the following structures described in Japanese Patent Publication No. 2004-205685, Japanese Patent Publication No. 2007-171895, and Japanese Patent Publication No. 2009-14816. [ka] (In equations (8) and (9), R 1 ~R 8 These are, independently of each other, a hydrogen atom, a hydroxyl group, a substituted alkyl group having 1 to 6 carbon atoms, a substituted alkoxy group having 1 to 6 carbon atoms, a substituted alkoxycarboxyl group having 2 to 6 carbon atoms, a substituted aryl group having 6 to 10 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an isocyanate group, or a glycidyl group. m and n are positive integers. Note that the symbols in the formula are only applicable within this formula.

[0080] [ka] (In formula (10), R 1 , R 6 R is a hydrogen atom or a methyl group. 2 , R 3 , R 4 R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydroxyl group, an acetoxy group or an alkoxycarbonyl group, or an aryl group having 6 to 10 carbon atoms. 5 These are condensed polycyclic hydrocarbon groups with 13 to 30 carbon atoms, -OR 7 , -C(=O)-OR 7 -OC(=O)-R 7 , or -C(=O)-NR 8 -R 7 Here, m is 1 or 2, n is an integer from 0 to 4, and p is an integer from 0 to 6.7 is an organic group having 7 to 30 carbon atoms, R 8 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Z is any one of a methylene group, -O-, -S-, -NH-. a, b, c, d, e are in the ranges of 0 < a < 1.0, 0 ≤ b ≤ 0.8, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.8, 0 ≤ e ≤ 0.8, and 0 < b + c + d + e < 1.0, respectively. Note that the symbols in the formula are applicable only within this formula.)

[0081]

Chemical formula

[0082] For example, the following compounds are exemplified. <000057>

Chemical formula

[0083]

Chemical formula

[0084] Examples of the resin for forming an organic film applied to the present invention include resins having the following structures described in JP-A-2007-199653, JP-A-2008-274250, and JP-A-2010-122656. [Chemical formula] (In formula (12), R 1 and R 2 are each independently the same or different hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms; R 3 is a single bond or an alkylene group having a linear, branched or cyclic structure having 1 to 30 carbon atoms, and may have a bridged cyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group; and n is an integer of 1 to 4. Note that the symbols in the formula are applicable only within this formula.)

[0085] [Chemical formula] (In formula (13), R 1 and R 2 are each independently the same or different hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms; R 3 is a single bond or an alkylene group having a linear, branched or cyclic structure having 1 to 30 carbon atoms, and may have a bridged cyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group; and R 6 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms. Note that the symbols in the formula are applicable only within this formula.)

[0086] [Chemical formula] (In formula (14), ring Z 1 and ring Z 2 are fused polycyclic aromatic hydrocarbon rings, R 1a , R 1b , R 2a , and R 2b represent substituents that are the same or different. k1 and k2 represent integers that are the same or different and are 0 or integers from 1 to 4, m1 and m2 each represent an integer of 0 or 1 or more, and n1 and n2 each represent an integer of 0 or 1 or more. However, n1 + n2 ≥ 1. Note that the symbols in the formula are applicable only within this formula.)

[0087]

Chemical formula

[0088] For example, the following compounds are exemplified.

Chemical formula

[0089]

Chemical formula

[0090]

Chemical formula

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] Examples of organic film-forming resins applicable to the present invention include resins containing the following structure described in Japanese Patent Application Publication No. 2012-214720. [ka] (In formula (16), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. x and z each independently represent 0 or 1. The symbols in the formula are applied only within this formula.)

[0095] Examples of organic film-forming resins applicable to the present invention include those described in Japanese Patent Publication No. 2014-29435, International Publication No. WO2012 / 077640, and International Publication No. WO2010 / 147155. [ka] (In formula (17), A represents a structure having a carbazole molecule, B represents a structure having an aromatic ring, and C represents a structure having a hydrogen atom, an alkyl group, or an aromatic ring. B and C may form a ring with each other. The combined structure of A, B, and C contains 1 to 4 carboxyl groups or their salts, or carboxylic acid ester groups. The symbols in the formula are applied only within this formula.)

[0096] Furthermore, examples of polymers can be given that include the unit structure represented by the following formula (18) and the unit structure represented by the following formula (19), as described in International Publication WO2012 / 077640, and the ratio of the unit structure represented by formula (18) to the unit structure represented by formula (19) is 3 to 97:97 to 3 in molar ratio. [ka] (In formula (18), R1 and R2 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups which may include an ether bond, a ketone bond, or an ester bond. R3 may also include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an ether bond, a ketone bond, or an ester bond.) These represent combinations of groups. R4 represents a hydrogen atom, or an aryl group with 6 to 40 carbon atoms that may be substituted with a halogen atom, nitro group, amino group, or hydroxyl group, or a heterocyclic group. R5 represents a hydrogen atom, or an alkyl group with 1 to 10 carbon atoms that may be substituted with a halogen atom, nitro group, amino group, or hydroxyl group, or an aryl group with 6 to 40 carbon atoms, or a heterocyclic group. R4 and R5 may form a ring with each other. n1 and n2 each represent integers from 1 to 3. Note that the symbols in the formula are only applicable within this formula. [ka] (In formula (19), Ar represents an aromatic ring group having 6 to 20 carbon atoms, R6 represents a hydroxyl group, R7 represents a combination of a hydrogen atom, a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an ether bond, a ketone bond, or an ester bond. R8 may be substituted with a hydrogen atom, a halogen atom, a nitro group, an amino group, or a hydroxyl group.) R8 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms, R9 may be substituted with a hydrogen atom, a halogen atom, a nitro group, an amino group, or a hydroxyl group, or R8 may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or heterocyclic group having 6 to 40 carbon atoms, and R8 and R9 may form a ring with each other. n6 represents an integer from 1 to p, and n7 represents an integer from p to n6. Here, p represents the maximum number that can be substituted on the aromatic ring group Ar. Note that the symbols in the formula are only applicable within this formula.

[0097] Examples of organic film-forming resins applicable to the present invention include polymers containing a unit structure represented by the following formula (20) as described in International Publication WO2010 / 147155. [ka] (In formula (20), R1 and R2 are each selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, alkenyl group or aryl group may contain an ether bond, a ketone bond or an ester bond, and R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, alkenyl group Alternatively, the aryl group may include an ether bond, a ketone bond, or an ester bond; R4 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms, which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxyl group; R5 represents an alkyl group having 1 to 10 carbon atoms, an aryl group or heterocyclic group having 6 to 40 carbon atoms, which may be substituted with a hydrogen atom, or a halogen group, a nitro group, an amino group, or a hydroxyl group; and R4 and R5 may form a ring together with the carbon atoms to which they are bonded, and n1 and n2 are integers from 1 to 3. Note that the symbols in the formula are applied only within this formula.

[0098] Examples of organic film-forming resins applicable to the present invention include novolac resins obtained by reacting one or more phenols such as phenol, cresol, xylenol, catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinol, and phloroglucinol with one or more aldehyde sources such as formaldehyde, paraformaldehyde, and trioxane using an acidic catalyst, and resins containing a repeating unit structure represented by the following formula (21) as described in International Publication WO2012 / 176767. [ka] (In formula (21), A represents a hydroxyl group-substituted phenylene group derived from polyhydroxybenzene, and B represents a monovalent condensed aromatic hydrocarbon ring group formed by the condensation of 2 to 6 benzene rings. Note that the symbols in the formula are applied only within this formula.)

[0099] Examples of organic film-forming resins applicable to the present invention include novolac resins having a fluorene or tetrahydrospirovindene structure as described in Japanese Patent Publication No. 2005-128509, Japanese Patent Publication No. 2006-259249, Japanese Patent Publication No. 2006-259482, Japanese Patent Publication No. 2006-293298, and Japanese Patent Publication No. 2007-316282, as well as resins containing a repeating unit structure represented by the following formulas (22-1) or (22-2). [ka] (In equations (22-1) and (22-2), R 1 , R 2 , R 6 , R 7 R is independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an allyl group, or a halogen atom. 3 , R 4 , R 8 , R 9 R is independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a glycidyl group. 5 , R 14 R is independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. n, m, p, and q are integers from 1 to 3. 10 ~R 13 These are independently a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched, or cyclic alkoxy group having 1 to 6 carbon atoms. Note that the symbols in the formula are applied only within this formula.

[0100] Examples of organic film-forming resins applicable to the present invention include reaction products obtained by the method described in Japanese Patent Application Publication No. 2012-145897. More specifically, examples include polymers obtained by condensing one or more compounds represented by the following general formulas (23-1) and / or (23-2) with one or more compounds represented by the following general formulas (24-1) and / or (24-2) and / or their equivalents. [ka] (In equations (23-1) and (23-2), R 1 ~R 8 These are, independently of each other, a hydrogen atom, a halogen atom, a hydroxyl group, an isocyanate group, a glycidyloxy group, a carboxyl group, an amino group, an alkoxy group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, an alkanoyloxy group having 1 to 30 carbon atoms, or a saturated or unsaturated organic group having 1 to 30 carbon atoms that may be substituted. Furthermore, within the molecule, R 1 ~R 4 or R 5 ~R 8 Two substituents, arbitrarily selected from each of these, may be bonded to further form a cyclic substituent. (Note that the symbols in the formula are applied only within this formula.) [ka] (In formulas (24-1) and (24-2), Q is an organic group having 1 to 30 carbon atoms that may be substituted, and two Qs may be arbitrarily selected within the molecule to bond to form a cyclic substituent. n1 to n6 are the number of substituents, and n1 to n6 = 0, 1, and 2, excluding hydroxybenzaldehyde in formula (24-1). Also, in formula (24-2), the relationships 0 ≤ n3 + n5 ≤ 3, 0 ≤ n4 + n6 ≤ 4, and 1 ≤ n3 + n4 ≤ 4 are satisfied. Note that the symbols in the formulas are applied only within these formulas.)

[0101] Furthermore, examples of polymers obtained by condensing one or more compounds represented by the above general formulas (23-1) and / or (23-2), one or more compounds represented by the above general formulas (24-1) and / or (24-2) and / or equivalents thereof, and one or more compounds represented by the following general formula (25) and / or equivalents thereof can be given. [ka] (In formula (25), Y is a hydrogen atom or a monovalent organic group having 30 or fewer carbon atoms which may have substituents. Formula (25) is different from formulas (24-1) and (24-2). The symbols in the formula are applied only within this formula.)

[0102] Examples of organic film-forming resins applicable to the present invention include resins containing the following structure as described in Japanese Patent Application Publication No. 2017-119671. [ka] (In formula (26-1), R is a single bond or an organic group having 1 to 50 carbon atoms, X is a group represented by the general formula (26-2) below, and m1 is an integer satisfying 2 ≤ m1 ≤ 10. Note that the symbols in the formula are applied only within this formula.) [ka] (In the formula, X 2 is a divalent organic group having 1 to 10 carbon atoms, where n1 is 0 or 1, n2 is 1 or 2, and X 3 The base is represented by the following general formula (26-3), where n5 is 0, 1, or 2. Note that the symbols in the formula are applied only within this formula. [ka] (In the formula, R 10 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group. Note that the symbols in the formula are applied only within this formula.

[0103] For example, the following compounds are given as examples. [ka]

[0104] [ka]

[0105] Examples of organic film-forming resins applicable to the present invention include polymers having repeating units represented by the following general formula (27-1) as described in Japanese Patent Application Publication No. 2019-44022. [ka] (In formula (27-1), AR1 and AR2 are benzene rings or naphthalene rings which may have substituents, R 1 , R 2 Each of these is independently a hydrogen atom or an organic group with 1 to 30 carbon atoms, R 1 and R 2 If it is an organic group, R 1 and R 2 A cyclic organic group may be formed by intramolecular bonding. n is either 0 or 1. When n=0, AR1 and AR2 do not form a bridged structure between their aromatic rings via Z. When n=1, AR1 and AR2 form a bridged structure between their aromatic rings via Z, and Z is either a single bond or one of the groups shown in formula (27-2) below. Y is the group shown in formula (27-3) below. Note that the symbols in the formulas are applied only within these formulas. [ka]

[0106] [ka] (In the formula, R 3 R is a single bond or a divalent organic group with 1 to 20 carbon atoms. 4∫ is a hydrogen atom or a monovalent organic group with 1 to 20 carbon atoms, and the dashed line indicates a bond. Note that the symbols in the formula are applied only within this formula.

[0107] For example, the following polymers are given as examples. [ka]

[0108] [ka]

[0109] [ka]

[0110] The resin for forming the organic film may be synthesized by known methods, or a commercially available product may be used.

[0111] The amount of the organic film-forming resin is not particularly limited as long as it satisfies the film-forming properties of the organic film-forming composition for spin coating. However, with 100 parts by mass of the organic film-forming composition, the content of the organic film-forming resin is more preferably 10 to 40 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 10 to 25 parts by mass. For example, when filling holes or trenches with a very high aspect ratio in a 3D NAND memory architecture with an organic film-forming composition, it is necessary to increase the amount of organic film-forming resin used. However, such organic film-forming compositions tend to have high viscosity, which degrades the in-plane uniformity and filling characteristics after spin coating. Even with the above-mentioned blending ratio of the organic film-forming resin, the organic film-forming composition of the present invention can form an organic film with excellent in-plane uniformity and filling characteristics, making it suitable for application.

[0112] [solvent] The solvent that can be used in the organic film-forming composition of the present invention is not particularly limited as long as it can dissolve the organic film-forming resin and the polymer, and is preferably one that can also dissolve the acid generator, crosslinking agent, surfactant, etc., which will be described later. Specifically, examples include ketones such as 2-heptanone, cyclopentanone, and cyclohexanone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, γ-butyrolactone, and propylene glycol monotert-butyl ether acetate. One or more of these can be used in combination, but are not limited to these.

[0113] In particular, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, γ-butyrolactone, and mixtures of two or more of these are preferably used.

[0114] [Other ingredients] Furthermore, the organic film-forming composition of the present invention may contain an acid generator or a crosslinking agent to further promote the crosslinking reaction. Acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation, and either type can be added. Specifically, examples of acid generators include those described in paragraphs (0061) to (0085) of Japanese Patent Application Publication No. 2007-199653.

[0115] Furthermore, as crosslinking agents, specific examples include those described in paragraphs (0055) to (0060) of Japanese Patent Publication No. 2007-199653.

[0116] Furthermore, surfactants may be added to the organic film-forming composition of the present invention to further improve in-plane uniformity in spin coating. Specific examples of surfactants include those described in paragraphs (0142) to (0147) of Japanese Patent Application Publication No. 2009-269953.

[0117] Furthermore, the organic film-forming composition of the present invention may be enriched with a basic compound to improve its storage stability. The basic compound acts as a quencher for the acid, preventing trace amounts of acid generated by the acid generator from driving the crosslinking reaction. Specific examples of such basic compounds include those described in paragraphs (0086) to (0090) of Japanese Patent Publication No. 2007-199653.

[0118] As described above, the organic film-forming composition of the present invention is an organic film-forming composition that excels in suppressing hump during the EBR process. Therefore, the organic film-forming composition of the present invention is extremely useful as a resist underlayer material for multilayer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing resist interlayer or silicon-containing inorganic hard mask, and a four-layer resist process using a silicon-containing resist interlayer or silicon-containing inorganic hard mask and an organic anti-reflective film or adhesion film.

[0119] [Organic film formation method] The present invention provides a method for forming an organic film used in the manufacturing process of a semiconductor device, comprising: rotatingly coating a substrate with the above-described organic film-forming composition of the present invention; and heat-treating the substrate coated with the organic film-forming composition at a temperature of 100°C to 600°C for a range of 10 to 600 seconds to form a cured film.

[0120] In this organic film formation method, first, the organic film formation composition of the present invention described above is applied to the substrate to be processed by spin coating. By using the spin coating method, good embedding characteristics can be obtained. After removing the film at the edges in the EBR process, baking (heat treatment) is performed to promote the crosslinking reaction. Furthermore, since this baking process allows the solvent in the composition to evaporate, mixing can be prevented even when forming a resist upper layer film or a silicon-containing resist interlayer film on the organic film.

[0121] The baking process is carried out at a temperature of 100°C to 600°C for 10 to 600 seconds, preferably at a temperature of 200°C to 500°C for 10 to 300 seconds. Considering the impact on device damage and wafer deformation, the upper limit of the heating temperature in the lithography wafer process is preferably 600°C or lower, and more preferably 500°C or lower. By performing heat treatment under these conditions, the crosslinking reaction is promoted, and an organic film can be formed without mixing with the film formed on top.

[0122] [Pattern formation method] [Three-layer resist process using silicon-containing resist interlayer] The present invention provides a pattern formation method comprising: forming an organic film on a workpiece using the above-described organic film forming composition of the present invention; forming a resist interlayer on the organic film using a resist interlayer material containing silicon atoms; forming a resist upper layer on the resist interlayer using a resist upper layer material made of a photoresist composition; forming a circuit pattern on the resist upper layer; transferring the pattern to the resist interlayer by etching using the resist upper layer on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the resist interlayer on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0123] Preferably, the workpiece is a semiconductor device substrate, or a semiconductor device substrate on which any of the following films are deposited: a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film. More specifically, although not particularly limited, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., or a substrate on which the above-mentioned metal films, etc., are deposited as the workpiece layer, can be used.

[0124] Various low-k films and their stopper films, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, can be used as the workpiece layer, and can typically be formed to a thickness of 50 to 10,000 nm, and especially 100 to 5,000 nm. When forming the workpiece layer, the substrate and the workpiece layer are made of different materials.

[0125] Furthermore, the metal constituting the workpiece is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0126] When forming an organic film on a workpiece using the organic film-forming composition of the present invention, the organic film-forming method of the present invention described above may be applied.

[0127] Next, a resist interlayer (silicon-containing resist interlayer) is formed on the organic film using a resist interlayer material containing silicon atoms. A polysiloxane-based interlayer material is preferred as the resist interlayer material containing silicon atoms. By giving the silicon-containing resist interlayer an anti-reflective effect, reflection can be suppressed. In particular, for 193nm exposure, if a material with a high etching selectivity with the substrate is used as the organic film forming composition, the k value will be high and substrate reflection will be high. However, by giving the silicon-containing resist interlayer an absorption that results in an appropriate k value, reflection can be suppressed, and substrate reflection can be reduced to 0.5% or less. As silicon-containing resist interlayers with an anti-reflective effect, anthracene is preferred for 248nm and 157nm exposure, and polysiloxane having a pendant structure of phenyl groups or absorbent groups having silicon-silicon bonds and being crosslinked by acid or heat is preferred for 193nm exposure.

[0128] Next, a resist upper film is formed on the resist interlayer using a resist upper film material consisting of a photoresist composition. The resist upper film material can be either positive or negative type, and the same photoresist compositions commonly used can be used. After spin-coating the resist upper film material, it is preferable to perform a pre-bake at 60-180°C for 10-300 seconds. Then, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain the resist upper film pattern. The thickness of the resist upper film is not particularly limited, but 30-500 nm is preferred, and 50-400 nm is particularly preferred.

[0129] Next, a circuit pattern (resist upper layer pattern) is formed on the resist upper layer. In forming the circuit pattern, it is preferable to form the circuit pattern by lithography using light with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0130] Examples of exposure light include high-energy rays with wavelengths of 300 nm or less, specifically far ultraviolet light, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 laser light (157 nm), Kr2 laser light (146 nm), Ar2 laser light (126 nm), soft X-rays (EUV) in the 3-20 nm range, electron beams (EB), ion beams, and X-rays.

[0131] Furthermore, in forming the circuit pattern, it is preferable to develop the circuit pattern using alkaline development or an organic solvent.

[0132] Next, the resist upper layer film on which the circuit pattern is formed is used as a mask to transfer the pattern to the resist interlayer film by etching. It is preferable to use a fluorocarbon-based gas for etching the resist interlayer film using the resist upper layer film pattern as a mask. This forms a silicon-containing resist interlayer film pattern.

[0133] Next, the pattern is transferred to the organic film by etching, using the resist interlayer with the transferred pattern as a mask. Since the silicon-containing resist interlayer exhibits etching resistance to oxygen or hydrogen gas, it is preferable to use an etching gas mainly composed of oxygen or hydrogen gas when etching the organic film using the silicon-containing resist interlayer pattern as a mask. This forms the organic film pattern.

[0134] Next, using the organic film onto which the pattern has been transferred as a mask, the pattern is transferred to the workpiece by etching. The etching of the next workpiece (etching layer) can be performed by a conventional method. For example, if the workpiece is SiO2, SiN, or a silica-based low dielectric constant insulating film, etching mainly using a fluorocarbon gas is performed; if it is p-Si, Al, or W, etching mainly using a chlorine-based or bromine-based gas is performed. When substrate processing is performed by etching using a fluorocarbon gas, the silicon-containing resist intermediate film pattern is peeled off simultaneously with the substrate processing. On the other hand, when substrate processing is performed by etching using a chlorine-based or bromine-based gas, in order to peel off the silicon-containing resist intermediate film pattern, it is necessary to separately perform dry etching peeling using a fluorocarbon gas after the substrate processing.

[0135] The organic film obtained by using the composition for forming an organic film of the present invention can be made excellent in etching resistance during etching of the workpiece as described above.

[0136] [Four-layer resist process using a silicon-containing resist intermediate film and an organic antireflection film or adhesion film] Further, in the present invention, an organic film is formed on a workpiece using the composition for forming an organic film of the present invention described above, a resist intermediate film is formed on the organic film using a resist intermediate film material containing a silicon atom, an organic antireflection film or adhesion film is formed on the resist intermediate film, a resist upper layer film is formed on the organic antireflection film or adhesion film using a resist upper layer film material composed of a photoresist composition, a circuit pattern is formed on the resist upper layer film, the pattern is transferred to the organic antireflection film or adhesion film and the resist intermediate film by etching using the resist upper layer film on which the circuit pattern is formed as a mask, the pattern is transferred to the organic film by etching using the resist intermediate film on which the pattern is transferred as a mask, and furthermore, a pattern forming method is provided in which the pattern is transferred to the workpiece by etching using the organic film on which the pattern is transferred as a mask.

[0137] Note that this method can be carried out in the same manner as the three-layer resist process using the above silicon-containing resist intermediate film, except that an organic anti-reflection film (BARC) or an adhesion film is formed between the resist intermediate film and the resist upper film.

[0138] The organic anti-reflection film and the adhesion film can be formed by spin coating using known organic anti-reflection film materials or adhesion film materials.

[0139] [Three-layer resist process using an inorganic hard mask] Further, in the present invention, as a pattern formation method by a three-layer resist process using the above composition for forming an organic film of the present invention, an organic film is formed on a workpiece using the above composition for forming an organic film of the present invention, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film, a resist upper film is formed on the inorganic hard mask using a resist upper film material composed of a photoresist composition, a circuit pattern is formed on the resist upper film, the inorganic hard mask is etched to transfer the pattern using the resist upper film on which the circuit pattern is formed as a mask, the organic film is etched to transfer the pattern using the inorganic hard mask on which the pattern is transferred as a mask, and further, the workpiece is etched to transfer the pattern using the organic film on which the pattern is transferred as a mask. A pattern formation method is provided.

[0140] Note that this method can be carried out in the same manner as the three-layer resist process using the above silicon-containing resist intermediate film, except that an inorganic hard mask is formed on the organic film instead of the resist intermediate film.

[0141] Inorganic hard masks selected from silicon oxide films, silicon nitride films, and silicon oxynitride films (SiON films) can be formed by CVD, ALD, or other methods. Methods for forming silicon nitride films are described, for example, in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. Among inorganic hard masks, the SiON film, which has a high effect as an anti-reflective film, is most preferably used.

[0142] [Four-layer resist process using an inorganic hard mask and an organic anti-reflective coating or adhesion coating] Furthermore, the present invention provides a pattern formation method using a four-layer resist process with the above-described organic film forming composition of the present invention, comprising: forming an organic film on a workpiece using the above-described organic film forming composition of the present invention; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming an organic anti-reflective film or adhesion film on the inorganic hard mask; forming a resist upper film on the organic anti-reflective film or adhesion film using a resist upper film material made of a photoresist composition; forming a circuit pattern on the resist upper film; transferring the pattern to the organic anti-reflective film or adhesion film and the inorganic hard mask by etching using the resist upper film on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0143] This method can be carried out in the same manner as the three-layer resist process using the inorganic hard mask described above, except that an organic anti-reflective coating (BARC) or adhesion film is formed between the inorganic hard mask and the resist upper layer.

[0144] In particular, when a SiON film is used as an inorganic hard mask, the two-layer anti-reflective coating of the SiON film and BARC makes it possible to suppress reflection even in immersion lithography with high NA values ​​exceeding 1.0. Another advantage of forming BARC is that it reduces the trailing of the resist upper layer pattern directly above the SiON film.

[0145] Here, an example of a pattern formation method using the three-layer resist process of the present invention is shown in Figures 3(A) to (F). In the three-layer resist process, as shown in Figure 3(A), an organic film 3 is formed on a workpiece layer 2 formed on a substrate 1 using the organic film forming composition of the present invention, then a silicon-containing resist interlayer 4 is formed, and a resist upper layer 5 is formed thereon. Next, as shown in Figure 3(B), the exposed portion 6 of the resist upper layer 5 is exposed and PEB (post-exposure bake) is performed. Next, as shown in Figure 3(C), development is performed to form a resist upper layer pattern 5a. Next, as shown in Figure 3(D), the silicon-containing resist interlayer 4 is dry-etched using a fluorocarbon gas with the resist upper layer pattern 5a as a mask to form a silicon-containing resist interlayer pattern 4a. Next, as shown in Figure 3(E), after removing the resist upper layer pattern 5a, the organic film 3 is oxygen-plasma-etched using the silicon-containing resist interlayer pattern 4a as a mask to form an organic film pattern 3a. Furthermore, as shown in Figure 3(F), after removing the silicon-containing resist interlayer pattern 4a, the workpiece layer 2 is etched using the organic film pattern 3a as a mask to form pattern 2a. The suppression of hump formation during organic film formation reduces defects that would otherwise occur during dry etching (Figures D, E, and F) due to hump formation in the organic film. This makes it possible to reduce the problem.

[0146] When forming an inorganic hard mask, the silicon-containing resist interlayer 4 can be replaced with an inorganic hard mask. When forming a BARC or adhesion film, the BARC or adhesion film can be formed between the silicon-containing resist interlayer 4 and the resist upper layer 5. The etching of the BARC may be performed consecutively prior to the etching of the silicon-containing resist interlayer 4, or the etching of the silicon-containing resist interlayer 4 may be performed after etching of only the BARC by changing the etching equipment.

[0147] As described above, with the pattern formation method of the present invention, it is possible to form fine patterns on a workpiece with high precision by a multilayer resist process, and to reduce defects originating from hump formation in the organic film by suppressing hump formation in the organic film. [Examples]

[0148] The present invention will be described in more detail below with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited thereto. The molecular weight was measured using the following method: The weight-average molecular weight (Mw) and number-average molecular weight (Mn) in polystyrene equivalent were determined by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent (solvent), and the degree of dispersion (Mw / Mn) was calculated.

[0149] [Preparation of polymers (A-1~24, a-1~10)] The monomers (B-1) to (B-6), (C-1) to (C-8), (D-1), and (E-1) to (E-3) shown below were used to synthesize the polymers (A-1) to (A-24) and comparative polymers (a-1) to (a-10) used in the preparation of the organic film-forming composition. [ka]

[0150] [Synthesis Example 1] Synthesis of Polymer (A-1) 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80 °C under a nitrogen atmosphere. To this, 3.18 g (0.010 mol) of (B-1) and a mixture of 7.74 g (0.035 mol) of (C-1), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate) and 34 g of PGMEA were added dropwise over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (A-1). As a result of analysis, the weight average molecular weight (Mw) of the polymer (A-1) was 6900 and the dispersity (Mw / Mn) was 1.4. [Chemical formula]

[0151] [Synthesis Examples 2 to 34] Synthesis of Polymers (A-2) to (A-24) and Comparative Polymers (a-1) to (a-10) Polymers (A-2) to (A-24) and comparative polymers (a-1) to (a-10) shown below were obtained as products by a method according to Synthesis Example 1, except that the types and molar ratios of the raw material monomers used were changed according to the structure of each polymer. Also shown are the weight average molecular weight (Mw) determined by GPC, the dispersity (Mw / Mn), and the fluorine content calculated from the raw material monomers and their blending ratios. All of the above polymers are random copolymers.

[0152] [Chemical formula]

[0153] (a-1) to (a-5) are comparative polymers because their fluorine contents are outside the range shown in Table 1, and (a-6) to (a-10) are comparative polymers because they contain structural units different from those of formula (II) or formula (III). [Chemical formula]

[0154] [Table 1-1]

[0155] [Table 1-2]

[0156] [Organic film forming resin] F-1: Resin represented by the following formula (F-1) F-2: Resin represented by the following formula (F-2) F-3: Resin represented by the following formula (F-3) F-4: Resin represented by the following formula (F-4) F-5: Resin represented by the following formula (F-5) F-6: Resin represented by the following formula (F-6)

[0157] [ka]

[0158] [ka]

[0159] [solvent] G-1: Propylene glycol monomethyl ether acetate G-2: Propylene glycol monoethyl ether

[0160] [Organic film-forming composition (UDL-1~102, comparison U DL Preparation of (1-33) The above polymers (A-1) to (A-24), (a-1) to (a-10), organic film-forming resins (F-1) to (F-6), and solvent are dissolved in the proportions shown in Table 2, and filtered through a 0.1 μm fluororesin filter to obtain an organic film material (U DL Samples -1 to 102 and comparative examples UDL-1 to 33 were prepared respectively. All of these organic membrane compositions contain random copolymers. [Table 2-1]

[0161] [Table 2-2]

[0162] [Table 2-3]

[0163] [Table 2-4]

[0164] [Table 2-5]

[0165] [Organic film-forming composition (UDL-1~102, comparison U DL [Fabrication of silicon wafers with organic cured films using (-1~33)] Using Tokyo Electron Limited's coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 mL of the organic film-forming compositions (UDL-1 to 102, comparative UDL-1 to 33) prepared above were dispensed onto the center of a silicon wafer. After baking, the wafer was rotated at a rotation speed that resulted in the average film thickness shown in Table 3, and the film was spread to form the film. While rotating the silicon wafer at a speed of 1000 rpm, the removal solution dispensing nozzle was moved at a speed of 5 mm / s from the outer edge of the silicon wafer to a position 3 mm from the center, dispensing the removal solution (a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30:70, mass ratio)) at a discharge rate of 2 mL / s. At that position, the removal solution was further dispensed at a discharge rate of 2 mL / s for 5 seconds. After that, the dispensing of the removal solution was stopped, and the wafer was rotated at a speed of 1000 rpm for another 30 seconds. Next, the silicon wafer on which the organic film-forming composition has been deposited is heated at 350 degrees Celsius for 60 seconds to form an organic cured film. Ta Shi Recon wafers were obtained.

[0166] [Solvent resistance evaluation: Examples 1-1 to 1-102, Comparative Examples 1-1 to 1-33] Organic film-forming compositions (UDL-1 to 102, comparative UDL1-1 to 1-33) were deposited on silicon wafers using the method described above. The film thickness was measured, PGMEA solvent was dispensed onto the wafers, left for 30 seconds, spin-dried, and baked at 100°C for 60 seconds to evaporate the PGMEA. The film thickness was then measured again. Let X be the film thickness before dispensing the PGMEA solvent, and X1 be the film thickness after dispensing the PGMEA solvent. The absolute value of the value calculated by (X1-X) / X×100 was defined as the film thickness change rate (%), and the results are shown in Table 3. A film thickness change rate of less than 0.5% was considered good, and a rate of 0.5% or more was considered poor.

[0167] [In-plane uniformity evaluation: Examples 1-1 to 1-102, Comparative Examples 1-1 to 1-33] Organic film-forming compositions (UDL-1 to 102, comparative UDL-1-1 to 1-33) were deposited on a silicon wafer using the method described above. The film thickness within a radius of 145 mm from the center of the cured organic film was measured, and the maximum film thickness Xmax, minimum film thickness Xmin, and average film thickness X average (X max -X min ) / X average The values ​​obtained were defined as in-plane uniformity (%), and the results are shown in Table 3. If the in-plane uniformity was less than 2%, it was classified as A (good); if it was between 2% and less than 3%, it was classified as B; and if it was 3% or more, it was classified as C (poor).

[0168] [Low-temperature storage stability evaluation: Examples 1-1 to 1-102, Comparative Examples 1-1 to 1-33] Organic film-forming compositions (UDL-1 to 102, comparative UDL-1-1 to 1-33) were stored in a freezer set to -20°C for one week. If no precipitate formed, the composition was considered good; if precipitate formed, it was considered poor. The results are shown in Table 3.

[0169] [Table 3-1]

[0170] [Table 3-2]

[0171] [Table 3-3]

[0172] [Table 3-4]

[0173] [Table 3-5]

[0174] [Hump suppression evaluation: Examples 2-1 to 2-102, Comparative Examples 2-1 to 2-25] Organic film-forming compositions (UDL-1 to 102, comparative UDL-1 to 6, 8, 10 to 14, 21 to 33) were deposited on silicon wafers using the method described above. The height change at a position from the outer edge of the organic film towards the center of the silicon wafer up to 1000 μm was measured using an Alpha-Step D-600 (contact profiler) manufactured by KLA-TENCOR. With the height of the silicon wafer set to 0, the results were evaluated as follows: A (good) if the maximum height was less than 110% of the film thickness, B if the maximum height was between 110% and 150%, and C (poor) if a region with a maximum height of 150% or more occurred, as shown in Figure 1. The results are shown in Table 4.

[0175] [Embedding Evaluation-1: Examples 2-1 to 2-102, Comparative Examples 2-1 to 2-25] As shown in Figure 4, organic film-forming compositions (UDL-1 to 102, comparative UDL-1 to 6, 8, 10 to 14, 21 to 33) were deposited on an SiO2 wafer substrate having a densely packed hole pattern (hole diameter 0.2 μm, hole depth 1.0 μm, distance between the centers of two adjacent holes 0.4 μm) using the method described above to form a resist underlayer film 8. The substrate used was a base substrate (SiO2 wafer substrate) 7 having a densely packed hole pattern as shown in Figure 4(G) (overhead view) and (H) (cross-sectional view). The cross-sectional shape of each obtained wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the resist underlayer film without any voids. When a resist underlayer film material with poor filling properties was used, voids were generated inside the holes. When a resist underlayer film material with good filling properties was used, the resist underlayer film was filled with the holes without any voids in this evaluation, as shown in Figure 4(I). If no voids were observed, the result was considered good; if voids were observed, the result was considered poor.

[0176] [Embedding Evaluation - 2: Examples 2-1 to 2-102, Comparative Examples 2-1 to 2-25] As shown in Figure 4, organic film-forming compositions (UDL-1 to 102, comparative UDL-1 to 6, 8, 10 to 14, 21 to 33) were deposited on an SiO2 wafer substrate having a dense hole pattern (hole diameter 0.2 μm, hole depth 2.0 μm, distance between the centers of two adjacent holes 0.4 μm) using the method described above to form a resist underlayer film 8. The substrate used was a base substrate (SiO2 wafer substrate) 7 having a dense hole pattern as shown in Figure 4(G) (overhead view) and (H) (cross-sectional view). The cross-sectional shape of each obtained wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the resist underlayer film without any voids. When a resist underlayer film material with poor filling properties was used, voids were generated inside the holes. When a resist underlayer film material with good filling properties was used, the resist underlayer film was filled with the holes without any voids in this evaluation, as shown in Figure 4(I). If no voids were formed, the result was considered good; if voids were formed, it was considered poor. In addition, if the ratio of the resin for forming the organic film to the organic film-forming composition was small, and the amount of resin was insufficient to fill the holes, film formation failure occurred.

[0177] [Table 4-1]

[0178] [Table 4-2]

[0179] [Table 4-3]

[0180] [Table 4-4]

[0181] [Table 4-5]

[0182] As shown in Tables 3-1 to 3-5 and Tables 4-1 to 4-5, the organic film-forming compositions (UDL-1 to 102) of the present invention were confirmed to be superior to the comparative examples in terms of solvent resistance, in-plane uniformity, hump suppression, and embedding characteristics.

[0183] [Pattern formation test: Examples 3-1 to 3-88] An organic cured film was formed on an SiO2 wafer substrate using an organic film-forming composition (UDL-1~88) as described above. The silicon-containing resist interlayer material (SOG1) described below was applied thereon and baked at 200°C for 60 seconds to form a silicon-containing resist interlayer with a thickness of 35 nm. The ArF single-layer resist described below was applied thereon as a resist top layer material and baked at 105°C for 60 seconds to form a photoresist film with a thickness of 100 nm. The immersion protective film material (TC-1) described below was applied on the photoresist film and baked at 90°C for 60 seconds to form a protective film with a thickness of 50 nm.

[0184] As silicon-containing resist interlayer material (SOG1), a 2% propylene glycol ethyl ether solution of the following polymers was prepared. [ka]

[0185] The resist top layer material (single-layer resist for ArF) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in the proportions shown in Table 5 in a solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Co., Ltd.), and filtering the mixture through a 0.1 μm fluororesin filter. [Table 5]

[0186] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) are shown below. [ka]

[0187] The immersion protective film material (TC-1) was prepared by dissolving the polymer (PP1) in an organic solvent in the proportions shown in Table 6 and filtering it through a 0.1 μm fluororesin filter. [Table 6]

[0188] The polymer (PP1) is shown below. [ka]

[0189] Next, the sample was exposed using an ArF immersion lithography system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s polarized illumination, 6% halftone phase shift mask), baked (PEB) at 100°C for 60 seconds, and developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 55 nm 1:1 positive-type line-and-space pattern (resist upper layer pattern).

[0190] Next, using the resist upper layer pattern as a mask, a silicon-containing resist interlayer was dry-etched (pattern transferred) using the Telius etching system manufactured by Tokyo Electron. The resulting silicon-containing resist interlayer pattern was then used as a mask to dry-etch (pattern transferred) an organic film. Finally, the resulting organic film pattern was used as a mask to dry-etch (pattern transferred) an SiO2 wafer substrate (SiO2 film). The etching conditions are as follows.

[0191] (Conditions for transferring the resist upper layer pattern to the silicon-containing resist interlayer) Chamber pressure 10.0 Pa RF Power 1,500W CF4 gas flow rate: 75 mL / min O2 gas flow rate: 15 mL / min Time 15sec

[0192] (Conditions for transferring silicon-containing resist interlayer patterns to organic films) Chamber pressure 2.0 Pa RF Power 500W Ar gas flow rate: 75 mL / min O2 gas flow rate: 45 mL / min Time 120sec

[0193] (Conditions for transferring organic film patterns onto SiO2 wafer substrates) Chamber pressure 2.0 Pa RF Power 2,200W C5F 12 Gas flow rate: 20 mL / min C2F6 gas flow rate: 10 mL / min Ar gas flow rate: 300 mL / min O2 gas flow rate: 60 mL / min Time 90sec

[0194] Tables 7-1 to 7-3 show the results of observing the cross-sections of the obtained patterns using an electron microscope (S-4700) manufactured by Hitachi, Ltd. [Table 7-1]

[0195] [Table 7-2]

[0196] [Table 7-3]

[0197] As shown in Tables 7-1 to 7-3, in Examples 3-1 to 3-88, which used the organic film-forming compositions (UDL-1 to 88) of the present invention, the resist upper layer film pattern was successfully transferred to the SiO2 wafer substrate in all cases, confirming that the organic film-forming compositions of the present invention are suitable for use in microfabrication using the multilayer resist method.

[0198] Based on the above, the organic film-forming composition of the present invention is extremely useful as an organic film material for use in multilayer resist processes because it has excellent film-forming properties, high embedding characteristics, and hump suppression. Furthermore, the pattern formation method of the present invention using this composition makes it possible to fill holes and trenches with very high aspect ratios without voids, form fine patterns with high precision, and form organic films with suppressed humps, thus enabling the efficient manufacture of semiconductor devices and the like.

[0199] This specification includes the following embodiments: [1]: An organic film-forming composition comprising an organic film-forming resin, a polymer comprising a structural unit represented by the following general formula (I), a structural unit represented by the following general formula (II), and a structural unit represented by the following general formula (III), and a solvent, wherein the structural unit represented by the following general formula (I), the structural unit represented by the following general formula (II), and the structural unit represented by the following general formula (III) form a random copolymer, and the fluorine content of the polymer is 5% to 16% by mass. [ka] (In the formula, R 1 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 2 This refers to an organic group containing a fluorine atom, with 1 to 20 carbon atoms, and that does not contain a sulfonyl group or an amino group. [ka] (In the formula, R 3R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 4 and R 5 Each of these is a divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched, R 6 (where m1 is a hydrogen atom or an alkyl group or phenyl group having 1 to 4 carbon atoms, m1 is 0 to 23, n1 is 0 to 23, and 23 ≥ m1 + n1 ≥ 2.) [ka] (In the formula, R 7 and R 8 R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 9 and R 10 Each of these groups is a divalent alkylene group with 1 to 4 carbon atoms, which can be either linear or branched. m2 has 0 to 23 carbon atoms, n2 has 0 to 23 carbon atoms, and 23 ≥ m2 + n2 ≥ 2. [2]: R of the structural unit represented by the general formula (I) of the polymer 2 An organic film-forming composition [1] characterized in that it contains a structure represented by the following general formula (IV) or (V). [ka] (In the formula, * indicates a bonding position.) [3]: The organic film-forming composition according to [1] or [2], characterized in that the resin for forming the organic film is a resin having an aromatic skeleton. [4]: The organic film-forming composition according to any one of [1] to [3], characterized in that the content of the polymer is 0.01 to 5 parts by mass, with 100 parts by mass of the organic film-forming resin. [5]: The organic film-forming composition according to any one of [1] to [4], characterized in that the content of the organic film-forming resin is 10 to 40 parts by mass, with the organic film-forming composition being 100 parts by mass. [6]: A method for forming an organic film used in the manufacturing process of a semiconductor device, characterized by rotating and coating an organic film forming composition described in any one of [1] to [5] onto a substrate to be processed, and then heat-treating the substrate coated with the organic film forming composition at a temperature of 100°C to 600°C for a range of 10 seconds to 600 seconds to form a cured film. [7]: A pattern formation method characterized by forming an organic film on a workpiece using an organic film forming composition described in any one of [1] to [5], forming a resist interlayer on the organic film using a resist interlayer material containing silicon atoms, forming a resist upper layer on the resist interlayer using a resist upper layer material made of a photoresist composition, forming a circuit pattern on the resist upper layer, transferring the pattern to the resist interlayer by etching using the resist upper layer on which the circuit pattern is formed as a mask, transferring the pattern to the organic film by etching using the resist interlayer on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask. [8]: A pattern formation method characterized by forming an organic film on a workpiece using an organic film forming composition described in any one of [1] to [5], forming a resist interlayer on the organic film using a resist interlayer material containing silicon atoms, forming an organic anti-reflective film or adhesion film on the resist interlayer, forming a resist upper layer on the organic anti-reflective film or adhesion film using a resist upper layer material made of a photoresist composition, forming a circuit pattern on the resist upper layer, transferring the pattern to the organic anti-reflective film or adhesion film and the resist interlayer by etching using the resist upper layer on which the circuit pattern is formed as a mask, transferring the pattern to the organic film by etching using the resist interlayer on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask. [9]: A pattern formation method characterized by forming an organic film on a workpiece using an organic film forming composition described in any one of [1] to [5], forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper film on the inorganic hard mask using a resist upper film material made of a photoresist composition, forming a circuit pattern on the resist upper film, transferring the pattern to the inorganic hard mask by etching using the resist upper film on which the circuit pattern is formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[10] : A pattern formation method characterized by forming an organic film on a workpiece using an organic film forming composition described in any one of [1] to [5], forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming an organic anti-reflective film or adhesion film on the inorganic hard mask, forming a resist upper film on the organic anti-reflective film or adhesion film using a resist upper film material made of a photoresist composition, forming a circuit pattern on the resist upper film, transferring the pattern to the organic anti-reflective film or adhesion film and the inorganic hard mask by etching using the resist upper film on which the circuit pattern is formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[11] : The pattern formation method of [9] or

[10] , characterized in that the inorganic hard mask is formed by CVD or ALD.

[12] : The pattern formation method according to any one of [7] to

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

[13] : The pattern formation method according to any one of [7] to

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

[14] : The pattern forming method according to any one of [7] to

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

[15] : The pattern forming method according to

[14] , characterized in that the metal constituting the workpiece is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0200] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0201] 1...Substrate, 2...Workpiece layer, 2a...Pattern formed on the workpiece layer 3...Organic film, 3a...Organic film pattern 4...Silicon-containing resist interlayer, 4a...Silicon-containing resist interlayer pattern, 5...Resist upper layer film, 5a...Resist upper layer film pattern, 6...Exposed area, 7…Underlayment substrate, 8…Resist underlayer film

Claims

1. An organic film-forming composition comprising an organic film-forming resin having an aromatic skeleton, a polymer comprising a structural unit represented by the following general formula (I), a structural unit represented by the following general formula (II), and a structural unit represented by the following general formula (III), and a solvent, wherein R2 of the structural unit represented by the following general formula (I) of the polymer comprises a structure represented by the following general formula (IV) or (V), 【Chemistry 1】 (In the formula, * indicates the bonding position.) An organic film-forming composition characterized in that a structural unit represented by the following general formula (I), at least one of the structural units represented by the following general formula (II) and the structural unit represented by the following general formula (III) form a random copolymer, and the fluorine content of the polymer is 5% to 16% by mass. 【Chemistry 2】 (In the formula, R １ R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ２ (This refers to an organic group containing a fluorine atom, having 1 to 20 carbon atoms, and not containing a sulfonyl group or an amino group.) 【Transformation 3】 (In the formula, R ３ R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ４ and R ５ Each of these is a divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched, R ６ (where m1 is an alkyl group or phenyl group having 1 to 4 carbon atoms, m1 is 0 to 23, n1 is 0 to 23, and 23 ≥ m1 + n1 ≥ 2.) 【Chemistry 4】 (In the formula, R ７ and R ８ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ９ and R １０ are each a divalent alkylene group having 1 to 4 carbon atoms which may be linear or branched, m2 is 0 to 23, n2 is 0 to 23, and 23 ≥ m2 + n2 ≥ 2.)

2. The organic film-forming composition according to claim 1, characterized in that the content of the polymer is 0.01 to 5 parts by mass, with 100 parts by mass of the organic film-forming resin.

3. The organic film-forming composition according to claim 1, characterized in that the organic film-forming composition is 100 parts by mass, and the content of the organic film-forming resin is 10 to 40 parts by mass.

4. A method for forming an organic film used in the manufacturing process of a semiconductor device, characterized by rotatingly coating a substrate to be processed with an organic film-forming composition according to any one of claims 1 to 3, and then heat-treating the substrate coated with the organic film-forming composition at a temperature of 100°C to 600°C for a period of 10 seconds to 600 seconds to form a cured film.

5. A pattern forming method characterized by forming an organic film on a workpiece using an organic film forming composition according to any one of claims 1 to 3; forming a resist interlayer on the organic film using a resist interlayer material containing silicon atoms; forming a resist upper layer on the resist interlayer using a resist upper layer material made of a photoresist composition; forming a circuit pattern on the resist upper layer; transferring the pattern to the resist interlayer by etching using the resist upper layer on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the resist interlayer on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

6. A method for forming a pattern, characterized by forming an organic film on a workpiece using an organic film forming composition according to any one of claims 1 to 3; forming a resist interlayer on the organic film using a resist interlayer material containing silicon atoms; forming an organic anti-reflective film or adhesion film on the resist interlayer; forming a resist upper film on the organic anti-reflective film or adhesion film using a resist upper film material made of a photoresist composition; forming a circuit pattern on the resist upper film; transferring the pattern to the organic anti-reflective film or adhesion film and the resist interlayer by etching using the resist upper film on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the resist interlayer on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

7. A pattern forming method characterized by forming an organic film on a workpiece using an organic film forming composition according to any one of claims 1 to 3; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a resist upper film on the inorganic hard mask using a resist upper film material made of a photoresist composition; forming a circuit pattern on the resist upper film; transferring the pattern to the inorganic hard mask by etching using the resist upper film on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

8. A pattern forming method characterized by forming an organic film on a workpiece using an organic film forming composition according to any one of claims 1 to 3; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming an organic anti-reflective film or an adhesion film on the inorganic hard mask; forming a resist upper film on the organic anti-reflective film or adhesion film using a resist upper film material made of a photoresist composition; forming a circuit pattern on the resist upper film; transferring the pattern to the organic anti-reflective film or adhesion film and the inorganic hard mask by etching using the resist upper film on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

9. The pattern forming method according to claim 7, characterized in that the inorganic hard mask is formed by a CVD method or an ALD method.

10. The pattern forming method according to claim 8, characterized in that the inorganic hard mask is formed by CVD or ALD.

11. The pattern formation method according to claim 5, characterized in that the circuit pattern is formed by lithography using light with a wavelength of 10 nm to 300 nm, direct drawing with an electron beam, nanoimprinting, or a combination thereof.

12. The pattern forming method according to claim 5, characterized in that the circuit pattern is developed using alkaline development or an organic solvent in the formation of the circuit pattern.

13. The pattern forming method according to claim 5, characterized in that the workpiece is a semiconductor device substrate, or a semiconductor device substrate on which any of the following films are formed: 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.

14. The pattern forming method according to claim 13, characterized in that the metal constituting the workpiece is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

Images