Thick film forming composition and method for producing cured film using the same

Abstract

A thick film forming composition comprising a hydrocarbon-containing compound (A) having a specific structure and a solvent (B): Here, the solvent (B) comprises an organic solvent (B1) and an organic solvent (B2) having a relative dielectric constant of 20.0 to 90.0; and the film formed from the thick film forming composition has a thickness of 0.5 to 10 μm.

Description

[Technical field]

[0001] The present invention relates to a thick film forming composition and a method for producing a cured film using the same. [Background technology]

[0002] In the manufacturing process of semiconductors, microfabrication is generally performed by lithography technology using photoresist (hereinafter, simply referred to as resist). The microfabrication process includes forming a thin photoresist layer on a semiconductor substrate such as a silicon wafer, covering the layer with a mask pattern corresponding to the pattern of the target device, exposing the layer to active light such as ultraviolet light through the mask pattern, obtaining a photoresist pattern by developing the exposed layer, and etching the substrate using the obtained photoresist pattern as a protective film, thereby forming fine irregularities corresponding to the above-mentioned pattern.

[0003] When using ultraviolet light with a single wavelength (e.g., 248 nm KrF light source), the problem of reduced dimensional accuracy of the resist pattern occurs due to the effect of standing waves. In order to solve this problem, a method of providing a bottom anti-reflection film has been widely studied. The characteristics required for such a bottom anti-reflection film include a high anti-reflection effect. To achieve even finer processing, methods using ArF light sources (193 nm) and EUV (13 nm) are being widely considered. In this case, if the resist film is too thick, the resist pattern is likely to collapse or develop residues are likely to be generated. Therefore, there is a problem that the resist alone does not provide sufficient protective film function. Therefore, a method known as multi-layering has become common, in which a new protective film is created under the photoresist, the photoresist pattern is transferred to the lower film, and the substrate is etched using this lower film as a protective film. There are various types of multi-layer protective films, and an amorphous carbon film is sometimes used as the protective film.

[0004] One method for improving the function of the protective carbon film by applying a solution and baking it is to apply a carbon film that can withstand baking at temperatures above 450° C., which is a common baking temperature, and bake it at, for example, 600° C. In addition, the function of the protective film can be improved by increasing the carbon concentration in the solid matter of the carbon film formation solution, but this generally involves a trade-off with other performance properties such as solubility.

[0005] In this technical situation, Patent Document 1 considers a method for forming a cured film by applying a composition containing an organic compound having an aromatic ring unit, heating the composition a first time in an atmosphere with an oxygen concentration of less than 10%, and then heating the composition a second time at a high temperature of, for example, 350°C in an atmosphere with an oxygen concentration of 10% or more. Patent Document 2 discusses a method of increasing the carbon concentration and improving etching resistance by applying a composition containing fullerene and curing it by heating at a high temperature of, for example, 350°C.

[0006] In the above study, a thin cured film of about 200 to 300 nm was examined, but it is required to produce a cured film having similar properties even in a thicker film than this range. It is more difficult to achieve a film quality that functions well as a protective film with a thicker film than with a thin film. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2014-219559 A [Patent Document 2] WO2018 / 115043 [Non-Patent Document 1] “Identification of high performance solvents for the sustainable processing of graphene”(HJSalavagione et al.,Green Chemistry 2017 Issue 19 p2550) Summary of the Invention [Problem to be solved by the invention]

[0008] The present inventors have considered that if it were possible to form a thick cured film that exhibits good properties even when heated at a low temperature, it would be useful in a manufacturing process. The present inventors have considered that there are one or more problems that still require improvement. These problems include, for example, the following: Obtaining a thick cured film; Obtaining a cured film by heating at a low temperature; Avoiding damage to other layers during the process; Obtaining a cured film with high film density; Obtaining a cured film with high film hardness; Obtaining a cured film with excellent indentation hardness; Obtaining a cured film with excellent indentation elastic modulus; Obtaining a cured film with high etching resistance; Obtaining a cured film with high resistance to ion implant treatment; Obtaining a cured film with little shrinkage even when subjected to ion implant treatment; Obtaining a cured film with excellent embedding properties; High solubility in solvents; Cured film with high flatness; Obtaining a composition with high viscosity; Promoting the curing reaction; Eliminating intermixing with the upper layer film and reducing diffusion of low molecular weight components into the upper layer film. [Means for solving the problem]

[0009] The thick film forming composition according to the present invention comprises a hydrocarbon-containing compound (A) and a solvent (B), Where: The hydrocarbon-containing compound (A) comprises a unit (A1) represented by the formula (A1): [ka] (where: Ar 11 is R 11 Substituted or unsubstituted C 6-60 It is a hydrocarbon R 11 is C 1-20 Alkyl, amino, or C 1-20 is alkylamino, R 12 is I, Br or CN, p 11 is a number between 0 and 5, and p 12 is a number between 0 and 1, and q11 is a number between 0 and 5, and q 12 is a number between 0 and 1, and r 11 is a number between 0 and 5, and s 11 is a number between 0 and 5, However, p 11 , q 11 and r 11 cannot be zero simultaneously within a unit); The solvent (B) comprises an organic solvent (B1) and an organic solvent (B2) having a relative dielectric constant of 20.0 to 90.0; and The film formed from the thick film forming composition has a thickness of 0.5 to 10 μm.

[0010] The method for producing a cured film according to the present invention comprises the following steps: (1) applying the composition described above over a substrate to form a hydrocarbon-containing film; and (2) Heating the hydrocarbon-containing film Where: The thickness of the cured film is 0.5 to 10 μm.

[0011] The method for producing a resist film according to the present invention comprises the following steps: A cured film is produced by the above method; (3) applying a resist composition over the cured film; and (4) The resist composition is heated to form a resist film.

[0012] The method for producing a resist pattern according to the present invention comprises the following steps: A resist film is produced by the above method. (5) exposing the resist film; and (6) The resist film is developed.

[0013] The method for producing a processed substrate according to the present invention comprises the following steps: Producing a resist pattern by the above method; and (7) Using the resist pattern as a mask, the layer below the resist pattern is processed.

[0014] A method for producing a device according to the present invention comprises the method described above. Effect of the Invention

[0015] By using the method for producing a cured film of the present invention, one or more of the following effects can be expected. A thick cured film can be obtained; A cured film can be obtained by heating at a low temperature; Damage to other layers in the process can be avoided; A cured film with high film density can be obtained; A cured film with high film hardness can be obtained; A cured film with excellent indentation hardness can be obtained; A cured film with excellent indentation elasticity can be obtained; A cured film with high etching resistance can be obtained; A cured film with high resistance to ion implant treatment can be obtained; A cured film with small shrinkage even after ion implant treatment can be obtained; A cured film with excellent embedding properties can be obtained; High solubility in solvents; High flatness of the cured film; A composition with high viscosity can be obtained; The curing reaction can be promoted by including an organic solvent with a high relative dielectric constant; It is possible to eliminate intermixing with the upper layer film or reduce the diffusion of low molecular weight components into the upper layer film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The embodiment of the present invention will be described in detail below.

[0017] [Definition] In this specification, unless otherwise specifically stated, the definitions and examples set forth in this paragraph shall be followed. The singular includes the plural, and "a" or "the" means "at least one." An element of a concept may be expressed by a plurality of species, and when an amount thereof (e.g., mass % or mole %) is stated, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of the elements as well as its use alone. When a numerical range is indicated using "~" or "-", it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less. "C x-y ", "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, these repeating units are copolymerized. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are shown by structural formulas, the n or m in parentheses indicates the number of repeats. Temperature is measured in degrees Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to a compound having that function (for example, in the case of a base generator, it is a compound that generates a base). The compound may be dissolved or dispersed in a solvent and added to the composition. In one embodiment of the present invention, such a solvent is preferably contained in the composition according to the present invention as the solvent (B) or another component.

[0018] [Thick film forming composition] The thick-film forming composition (hereinafter sometimes referred to as the composition) according to the present invention comprises a hydrocarbon-containing compound (A) having a specific structure and a solvent (B). Here, the solvent (B) comprises an organic solvent (B1) and an organic solvent (B2) having a relative dielectric constant of 20.0 to 90.0, and the thickness of the film formed from the thick-film forming composition is 0.5 to 10 μm (preferably 0.8 to 8 μm; more preferably 1.0 to 7.0 μm). The thick film forming composition according to the present invention is preferably a resist underlayer film forming composition. One example of the resist underlayer film forming composition is a bottom antireflective film forming composition. In one embodiment of the present invention, the thick film forming composition according to the present invention is preferably a spin-on carbon (SOC) film forming composition. Examples of SOC include SOC for hard masks and SOC for core materials. SOC is useful as a coating organic film (or mask) with high resistance to dry etching and ion implantation to protect a film or substrate present below.

[0019] (A) Hydrocarbon-containing compounds The composition according to the present invention comprises a hydrocarbon-containing compound (A) (hereinafter, sometimes referred to as component (A). The same applies to other components.) The hydrocarbon-containing compound (A) comprises a unit (A1) represented by formula (A1). Component (A) only needs to contain unit (A1), and it is permissible for it to contain other structural units. When component (A) contains other structural units and is a polymer, a preferred embodiment is that unit (A1) is copolymerized with other structural units. In a preferred embodiment of the present invention, component (A) is substantially composed of unit (A1) only. However, modification of the terminals is permissible.

[0020] Equation (A1) is as follows: [ka] Where: Ar 11 is R 11 Substituted or unsubstituted C 6-60 It is a hydrocarbon. 11 Preferably, Ar does not contain a naphthyl ring (more preferably does not contain a fused aromatic ring). 11 9,9-diphenylfluorene, 9-phenylfluorene, phenyl, C 6-60 Linear polyphenylene and C 6-60 branched polyphenylenes, each of which is independently R 11 may be substituted or unsubstituted with Ar 11 In a preferred embodiment of the present invention, is unsubstituted. R 11 is C 1-20Alkyl, amino, or C 1-20 R is an alkylamino group, where the alkyl group may be linear, branched, or cyclic. 11 is preferably C 1-10 Alkyl, or C 1-10 Alkylamino (more preferably C 1-3 Straight chain alkyl, C 1-3 branched alkyl, cyclopentyl, cyclohexyl, or dimethylamino). R 12 is I, Br or CN (preferably I or Br; more preferably I). p 11 is a number from 0 to 5. In one embodiment of the present invention, the component (A) may have only one of each of the two types of units (A1) as a constituent. 11 are both phenyl and one Ar 11 Related to p 11 = 1, and the other Ar 11 Related to p 11 = 2. In this case, p 11 = 1.5. In this specification, the same applies to numbers unless otherwise specified. 11 is preferably 0, 1, 2 or 3 (more preferably 0, 1 or 2; even more preferably 1). 11 =0 is also a preferred embodiment of the present invention. p 12 is a number from 0 to 1 (preferably 0 or 1; more preferably 1). q 11 is a number from 0 to 5 (preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; even more preferably 1). 11 =0 is also a preferred embodiment of the present invention. q 12 is a number from 0 to 1 (preferably 0 or 1; more preferably 1). r 11 is a number from 0 to 5 (preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; and even more preferably 1). 11 =0 is also a preferred embodiment of the present invention. s 11is a number from 0 to 5 (preferably 0, 1, 2 or 3; more preferably 0, 1 or 2; and even more preferably 1). 11 =0 is also a preferred embodiment of the present invention. However, p 11 , q 11 and r 11 are never simultaneously zero within one unit. When component (A) has multiple units (A1), R 11 Ar is used as a linker. 11 One Ar may be bonded to another. 11 Replace R 11 may be one or more; preferably it is one. In one unit (A1), the group enclosed in brackets (e.g., p 11 (group enclosed in brackets with R 11 In this case, the group may be bonded to Ar 11 R 11 acts as a linker to bind.

[0021] For example, the compound on the left below can be interpreted as a component (A) composed of two units (A1). 11 is 9-phenylfluorene, and the other unit (A1) is Ar 11 is 9,9-diphenylfluorene. In each unit (A1), p 11 = 1, and q 11 =r 11 =s 11 = 0. As shown on the right side below, in each of the two units (A1), one bond, indicated by an arrow, is not used to bond to the other unit. [ka]

[0022] Formula (A1) is preferably formula (A1-1), (A1-2), (A1-3) and / or (A1-4).

[0023] Formula (A1-1) is as follows. [ka] Where: Ar 21 is C 6-50 It is an aromatic hydrocarbon group. Without being bound by theory, it is expected that Ar can ensure the solubility of component (A) in the solvent and form a thick film, and other advantageous effects can be expected. 21 is preferably phenyl. 21 preferably does not contain a fused aromatic ring. R 21 , R 22 and R 23 are each independently 6-50 It is a single bond that connects to an aromatic hydrocarbon group, hydrogen, or other structural unit. Preferably, R 21 , R 22 and R 23 does not contain naphthyl (more preferably a condensed aromatic ring). 21 , R 22 and R 23 is preferably phenyl, hydrogen, or a single bond bonded to another structural unit (more preferably a single bond bonded to a phenyl or other structural unit; even more preferably phenyl). n21 is 0 or 1 (preferably 0). R 12 , p 11 , p 12 , q 11 , q 12 , r 11 and s 11 The definitions and preferred examples of are independently the same as above.

[0024] Examples of the component (A) having the structure of formula (A1-1) include the following: [ka]

[0025] For example, the compound on the left below can be understood as a component (A) composed of two units represented by formula (A-1). In one structure of formula (A-1), R21 is a single bond to another structural unit, and Ar 21 is 9,9-diphenylfluorene, and p 11 = 2, and q 11 =r 11 =s 11 = 0. 11 The bracketed groups with the subscript are all Ar 21 In the other structure of formula (A-1), R 21 is hydrogen, and Ar 21 is 9,9-diphenylfluorene, and p 11 = 2, and q 11 =r 11 =s 11 = 0. 11 All groups enclosed in are Ar 21 Bind to. [ka]

[0026] In a further preferred embodiment of the present invention, the unit (A1-1) is the unit (A1-1-1): The structural unit (A1-1-1) is represented by the formula (A1-1-1). [ka] p 11 , p 12 , q 11 , q 12 , r 11 and s 11 The definitions and preferred examples of are the same as above, provided that 1≦p 11 +q 11 +r 11 Satisfying ≦4.

[0027] Formula (A1-2) is as follows. [ka] Where: L 31 and L 32are each independently a single bond or phenylene (preferably a single bond). n 31 , n 32 , m 31 and m 32 are each independently 0 to 6 (preferably 0, 1, 2, or 3). 31 +n 32 = 5 or 6 is a preferred embodiment. 31 When is a single bond, m 31 = 1. 32 When is a single bond, m 32 =1. R 12 , p 11 , p 12 , q 11 , q 12 , r 11 and s 11 The definitions and preferred examples of are independently the same as above.

[0028] Examples of the component (A) having the structure of formula (A1-2) include the following: [ka]

[0029] Formula (A1-3) is as follows. [ka] Where: Ar 41 is C 6-50 It is an aromatic hydrocarbon group (preferably phenyl). R 41 and R 42 are each independently C 1-10 Alkyl (preferably straight-chain C 1-6 alkyl), and R 41 and R 42 may be bonded together to form a ring (preferably a saturated hydrocarbon ring). *The carbon atom at position 41 is a quaternary carbon atom. L 41 is C 6-50It is an arylene, or a single bond bonded to another structural unit (preferably a phenylene or a single bond bonded to another structural unit; more preferably a single bond bonded to another structural unit). R 12 , p 11 , p 12 , q 11 , q 12 , r 11 and s 11 The definitions and preferred examples of are the same as those described above.

[0030] Examples of component (A) having formula (A1-3) include the following: [ka]

[0031] Formula (A1-4) is as follows. [ka] Here, y is 0 to 2 (preferably 0.5 to 1.5; more preferably 0 or 1). Formula (A1-4) is preferably formula (Q-1a), (Q-1b), (Q-1c), or (Q-1d). [ka]

[0032] In a preferred embodiment, component (A) is a polymer comprising units selected from the group consisting of formulae (Q-1a), (Q-1b), (Q-1c), and (Q-1d) (hereinafter, sometimes referred to as polymer Q). More preferably, polymer Q consists only of units selected from the group consisting of formulae (Q-1a), (Q-1b), (Q-1c), and (Q-1d), and more preferably, consists only of repeating units of formulae (Q-1a) and (Q-1b).

[0033] In the polymer Q, the number Nqa of the repeating units of (Q-1a), the number Nqb of the repeating units of (Q-1b), the number Nqc of the repeating units of (Q-1c), and the number Nqd of the repeating units of (Q-1d) are expressed by the following formula: 30%≦Nqa / (Nqa+Nqb+Nqc+Nqd)≦100%; 0%≦Nqb / (Nqa+Nqb+Nqc+Nqd)≦70%; 0%≦Nqc / (Nqa+Nqb+Nqc+Nqd)≦50%; and 0%≦Nqd / (Nqa+Nqb+Nqc+Nqd)≦70% It is preferable that the following is satisfied. Nqa / (Nqa+Nqb+Nqc+Nqd) is more preferably 30 to 90% (even more preferably 40 to 80%; even more preferably 50 to 70%). Nqb / (Nqa+Nqb+Nqc+Nqd) is more preferably 10 to 60% (even more preferably 20 to 50%; even more preferably 30 to 50%). Nqc / (Nqa+Nqb+Nqc+Nqd) is more preferably 0 to 40% (even more preferably 10 to 30%). It is also a suitable embodiment that Nqc / (Nqa+Nqb+Nqc+Nqd) is 0%. Nqd / (Nqa+Nqb+Nqc+Nqd) is more preferably 0 to 40% (still more preferably 10 to 30%). A preferred embodiment is one in which Nqd / (Nqa+Nqb+Nqc+Nqd) is 0%. A preferred embodiment is also one in which the polymer Q has either one of the repeating units of formula (Q-1c) and (Q-1d) and does not have the other.

[0034] The weight average molecular weight (hereinafter sometimes referred to as Mw) of polymer Q is preferably 400 to 100,000 (more preferably 5,000 to 75,000; even more preferably 6,000 to 50,000; even more preferably 9,000 to 20,000). In the present invention, Mw can be measured by gel permeation chromatography (GPC). In this measurement, a preferred example is to use a GPC column at 40° C., an elution solvent of tetrahydrofuran at 0.6 mL / min, and monodisperse polystyrene as a standard. The same applies hereinafter.

[0035] Component (A) is preferably a polymer. When component (A) is a polymer containing a unit represented by formula (A1-1), (A1-2) or (A1-3), in a preferred embodiment of the present invention, the aldehyde derivative used when synthesizing component (A) is preferably 0 to 30 mol% (more preferably 0 to 15 mol%; even more preferably 0 to 5 mol%; even more preferably 0 mol%) based on the sum of all elements used in the synthesis. An example of the aldehyde derivative is formaldehyde. In one preferred embodiment of the present invention, a ketone derivative is used instead of an aldehyde derivative. The polymer thus synthesized may be characterized by having no or few secondary and tertiary carbon atoms in the main chain. In a preferred embodiment of the present invention, the polymer is substantially free of secondary and tertiary carbon atoms in the main chain. Without being bound by theory, this is expected to ensure the solubility of the polymer while improving the heat resistance of the film formed. However, it is acceptable for the polymer to have secondary and tertiary carbon atoms at its terminal, as in terminal modification. Without being bound by theory, it is believed that the inclusion of component (A) can harden the film formed from the composition and improve its etching resistance. Examples of such component (A) include those in which unit (A1) is represented by formula (A1-1), formula (A1-2) and / or formula (A1-3). Without being bound by theory, it is believed that the inclusion of component (A) can increase the viscosity of the composition and can increase the crack resistance of the film formed from the composition. Examples of such component (A) include those in which unit (A1) is represented by formula (A1-4).

[0036] In one embodiment of the present invention, the molecular weight of component (A) is preferably 400 to 100,000 (more preferably 1,000 to 5,000; further preferably 2,000 to 20,000). When component (A) is a polymer, Mw is used to represent the molecular weight. In component (A), the substance containing a unit represented by formula (A1-1), (A1-2) or (A1-3) preferably has a molecular weight of 500 to 6,000 (more preferably 500 to 4,000; even more preferably 1,500 to 3,000).

[0037] Component (A) may be one or more types. Component (A) preferably comprises a structure of formula (A1-1), (A1-2) or (A1-3), more preferably comprises a structure of formula (A1-1). When component (A) is two or more types, component (A) preferably comprises a combination of a compound having a structure of formula (A1-1), (A1-2) or (A1-3) and polymer Q, and more preferably comprises a combination of a compound having a structure of formula (A1-1) and polymer Q.

[0038] The content of component (A) is preferably 3 to 40 mass % (more preferably 10 to 35 mass %; further preferably 20 to 30 mass %) based on the composition.

[0039] (B) Solvent The composition according to the present invention comprises a solvent (B). The solvent (B) comprises an organic solvent (B1) and an organic solvent (B2) having a relative dielectric constant of 20.0 to 90.0. The organic solvent (B1) preferably has a relative dielectric constant other than 20.0 to 90.0; more preferably has a relative dielectric constant less than 20; even more preferably has a relative dielectric constant of 1 to 19; and even more preferably has a relative dielectric constant of 5 to 15. The organic solvent (B2) has a relative dielectric constant of preferably 25 to 50 (more preferably 30 to 40; further preferably 35 to 40). The dielectric constant can be measured by the LCR meter method. For example, it can be calculated using an LCR meter HP4284A (Agilent Technologies) at a measurement frequency of 1 MHz and 20°C.

[0040] By including the solvent (B2) with a high dielectric constant in the solvent (B), a cured film with high hardness can be obtained even if the film is thick and heated at a low temperature. Without being bound by theory, it is believed that the presence of the solvent (B2) promotes the curing reaction. For example, it is believed that the intermediate is more likely to be generated in the curing reaction, the intermediate is more stable, or the range of movement of the component (A) is more likely to be expanded.

[0041] The boiling point of the organic solvent (B2) at 1 atmospheric pressure is preferably 100 to 400° C. (more preferably 150 to 250° C.; further preferably 190 to 250° C.). The Δp / (ΔD+Δp+ΔH) of the organic solvent (B2) is preferably 20 to 50% (more preferably 20 to 40%; further preferably 30 to 40%). ΔD, Δp and ΔH are the three parameters of the Hansen solubility parameter. The Hansen solubility parameter can be obtained by a known method. For example, the method described in Non-Patent Document 1 can be used. Examples of organic solvents (B2) and their boiling points, relative dielectric constants, and δp / (δD+δp+δH) are listed in the table below. [Table 1]

[0042] The organic solvent (B1) is not particularly limited, except for the organic solvent (B2). The organic solvent (B1) is a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or a mixture thereof. Examples of the organic solvent (B1) include propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monomethyl ether (PGME), anisole, ethyl lactate (EL), n-butyl acetate (nBA), n-butyl ether (DBE), or a mixture thereof. The organic solvent (B1) is preferably PGMEA, PGME, or a mixture thereof (more preferably a mixture of PGMEA and PGME). When two types are mixed, the mass ratio is preferably 95:5 to 5:95 (more preferably 90:10 to 10:90; even more preferably 80:20 to 20:80).

[0043] The solvent (B) may contain a solvent other than the organic solvent (B1) and the organic solvent (B2), such as water. In relation to other layers or films, it is also a favorable embodiment that the solvent (B) does not substantially contain water. The amount of water in the entire (B) solvent is preferably 0.1 mass % or less (more preferably 0.01 mass % or less; even more preferably 0.001 mass % or less). It is also a suitable embodiment that the solvent (B) does not contain water (0.000 mass %).

[0044] The content of the solvent (B) is preferably 50 to 97 mass % (more preferably 60 to 90 mass %; further preferably 65 to 80 mass %) based on the composition. The content of the organic solvent (B1) is preferably 70 to 99 mass % (more preferably 80 to 99 mass %; further preferably 90 to 98 mass %) based on the solvent (B). The content of the organic solvent (B2) is preferably 1 to 20 mass % (more preferably 1 to 15 mass %; further preferably 2 to 10 mass %) based on the solvent (B).

[0045] (C) A component comprising a crosslinking group The composition according to the present invention may further include a component (C) containing a crosslinking group. The component (C) is a component different from the components (A) represented by formulae (A1-1), (A1-2), (A1-3) and (A1-4). In other words, when the component (C) meets the definition of the component (A), even if it has a crosslinking group, it is the component (A) and not the component (C). Bridging groups include, for example, hydroxy, methoxy, acryloyloxy, methacryloyloxy, ethenyl, ethenyloxy, 2-propenyl, 1-propenyl, and the like. Without being bound by theory, it is believed that component (C) contributes to improving density when a cured film is formed, and can eliminate intermixing with an overlying film (e.g., a resist film) and reduce diffusion of low molecular weight components into the overlying film.

[0046] The component (C) comprising a crosslinking group is preferably represented by formula (C1). [ka] Where: n c1 is 1, 2, 3, or 4 (preferably 1, 2, or 3; more preferably 1 or 2). n c2 is n c1 is 0 when is 1, and n c1 is 1 when is 2 or more. n c3 is 0, 1, or 2 (preferably 2). n c4 is 1 or 2 (preferably 1). n c5 is 0 or 1 (preferably 0). L c is a single bond, or C 1-30 Hydrocarbon group (preferably a single bond, C 1-20 Alkylene, C 6-30 arylene; more preferably a single bond). R c are each independently 1-6 Alkyl, or C 6-10R is an aryl, and a methylene in the alkyl is or is not replaced by -O-. c is preferably methyl or phenyl. R' is hydrogen or methyl (preferably methyl).

[0047] Examples of component (C) include the following: [ka] [ka]

[0048] The content of component (C) is preferably 0 to 30 mass% (more preferably 1 to 20 mass%; even more preferably 5 to 15 mass%) based on the sum of the contents of components (A) and (E) (when component (E) is not included, this means the content of component (A); the same applies below).

[0049] (D) Acid generator The composition according to the present invention may further comprise an acid generator (D). Component (D) is useful from the viewpoint of improving heat resistance (accelerating the crosslinking reaction).

[0050] Component (D) includes thermal acid generators (TAGs) capable of generating strong acids by heating. Preferred thermal acid generators are those that are activated at temperatures above 80°C. Examples of thermal acid generators are metal-free sulfonium and iodonium salts, such as triarylsulfonium, dialkylarylsulfonium, and diarylalkylsulfonium salts of strong non-acidophiles, alkylaryliodonium, diaryliodonium salts of strong non-acidophiles; and ammonium, alkylammonium, dialkylammonium, trialkylammonium, and tetraalkylammonium salts of strong non-acidophiles. Covalent thermal acid generators are also considered as useful additives, such as 2-nitrobenzyl esters of alkyl or aryl sulfonic acids and other esters of sulfonic acids that thermally decompose to give free sulfonic acids. Examples are diaryliodonium perfluoroalkylsulfonates, diaryliodonium tris(fluoroalkylsulfonyl)methides, diaryliodonium bis(fluoroalkylsulfonyl)methides, diaryliodonium bis(fluoroalkylsulfonyl)imides, diaryliodonium quaternary ammonium perfluoroalkylsulfonates. Examples of unstable esters are 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, 4-nitrobenzyl tosylate; benzenesulfonates such as 2-trifluoromethyl-6-nitrobenzyl 4-chlorobenzenesulfonate, 2-trifluoromethyl-6-nitrobenzyl 4-nitrobenzenesulfonate; phenolic sulfonate esters such as phenyl 4-methoxybenzenesulfonate; quaternary ammonium tris(fluoroalkylsulfonyl)methides, and quaternary alkylammonium bis(fluoroalkylsulfonyl)imides, alkylammonium salts of organic acids, such as the triethylammonium salt of 10-camphorsulfonic acid. A variety of aromatic (anthracene, naphthalene, or benzene derivative) sulfonic acid amine salts can be used as the TAGs, including those disclosed in US Pat. Nos. 3,474,054, 4,200,729, 4,251,665, and 5,187,019.

[0051] The content of component (D) is preferably 0 to 5 mass % (more preferably 0.1 to 3 mass %; further preferably 0.5 to 2 mass %) based on the total content of components (A) and (E).

[0052] (E) Polymer The composition according to the present invention may further comprise a polymer (E). For clarity, the polymer (E) is different from other components in the composition, such as components (A) and (F). The polymer (E) may be, but is not limited to, styrene, hydroxystyrene, or a copolymer of either of these. The content of polymer (E) is preferably 0 to 300 mass% (more preferably 0.1 to 50 mass%; further preferably 0.1 to 10 mass%) based on component (A). A preferred embodiment of the present invention is one in which no polymer (E) is contained (0.0 mass%). The Mw of the polymer (E) is preferably from 1,000 to 100,000 (more preferably from 2,000 to 10,000).

[0053] (F) High carbon material The composition according to the present invention may further include (F) a high carbon material. By adding component (F), the composition as a whole can satisfy formula (X) described below, and a cured film with excellent etching resistance can be formed. For clarity, component (F) is different from other components in the composition. For example, component (F) is different from component (A) containing structures represented by formulas (A1-1), (A1-2), (A1-3) and (A1-4). For example, component (F) is different from component (C) represented by formula (C1). Component (F) may be a low molecular weight or a high molecular weight, and is preferably composed only of carbon (C), oxygen (O) and hydrogen (H), more preferably composed only of carbon (C) and hydrogen (H). Without being bound by theory, by including component (F) in the composition of the present invention, a thick film with better etching resistance can be obtained.

[0054] The high carbon material (F) is preferably represented by the formula (F1). [ka] Where: Ar1 is a single bond, C 1-6 Alkyl, C 6-12 Cycloalkyl, or C 6-14 Aryl (preferably a single bond, C 1~6 alkyl or phenyl; more preferably a single bond, a straight chain C3 alkyl, a straight chain C6 alkyl, tertiary butyl or phenyl; even more preferably a single bond or phenyl). Ar2 is C 1-6 Alkyl, C 6-12 Cycloalkyl, or C 6-14 Aryl (preferably isopropyl, tertiary butyl, C6 cycloalkyl, phenyl, naphthyl, phenanthryl or biphenyl; more preferably phenyl). R f1 and R f2 are each independently 1-6 It is alkyl, hydroxy, halogen, or cyano (preferably, methyl, ethyl, propyl, isopropyl, tertiary butyl, hydroxy, fluorine, chlorine or cyano; more preferably, methyl, hydroxy, fluorine or chlorine). R f3 is hydrogen, C 1-6 Alkyl, or C 6-14 Aryl (preferably hydrogen, C 1~6 alkyl or phenyl; more preferably hydrogen, methyl, ethyl, straight chain C5 alkyl, tertiary butyl or phenyl; even more preferably hydrogen or phenyl; still more preferably hydrogen). However, Ar2 is C 1-6 Alkyl or C 6-14 Aryl and R f3 C 1-6 Alkyl or C 6-14 If it is aryl, Ar2 and R f3 may be bonded to each other to form a ring. Each of r and s is independently 0, 1, 2, 3, 4 or 5 (preferably 0 or 1; more preferably 0). At least one of the Cy3, Cy4 and Cy5 rings surrounded by dashed lines is an aromatic hydrocarbon ring fused with the adjacent aromatic hydrocarbon ring Ph7, and the number of carbon atoms in the aromatic hydrocarbon ring, including the carbon atom in the aromatic hydrocarbon ring Ph7, is C 10-14 Preferably, C 10 It is more preferable that: At least one of the rings Cy6, Cy7, and Cy8 surrounded by dashed lines is an aromatic hydrocarbon ring fused with an adjacent aromatic hydrocarbon ring Ph8, and the number of carbon atoms in the aromatic hydrocarbon ring, including the carbon atom in the aromatic hydrocarbon ring Ph8, is C 10~14 Preferably, C 10 It is even more preferable that: In formula (F1), R f1 , R f2 The bonding position of OH is not limited.

[0055] For example, the following compound can have the following structure in formula (F1): The aromatic hydrocarbon ring Ph7 and the aromatic hydrocarbon ring Cy5 are condensed to form a naphthyl ring, and OH is bonded to the aromatic hydrocarbon ring Cy5. In addition, Ar1 is a single bond, and Ar2 and R f3 is phenyl, and A r2 and R f3 are linked to form a hydrocarbon ring (fluorene). [ka]

[0056] Specific examples of the high carbon material represented by formula (F1) include the following. [ka]

[0057] The content of component (F) is preferably 0 to 200 mass% (more preferably 0 to 75 mass%; even more preferably 1 to 50 mass%; still more preferably 15 to 30 mass%) based on the total content of components (A) and (E). A preferred embodiment of the present invention is one in which component (F) is not contained (0.0 mass%).

[0058] (G) Surfactants The composition according to the present invention may further comprise a surfactant (G). By including the component (G), the coating properties can be improved. Surfactants that can be used in the present invention include (I) anionic surfactants, (II) cationic surfactants, and (III) nonionic surfactants. More specifically, (I) alkylsulfonates, alkylbenzenesulfonic acids, and alkylbenzenesulfonates, (II) laurylpyridinium chloride and laurylmethylammonium chloride, and (III) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, and polyoxyethylene acetylenic glycol ether, fluorine-containing surfactants such as Fluorad (Sumitomo 3M), MEGAFACE (DIC), Sulfuron (Asahi Glass), or organosiloxane surfactants (e.g., KP341, Shin-Etsu Chemical Co., Ltd.) are preferred.

[0059] The content of component (G) is preferably 0 to 20 mass % (more preferably 0 to 2 mass %; even more preferably 0.01 to 1 mass %) based on the total content of components (A) and (E).

[0060] (H) Additives The composition according to the present invention may further contain an additive (H) other than the above components. The additive (H) is preferably selected from the group consisting of an acid, a base, a radical generator, a photopolymerization initiator, and a substrate adhesion enhancer. The content of component (H) is preferably 0 to 10 mass% (more preferably 0.001 to 10 mass%; further preferably 0.001 to 5 mass%) based on the total content of components (A) and (E). In one preferred embodiment of the present invention, the composition does not contain component (H) (0%).

[0061] The composition according to the present invention preferably has a high carbon content in the solid components contained therein. That is, when one or more solid components contained in the composition (the total of the solid components in the composition) satisfy the following formula (X), the carbon content is high and is preferable. For example, when the thick-film forming composition has three solid components, namely, a hydrocarbon-containing compound (A), a polymer (E) and a surfactant (G), it is preferable that the solid components as a whole satisfy formula (X). It can be calculated using a molar ratio. 1.5≦{total number of atoms / (number of C-number of O)}≦3.5 Formula (X) Where: The number of C is the number of carbon atoms, and The number of O's is the number of oxygen atoms. Preferably, formula (X) is formula (X)' or formula (X)''. 1.5≦{Total number of atoms / (Number of C-Number of O)}≦2.4 Formula (X)' 1.8≦{Total number of atoms / (Number of C-Number of O)}≦2.4 Formula (X)''

[0062] [Method of manufacturing the cured film] The method for producing a cured film according to the present invention comprises the following steps. (1) applying the composition according to the present invention above a substrate to form a hydrocarbon-containing film; and (2) heating the hydrocarbon-containing film; Here, the thickness of the cured film is 0.5 to 10 μm (preferably 1 to 8 μm; more preferably 1.5 to 5 μm; even more preferably 2 to 4 μm). In the following, the numbers in parentheses indicate the order of the steps. For example, when steps (1), (2), and (3) are described, the order of the steps is as described above.

[0063] Process (1) Examples of the substrate include a semiconductor wafer, a glass substrate for a liquid crystal display device, a glass substrate for an organic electroluminescence display device, a glass substrate for a plasma display device, a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, a glass substrate for a photomask, and a substrate for a solar cell. The substrate may be a flat substrate or a non-flat substrate that has been processed, but is preferably a non-flat substrate. The substrate may be formed by laminating a plurality of layers. The surface of the substrate is preferably a semiconductor. The semiconductor may be formed of an oxide, a nitride, a metal, or any combination thereof. In addition, the surface of the substrate is preferably selected from the group consisting of Si, Ge, SiGe, Si3N4, TaN, SiO2, TiO2, Al2O3, SiON, HfO2, Ta2O5, HfSiO4, Y2O3, GaN, TiN, TaN, Si3N4, NbN, Cu, Ta, W, Hf, and Al. The composition according to the present invention is applied above the substrate by a suitable method. In the present invention, above includes the case where the composition is formed directly above the substrate and the case where the composition is formed via another layer. The application method is not particularly limited, but examples thereof include a method of coating with a spinner or coater, thereby forming a hydrocarbon-containing film.

[0064] Process (2) A cured film is produced by heating the hydrocarbon-containing film. The heating temperature in (2) is preferably less than 340°C (more preferably 70 to 330°C). The temperature here is the temperature of the heating atmosphere, for example, the heating surface of a hot plate. The heating time is preferably 30 to 300 seconds (more preferably 60 to 240 seconds). Heating can also be performed in multiple steps (step baking). Preferably, the heating in (2) is performed in two stages, the first one at 70 to 330°C and the second one at 200 to 330°C. When two-stage heating is performed, it is preferable that the first one is performed for 30 to 120 seconds and the second one for 60 to 180 seconds. When two-stage heating is performed, it is preferable that the temperature in the second stage is higher than that in the first stage. When two-stage heating is performed, it is preferable that the time for the second stage is longer than that for the first stage. Generally, high-temperature heating can promote the curing reaction and contribute to densifying the cured film. Without being bound by theory, according to the present invention, densifying the cured film can be achieved without high-temperature heating. Air is a suitable atmosphere for heating. The oxygen concentration can be reduced to prevent oxidation of the hydrocarbon-containing film. For example, an inert gas (N2, Ar, He or a mixture thereof) can be injected into the atmosphere to reduce the oxygen concentration to 1,000 ppm or less (preferably 100 ppm or less).

[0065] The surface resistivity of the cured film is preferably 10 9 ~10 16 The surface resistivity is preferably 10 12 ~10 16 Ω□; more preferably 10 13 ~10 16 The cured film formed is not a conductive polymer film.

[0066] [Method of manufacturing resist film and resist pattern] A resist film can be produced on the cured film produced by the method according to the present invention. The method for producing the resist film comprises the following steps. Producing a cured film by the method described above; (3) applying a resist composition over the cured film; and (4) The resist composition is heated to form a resist film. A resist pattern can also be produced from the resist film produced by the method according to the present invention. The method for producing a resist pattern according to the present invention comprises the following steps. A resist film is produced by the method described above. (5) exposing the resist film; and (6) The resist film is developed.

[0067] Steps (3) and (4) A resist composition is applied onto the cured film by an appropriate method. The application method is not particularly limited, but examples include coating methods using a spinner or a coater. After application, the resist film is formed by heating. The heating in (4) is performed, for example, by a hot plate. The heating temperature is preferably 100 to 250°C. The temperature here refers to the heating atmosphere, for example, the heating surface temperature of a hot plate. The heating time is preferably 30 to 300 seconds (more preferably 60 to 180 seconds). Heating is preferably performed in air or nitrogen gas atmosphere. The thickness of the resist film is selected according to the purpose. It is possible to make the resist layer thicker than 1 μm.

[0068] Process (5) The resist film is exposed through a predetermined mask. The wavelength of light used for exposure is not particularly limited, but it is preferable to use light having a wavelength of 190 to 440 nm. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), g-line (wavelength 436 nm), etc. can be used. The wavelength is more preferably 240 to 440 nm, even more preferably 360 to 440 nm, and even more preferably 365 nm. These wavelengths are allowed to have a range of ±1%.

[0069] After exposure, post exposure bake (hereinafter sometimes referred to as PEB) may be optionally performed. The post exposure bake is performed, for example, by using a hot plate. The temperature of the post exposure bake is preferably 80 to 160°C (more preferably 105 to 115°C), and the heating time is 30 to 600 seconds (preferably 60 to 200 seconds). The heating is preferably performed in air or nitrogen gas atmosphere.

[0070] Process (6) After exposure (PEB as necessary), development is performed using a developer to produce a resist pattern. As the development method, a method conventionally used for developing photoresists, such as a paddle development method, an immersion development method, and a swing immersion development method, can be used. As the developer, an aqueous solution containing an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium silicate, an organic amine such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol, or triethylamine, or a quaternary amine such as tetramethylammonium hydroxide (TMAH), is used, and preferably a 2.38 mass % TMAH aqueous solution. A surfactant can also be added to the developer. The temperature of the developer is preferably 5 to 50°C (more preferably 25 to 40°C), and the development time is preferably 10 to 300 seconds (more preferably 30 to 60 seconds). After development, washing with water or a rinsing treatment can be performed as necessary.

[0071] [Method of manufacturing processed substrates] A processed substrate can be manufactured using the resist pattern manufactured by the method according to the present invention. The method for manufacturing a processed substrate according to the present invention comprises the following steps. Producing a resist pattern by the method described above; and (7) Using the resist pattern as a mask, the layer below the resist pattern is processed. The processing in (7) above includes not only structural changes, but also physical or chemical changes. For example, in the following process (7a), the structural change caused by etching the lower layer corresponds to processing. In the following processes (7b) and (7c), for example, the physical properties of the target are changed by ion implantation.

[0072] A processed substrate can be manufactured by performing dry etching using the resist pattern manufactured by the method according to the present invention as a mask. Thus, in a preferred embodiment, the method for manufacturing a processed substrate according to the present invention comprises the following steps: Producing a resist pattern by the method described above; and (7a) Using the resist pattern as a mask, the lower layer is dry etched. Preferably, the lower layer of (7a) is a cured film, an intermediate layer, or a substrate (more preferably a substrate). The intermediate layer may be present between the resist pattern and the cured film of the present invention, or between the cured film and the substrate. More preferably, the intermediate layer is the latter, and examples of such intermediate layers include a SiON film and a spin-on-glass film. In (7a), it is also a preferred embodiment of the present invention to use a resist pattern as a mask to etch the cured film of the present invention to form a cured film pattern, and then etch a substrate using the cured film pattern as a mask. It is also a preferred embodiment of the present invention to directly etch a substrate using a resist pattern as a mask. In (7a), it is also a preferred embodiment of the present invention to use a resist pattern as a mask to etch an intermediate layer to form an intermediate layer pattern, and then etch a substrate using the intermediate layer pattern as a mask. The gas in step (7a) is preferably O2, CF4, Ar, CHF3, Cl2, BCl3, or a mixture of any of these (more preferably a mixture of O2, CF4, and Ar).

[0073] A processed substrate can be manufactured by carrying out ion etching using the resist pattern manufactured by the method of the present invention or an underlying layer thereof as a mask. Thus, in another preferred embodiment, the method of manufacturing a processed substrate according to the present invention comprises the following steps: Producing a resist pattern by the method described above; and (7b) performing ion implantation using the resist pattern as a mask; or (7c) Using the resist pattern as a mask, the layer below the resist pattern is processed to form a lower layer pattern, and ion implantation is performed using the lower layer pattern as a mask. In the above (7b) and (7c), the explanation and preferred examples of the lower layer and the intermediate layer are the same as those in the above (7a), respectively, unless otherwise stated. In the above (7b), the target of ion implantation is preferably a substrate or an intermediate layer (more preferably a substrate). In the above (7c), the lower layer is preferably a hardened film or an intermediate layer (more preferably a hardened film). In the above (7c), the target of ion implantation using the lower layer pattern as a mask is preferably a substrate or an intermediate layer (more preferably a substrate). Comparing (7b) and (7c), the method including (7c) is more suitable as the method for manufacturing the processed substrate of the present invention. The ion implantation can be carried out by a known method using a known ion implantation device. In the manufacture of semiconductor elements, liquid crystal display elements, and the like, an impurity diffusion layer is formed on the surface of a substrate. The formation of an impurity diffusion layer is usually performed in two stages: introduction and diffusion of impurities. One of the introduction methods is ion implantation, in which impurities such as phosphorus and boron are ionized in a vacuum, accelerated by a high electric field, and implanted into the surface of a support. The resist pattern or the lower layer pattern is used as a mask when selectively implanting impurity ions into the surface of the substrate. As the ion acceleration energy during ion implantation, an energy load of 10 to 200 keV is applied to the resist pattern, and the mask pattern may be destroyed. Although not bound by theory, the cured film of the present invention is suitable for ion implantation because it can harden the film even if it is made thick and the amount of shrinkage of the film can be reduced. Examples of ion sources (impurity elements) include ions of boron, phosphorus, arsenic, argon, and the like. Examples of thin films on a substrate include silicon, silicon dioxide, silicon nitride, and aluminum.

[0074] [Device manufacturing method] A device can be manufactured by a manufacturing method including the above-mentioned method. The device manufacturing method according to the present invention preferably further includes forming wiring on the processed substrate. Examples of the device include a semiconductor element, a liquid crystal display element, an organic EL display element, a plasma display element, and a solar cell element. The device is preferably a semiconductor.

[0075] [Example] The present invention will be described below with reference to various examples. However, the present invention is not limited to these examples.

[0076] In the examples, the weight average molecular weight is measured using GPC.

[0077] <Preparation of the composition of Example 1> PGME and PGMEA are used as the organic solvent (B1), and γ-valerolactone is used as the organic solvent (B2). They are mixed in a mass ratio of 67.5:27.5:5 (=PGME:PGMEA:γ-valerolactone) to obtain solvent (B). As solid components, a1 as a hydrocarbon-containing compound (A), c1 as a component (C) containing a crosslinking group, and d1 as an acid generator (D) are added to the solvent (B) in a mass ratio of 90:9:1. In Example 1, in order to form a film with a thickness of 3.0 μm, the solid components are prepared to be 29 mass% relative to the total mass of the composition. MEGAFACE R-40 (DIC) is added as a surfactant (G) to be 0.1 mass% relative to the total mass of the composition. This is stirred at room temperature for 30 minutes to obtain a solution. It is visually confirmed that each solid component is completely dissolved. The obtained solution is filtered through a 0.1 μm polyethylene resin filter (Integris, CWUV031S2) to obtain the composition of Example 1. [ka] a1: the above polymer, Mw=2,100 [ka] c1: Tetramethoxymethyl-bisphenol [ka] d1: Thermal acid generator Dodecylbenzenesulfonic acid, triethylamine salt

[0078] <Preparation of Compositions of Examples 2 to 5, Reference Examples 1 to 5, and Comparative Examples 1 to 5> The same operation as in the preparation of the composition of Example 1 is carried out, except that the solid components, the type of solvent, and the amount added are changed as shown in Table 2. The solid components are visually confirmed to be completely dissolved, and filtration is carried out in the same manner as in the preparation of the composition of Example 1. In this manner, the compositions of Example compositions 2 to 5, Reference example compositions 1 to 5, and Comparative examples 1 to 5 are prepared. The composition forming a film having a thickness of 3.0 μm is prepared so that the solid components are 29% by mass relative to the total mass of the composition. The composition forming a film having a thickness of 0.3 μm is prepared so that the solid components are 15% by mass relative to the total mass of the composition. Whether the film thickness is 3.0 μm or 0.3 μm, MEGAFACE R-40 (DIC) is added as a surfactant (G) so that the solid components are 0.1% by mass relative to the total mass. [ka] a2: The above polymer, Mw=2,100 a3: Novolac resin, a random copolymer of m-cresol and p-cresol (mass ratio 6:4), Mw 12,000 [Table 2] The physical properties of the solvent used are as follows: [Table 3]

[0079] <Membrane formation> Using a spin coater (Mikasa), each composition is applied to a 4-inch Si bare wafer at 1,500 rpm. The first heating step is performed by heating the wafer at 250°C for 60 seconds using a hot plate in an air atmosphere. The second heating step is performed by heating the wafer at the temperature shown in Table 4 for 120 seconds using a hot plate in an air atmosphere. This results in a cured film from the composition.

[0080] <Film thickness measurement> A slice is prepared from the substrate having the film formed as described above, and an SEM photograph is taken with a JSM-7100F (JEOL) to measure the film thickness.

[0081] <Etching rate measurement> Using an etching device NE-5000N (ULVAC), each film on the wafer is dry etched with a chamber pressure of 0.17 mT, RF power of 200 W, gas flow rates of CF4 (50 sccm), Ar (35 sccm), and O2 (4 sccm) for 30 seconds. The film thickness before and after etching is measured as described in the above "Film thickness measurement", and the difference between the former and the latter is obtained to calculate the etching rate per unit time. The etching rate of Reference Example 3 is set as 100%, and the etching rate of the film formed from each composition is calculated and shown in Table 4. As can be seen by comparing Reference Example 1 with Comparative Example 1, Reference Example 2 with Comparative Example 2, Reference Example 3 with Comparative Example 3, and Reference Example 4 with Comparative Example 4, increasing the film thickness reduces the etching resistance. Reference Examples 1, 2, 3, and 4, which have a film thickness of 0.3 μm, have high etching resistance, but the Examples show good etching resistance despite having a film thickness of 3.0 μm.

[0082] <Film hardness measurement> The hardness of the cured film described above is measured. Using an ENT-2100 indentation hardness tester (Elionix), an indentation load is applied to each film on the wafer with a thickness of 10 μN for 0.3 μm and 100 μN for 3 μm, 100 measurements, and a step interval of 100 ms. The indentation hardness (GPa) and indentation modulus (GPa) are calculated from this. The results are shown in Table 4. The reason for changing the pressing force depending on the film thickness is to eliminate the cause of film thickness differences and to match the ratio of film thickness to the amount of needle pressing. As can be seen by comparing Reference Example 1 with Comparative Example 1, Reference Example 2 with Comparative Example 2, Reference Example 3 with Comparative Example 3, and Reference Example 4 with Comparative Example 4, the film hardness decreases by increasing the film thickness. As can be seen by comparing Reference Example 3 with Reference Example 4, when the firing temperature is increased from 300°C to 350°C, the film hardness increases at a film thickness of 0.3 μm. On the other hand, as can be seen by comparing Comparative Example 3 with Comparative Example 4, even when the firing temperature is increased from 300°C to 350°C, the film hardness does not increase much at a film thickness of 3.0 μm. The examples show high film hardness even at a film thickness of 3.0 μm. On the other hand, Comparative Example 5, which uses anisole with a relative dielectric constant of 4.33 as a solvent, has low film hardness. [Table 4]

[0083] <Measurement of membrane contraction after ion implant treatment> The amount of film shrinkage after ion implantation treatment is measured for the cured film formed from the composition shown in Table 5. The film shrinkage is measured using an apparatus named EXCEED2300H (Nissin Ion Equipment) at a voltage of 180 kV and an irradiation dose of 10 15 ion / cm 2 Ion implantation is performed under the conditions of an incident angle of 0°, ion species B, and a target depth of 1 μm. The membrane thickness before and after ion implantation was measured as described in "Measurement of membrane thickness" above, and the difference between the former and latter was calculated to obtain the membrane shrinkage amount. The results are shown in Table 5. The amount of film shrinkage due to ion implantation treatment in the example is smaller than that in the comparative example.

[0084] <Evaluation of embeddability> The embeddability of the cured film formed from the composition listed in Table 5 is evaluated. An 8-inch Si processed substrate is prepared, with a substrate surface having a trench pattern of 0.5 μm in height, 1:1 line space ratio, and 250 nm in thickness. Each composition is applied to the processed substrate at 1,500 rpm. The first heating step is performed by heating the substrate at 250° C. for 60 seconds using a hot plate in an air atmosphere. The second heating step is performed by heating the substrate at the heating temperature listed in Table 5 for 120 seconds using a hot plate in an air atmosphere. This results in the formation of a cured film from each composition. A section is formed from the substrate on which the film is formed, and observed by SEM. The embeddability evaluation criteria are as follows. The results are listed in Table 5. A: No voids or bubbles were observed and the trench was filled with film. B: Voids or bubbles are observed and the trench is not filled with film. [Table 5]

Claims

1. A thick film-forming composition comprising a hydrocarbon-containing compound (A) and a solvent (B): where: The hydrocarbon-containing compound (A) comprises a unit (A1) represented by the formula (A1): 【Chemistry 1】 (where, Ar １１ is R １１ substituted or unsubstituted C ６－６０ is a hydrocarbon, R １１ is C １－２０ Alkyl, amino, or C １－２０ alkylamino, R １２ is I, Br or CN, p １１ is a number from 0 to 5, and p １２ is a number between 0 and 1, and q １１ is a number from 0 to 5, and q １２ is a number between 0 and 1, and r １１ is a number from 0 to 5, and s １１ is a number between 0 and 5, However, p １１ , q １１ and r １１ are never simultaneously zero within a unit); The solvent (B) comprises an organic solvent (B1) and an organic solvent (B2) having a relative dielectric constant of 20.0 to 90.0; and The film formed from the thick film forming composition has a thickness of 0.5 to 10 μm.

2. The composition according to claim 1, wherein the organic solvent (B2) has a boiling point of 100 to 400°C at 1 atmosphere. Preferably, the δp / (δD+δp+δH) of the organic solvent (B2) is 20 to 50%.

3. 3. The composition of claim 1 or 2, further comprising a component (C) comprising a crosslinking group.

4. 3. The composition of claim 1 or 2, wherein component (C) comprising a crosslinking group is represented by formula (C1): 【Chemistry 2】 (where, n ｃ１ is 1, 2, 3, or 4, n ｃ２ is n ｃ１ is 0 when n ｃ１ is 1 when is 2 or more, n ｃ３ is 0, 1, or 2, n ｃ４ is 1 or 2, n ｃ５ is 0 or 1, L ｃ is a single bond, or C １－３０ is a hydrocarbon group, R ｃ are each independently C １－６ Alkyl, or C ６－１０ aryl, wherein a methylene in said alkyl is or is not replaced by —O—; R' is hydrogen or methyl.

5. The composition according to claim 1 or 2, further comprising an acid generator (D).

6. The composition according to claim 1 or 2, wherein the solid components in the composition satisfy the following formula (X): 1.5≦{total number of atoms / (number of C−number of O)}≦3.5 Formula (X) (where, The number C is the number of carbon atoms, and The number of O's is the number of oxygen atoms.

7. The composition of claim 1 or 2, further comprising a polymer (E): Preferably, the composition comprises a high carbon material (F); Preferably, the composition comprises a surfactant (G); Preferably, the composition comprises an additive (H); or Preferably, the additive (H) is selected from the group consisting of an acid, a base, a radical generator, a photopolymerization initiator, and a substrate adhesion promoter.

8. 3. The composition according to claim 1, wherein formula (A1) is formula (A1-1), (A1-2), (A1-3) and / or (A1-4). 【Transformation 3】 (where, Ar ２１ is C ６－５０ is an aromatic hydrocarbon group, R ２１ , R ２２ and R ２３ are each independently C ６－５０ a single bond that connects to an aromatic hydrocarbon group, hydrogen, or other structural unit, n21 is 0 or 1, R １２ , p １１ , p １２ , q １１ , q １２ , r １１ and s １１ have the same meaning as in claim 1) 【Chemistry 4】 (where, L ３１ and L ３２ are each independently a single bond or phenylene, n ３１ , n ３２ , m ３１ and m ３２ are each independently 0 to 6, R １２ , p １１ , p １２ , q １１ , q １２ , r １１ and s １１ have the same meaning as in claim 1) 【Transformation 5】 (where, Ar ４１ is C ６－５０ is an aromatic hydrocarbon group, R ４１ and R ４２ are each independently C １－１０ alkyl, and R ４１ and R ４２ and may be bonded together to form a ring, * The carbon atom at position 41 is a quaternary carbon atom, L ４１ is C ６－５０ a single bond that connects to an arylene or other structural unit, R １２ , p １１ , p １２ , q １１ , q １２ , r １１ and s １１ have the same meaning as in claim 1) 【Transformation 6】 (where y is 0 to 2)

9. 3. The composition of claim 1 or 2, wherein the hydrocarbon-containing compound (A) is a polymer: Preferably, the molecular weight of the hydrocarbon-containing compound (A) is 400 to 100,000; Preferably, the aldehyde derivative used when synthesizing the polymer is 0 to 30 mol % based on the sum of all elements used in the synthesis; or Preferably, the polymer is substantially free of secondary and tertiary carbon atoms in its backbone.

10. The composition according to claim 7, wherein the high carbon material (F) is represented by formula (F1): 【Transformation 7】 (where, Ar １ is a single bond, C １－６ Alkyl, C ６－１２ cycloalkyl, or C ６－１４ is aryl, Ar ２ is C １－６ Alkyl, C ６－１２ cycloalkyl, or C ６－１４ is aryl, R ｆ１ and R ｆ２ are each independently C １－６ alkyl, hydroxy, halogen, or cyano; R ｆ３ is hydrogen, C １－６ Alkyl, or C ６－１４ is aryl, However, Ar ２ is C １－６ Alkyl or C ６－１４ aryl, and R ｆ３ is C １－６ Alkyl or C ６－１４ When it is aryl, Ar ２ and R ｆ３ and may be bonded to each other to form a ring, r and s are each independently 0, 1, 2, 3, 4, or 5; Cy surrounded by dashed lines ３ , Cy ４ and Cy ５ At least one of the rings is adjacent to an aromatic hydrocarbon ring Ph ７ and an aromatic hydrocarbon ring fused with Cy surrounded by dashed lines ６ , Cy ７ and Cy ８ At least one of the rings is adjacent to an aromatic hydrocarbon ring Ph ８ is an aromatic hydrocarbon ring fused with

11. The composition according to claim 1 or 2, wherein the content of the hydrocarbon-containing compound (A) is 3 to 40 mass% based on the composition: Preferably, the content of the solvent (B) is 50 to 97 mass% based on the composition; Preferably, the content of the component (C) containing a crosslinking group is 0 to 30 mass% based on the total content of the hydrocarbon-containing compound (A) and the polymer (E); Preferably, the content of the acid generator (D) is 0 to 5 mass% based on the total content of the hydrocarbon-containing compound (A) and the polymer (E); Preferably, the content of the organic solvent (B1) is 70 to 99 mass% based on the solvent (B); Preferably, the content of the organic solvent (B2) is 1 to 20 mass% based on the solvent (B); Preferably, the content of the polymer (E) is 0 to 300 mass% based on the hydrocarbon-containing compound (A): Preferably, the content of the high-carbon material (F) is 0 to 200 mass % based on the total content of the hydrocarbon-containing compound (A) and the polymer (E); or Preferably, the content of the surfactant (G) is 0 to 20 mass % based on the total content of the hydrocarbon-containing compound (A) and the polymer (E).

12. The composition according to claim 1 or 2, which is a resist underlayer film-forming composition: Preferably, the composition is a spin-on-carbon (SOC) film-forming composition.

13. A method for producing a cured film, comprising the following steps: (1) applying the composition of claim 1 over a substrate to form a hydrocarbon-containing film; and (2) Heating the hydrocarbon-containing film where: The thickness of the cured film is 0.5 to 10 μm; Preferably, the substrate is a planar or non-planar substrate; more preferably a non-planar substrate; Preferably, the heating in (2) is carried out at less than 340°C; Preferably, the heating in (2) is carried out at 70 to 330°C; Preferably, the heating in (2) is carried out in two stages, the first heating being at 70 to 330°C and the second heating being at 200 to 330°C; or Preferably, the surface resistivity of the cured film is 10 ９ ~10 １６ Ω□ (preferably 10 １２ ~10 １６ Ω□, more preferably 10 １３ ~10 １６ Ω□).

14. A method for producing a resist film, comprising the following steps:

14. Producing a cured film by the method of claim 13. (3) applying a resist composition over the cured film; and (4) The resist composition is heated to form a resist film: where: Preferably, the heating in (4) is carried out at 100 to 250°C and / or for 30 to 300 seconds; or Preferably, the heating in (4) is carried out in air or nitrogen gas atmosphere.

15. A method for producing a resist pattern comprising the following steps: A resist film is produced by the method according to claim 14. (5) exposing the resist film; and (6) The resist film is developed.

16. A method for producing a processed substrate comprising the steps of: Producing a resist pattern by the method of claim 15; and (7) Using the resist pattern as a mask, the layer below the resist pattern is processed.

17. 17. A method for producing a processed substrate according to claim 16, comprising the steps of: Producing a resist pattern by the method of claim 15; and (7a) Dry etching the lower layer using the resist pattern as a mask: where: Preferably, the underlayer of (7a) is a cured film, an interlayer, or a substrate.

18. 17. A method for producing a processed substrate according to claim 16, comprising the steps of: Producing a resist pattern by the method of claim 15; and (7b) performing ion implantation using the resist pattern as a mask; or (7c) Using the resist pattern as a mask, the layer below the resist pattern is processed to form a lower layer pattern, and ions are implanted using the lower layer pattern as a mask.

19. A method for manufacturing a device comprising the method of claim 16: Preferably, the method further comprises forming wiring on the processed substrate.

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