Ion implantation thick film resist composition, method for manufacturing processed substrate using same, and method for manufacturing device using same

Abstract

Provided is an ion implantation thick film resist composition. [Solution] An ion implantation thick-film resist composition comprising a polymer (A) having a specific structure, a photoacid generator (B) and a solvent (C), wherein the thickness of the formed resist film is 1.0 to 50 μm, and the mass average molecular weight of the polymer (A) is 5,000 to 19,000.

Description

[Technical field]

[0001] The present invention relates to an ion implantation thick-film resist composition, a method for manufacturing a processed substrate using the same, and a method for manufacturing a device using the same. [Background technology]

[0002] In the manufacture of semiconductor devices, an ion implantation process is adopted in which impurity ions are introduced into a semiconductor substrate using a resist pattern as a mask. The impurity ions are implanted with high energy using an ion implanter. As designs become finer and the amount of ions implanted increases, the resist pattern used in the ion implantation process is required to be thicker, have a higher rectangular shape, and have high heat resistance.

[0003] Although thick-film resist compositions have been proposed for plating processes, etching processes, and the like (for example, Patent Document 1), there is still a demand for compositions with improved resolution and rectangularity. Although thick-film resist compositions have been proposed for use in high-energy ion implantation processes and the like, improvements in terms of resolution and the like are still required (for example, Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2007-206425 A [Patent Document 2] International Publication No. 2004 / 104702 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have found that there are one or more problems that need to be improved regarding ion implantation resist compositions and their use, such as the following: a resist pattern with sufficiently high rectangularity cannot be obtained; sufficient resolution cannot be obtained; the ion implantation resistance of the resist pattern is insufficient; the transmittance of the resist film is low; a resist pattern with a high aspect ratio cannot be formed; and the heat resistance of the resist pattern is insufficient. The present invention has been made based on the above-mentioned technical background, and provides an ion implantation thick-film resist composition and a method for manufacturing a processed substrate using the same. [Means for solving the problem]

[0006] The ion implantation thick film resist composition according to the present invention comprises: A composition comprising a polymer (A), a photoacid generator (B) and a solvent (C), The thickness of a resist film formed from the composition is 1.0 to 50 μm; The mass average molecular weight of the polymer (A) is 5,000 to 19,000, and The polymer (A) comprises at least one of repeating units represented by formulae (A-1), (A-2), (A-3) and (A-4). [ka] (where: R 11 , R 21 , R 41 and R 45 are each independently C 1-5 alkyl, in which methylene may be replaced by oxy; R 12 , R 13 , R 14 , R 22 , R 23 , R 24 , R 32 , R 33 , R 34 , R 42 , R43 , and R 44 are each independently hydrogen, C 1-5 Alkyl, C 1-5 alkoxy, or -COOH; p11 is 0 to 4, p15 is 1 to 2, and p11 + p15 ≦ 5; p21 is 0 to 5; p41 is 0-4, p45 is 1-2, and p41+p45≦5; P 31 is C 4-20 Alkyl (wherein a part or all of the alkyl may form a ring, a part or all of the H in the alkyl may be replaced with halogen, and a methylene in the alkyl may be replaced with an oxy or a carbonyl)

[0007] The method for producing a processed substrate according to the present invention comprises the following steps: Using the above ion implantation thick film resist composition, a resist pattern is produced; and performing ion implantation using the resist pattern as a mask; or 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.

[0008] The method for producing a device according to the present invention comprises the method for producing the processed substrate described above. Effect of the Invention

[0009] In the process of arriving at the present invention, the inventors came up with the following considerations. Since the resist pattern itself, which serves as a mask, is also removed by the implantation of ionized impurities, it is necessary to form a thick resist film. In order to form a thick film, the film must be highly transparent. The thicker the film, the higher the rectangularity required. Furthermore, since heat is generated during the process of ion implantation resist patterns, the resist pattern must also have excellent heat resistance. As a result of extensive investigations, the inventors obtained the composition of the present invention. According to the present invention, one or more of the following effects can be achieved. A resist pattern with high rectangularity can be obtained; a resist film with high resolution can be obtained; the resist pattern has high ion implantation resistance; the resist film has high transmittance; a resist pattern with a high aspect ratio can be formed; and the resist pattern has high heat resistance. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a conceptual diagram showing a cross-sectional shape of a trench pattern. [Diagram 2] A conceptual diagram showing the cross-sectional shapes of resist patterns with different Wt / Wb. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] [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 of the present invention as the solvent (C) or another component.

[0012] Hereinafter, an embodiment of the present invention will be described in detail.

[0013] <Ion implantation thick film resist composition> The ion implantation thick-film resist composition (hereinafter sometimes simply referred to as the composition) according to the present invention comprises a polymer (A) having a specific structure, a photoacid generator (B), and a solvent (C). The composition according to the present invention is a thick-film resist composition. Here, in the present invention, the thick film means a film having a thickness of 1.0 to 50 μm, and preferably a film having a thickness of 1.2 to 30 μm (more preferably 1.5 to 20 μm, and further preferably 2 to 10 μm). The viscosity of the composition according to the present invention is preferably 10 to 1,000 mPa·s; more preferably 12 to 500 mPa·s. Here, the viscosity is measured at 25° C. using a capillary viscometer. The composition according to the present invention is preferably a KrF chemically amplified resist composition; more preferably a KrF positive chemically amplified resist composition.

[0014] Polymer (A) The composition according to the present invention comprises a polymer (A). The polymer (A) comprises at least one of the repeating units represented by the following formulae (A-1), (A-2), (A-3) and (A-4). The polymer (A) reacts with an acid to increase its solubility in an alkaline aqueous solution. Such a polymer has, for example, an acid group protected by a protecting group, and when an acid is added from the outside, the protecting group is eliminated, thereby increasing the solubility in an alkaline aqueous solution.

[0015] Formula (A-1) is as follows: [ka] Where: R 11 are each independently C 1-5 Alkyl (wherein methylene in the alkyl may be replaced by oxy); preferably methyl or ethyl; more preferably methyl. In the present invention, the expression "methylene in the alkyl may be replaced by oxy" means that oxy may be present between carbons in the alkyl, and does not intend that the terminal carbon in the alkyl becomes oxy, that is, that it has alkoxy or hydroxy. R 12 , R 13 , and R 14 are each independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy, or -COOH; preferably hydrogen or methyl; more preferably hydrogen. p11 is 0 to 4; preferably 0 or 1; and more preferably 0. p15 is 1 to 2; preferably 1. p11+p15≦5.

[0016] Polymer (A) can contain multiple repeating units represented by formula (A-1). For example, it can have a 1:1 ratio of a structural unit with p15=1 and a structural unit with p15=2. In this case, p15=1.5 as a whole. Hereinafter, unless otherwise specified, the same applies to the numbers expressing polymers in the present invention.

[0017] Specific examples of formula (A-1) include the following. [ka]

[0018] Formula (A-2) is as follows. [ka] Where: R 21 are each independently C 1-5 It is alkyl (wherein methylene in the alkyl may be replaced by oxy); preferably it is methyl, ethyl, t-butyl or t-butoxy; more preferably it is methyl or ethyl; more preferably it is methyl. R 22 , R 23 , and R 24 are each independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy, or -COOH; preferably hydrogen, or methyl; more preferably hydrogen. p21 is an integer of 0 to 5; preferably 0, 1, 2, 3, 4 or 5; more preferably 0 or 1; and even more preferably 0.

[0019] Specific examples of formula (A-2) include the following. [ka]

[0020] Equation (A-3) is as follows. [ka] Where: R 32 , R 33 and R 34 are each independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy, or -COOH; preferably hydrogen, methyl, ethyl, t-butyl, methoxy, t-butoxy, or -COOH; more preferably hydrogen or methyl; and even more preferably hydrogen. P 31 is C 4-20 Here, a part or all of the alkyl may form a ring, a part or all of the H in the alkyl may be replaced with a halogen, and a methylene in the alkyl may be replaced with an oxy or a carbonyl. 31 The alkyl portion of P is preferably branched or cyclic. 31 C 4-20 When the alkyl is substituted with a halogen, it is preferable that the entire alkyl group is substituted, and the halogen is preferably F or Cl; more preferably F. 31 C 4-20 In a preferred embodiment of the present invention, H in the alkyl group is not substituted with a halogen. 31 is preferably methyl, isopropyl, t-butyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, adamantyl, methyladamantyl or ethyladamantyl; more preferably t-butyl, ethylcyclopentyl, ethylcyclohexyl or ethyladamantyl; even more preferably t-butyl, ethylcyclopentyl or ethyladamantyl; and even more preferably t-butyl.

[0021] Specific examples of formula (A-3) include the following. [ka]

[0022] Equation (A-4) is as follows. [ka] Where: R 41 are each independently C 1-5 It is alkyl (wherein methylene in the alkyl may be replaced by oxy); preferably, it is methyl, ethyl or t-butyl; more preferably, it is methyl. R 45 are each independently C 1-5 alkyl (wherein methylene in the alkyl may be replaced by oxy); preferably methyl, t-butyl or -CH(CH 3 )-O-CH 2 CH 3 It is. R 42 , R 43 , and R 44 are each independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy, or -COOH; preferably hydrogen or methyl; more preferably hydrogen. p41 is an integer of 0 to 4; more preferably 0 or 1; and even more preferably 0. p45 is 1 to 2; more preferably 1. p41+p45≦5.

[0023] Specific examples of formula (A-4) include the following. [ka]

[0024] These structural units are appropriately mixed depending on the purpose. In a preferred embodiment, they are mixed so that the increase in solubility in an alkaline aqueous solution due to the acid is appropriate. The number of repeating units n of the repeating units (A-1), (A-2), (A-3) and (A-4) in the polymer (A) A-1 , n A-2 , nA-3 and n A-4 The following explains this. n A-1 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 40 to 80%; more preferably 50 to 80%; even more preferably 55 to 75%; and still more preferably 55 to 65%. n A-2 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 0 to 40%; more preferably 0 to 30%; even more preferably 5 to 25%; and still more preferably 15 to 25%. n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 10 to 50%; more preferably 10 to 40%; even more preferably 15 to 35%; and still more preferably 15 to 25%. n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 0 to 40%; more preferably 0 to 30%; even more preferably 0 to 10%; and even more preferably 0 to 5%. A-4 In a preferred embodiment of the present invention, n is 0. A-1 / (n A-1 +n A-2 +n A-3 +n A-4 )=40~80%, n A-2 / (n A-1 +n A-2 +n A-3 +n A-4 )=0~40%, n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) = 10 to 50%, and n A-4 / (n A-1 +nA-2 +n A-3 +n A-4 )=0 to 40% is a preferred embodiment. In one aspect of the present invention, n A-3 >0 and n A-4 =0.

[0025] The polymer (A) may also contain further repeating units other than the repeating units represented by (A-1), (A-2), (A-3) and (A-4). The further repeat unit is preferably a repeat unit comprising an arylcarbonyl. The content of the further repeating unit contained in the polymer (A) is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, and further preferably 0 to 1 part by mass, based on 100 parts by mass of the polymer (A). A preferred embodiment of the polymer (A) is one in which the polymer does not contain any further repeating unit. In other words, a preferred embodiment is one in which the polymer does not contain any repeating unit containing an arylcarbonyl.

[0026] Specific examples of the polymer (A) include the following. [ka]

[0027] The mass average molecular weight (hereinafter sometimes referred to as Mw) of polymer (A) is 5,000 to 19,000, more preferably 8,000 to 19,000, even more preferably 10,000 to 19,000, and still more preferably 11,000 to 13,000. Without being bound by theory, it is believed that by having polymer (A) with this Mw, it becomes possible to form a resist pattern with good rectangularity or resolution from the composition of the present invention. In the present invention, Mw can be measured by gel permeation chromatography (GPC). In one preferred example, the GPC column is set at 40° C., the elution solvent is tetrahydrofuran at 0.6 mL / min, and monodisperse polystyrene is used as the standard.

[0028] For the purpose of explanation, the polymer (A) in the composition according to the present invention may be used in combination of two or more kinds as long as it is represented by the above formula. For example, a composition containing both of the following two kinds of polymer (A) is also an embodiment of the present invention. [ka] The same applies to the composition of the present invention in the following description unless otherwise specified. The polymer (A) contained in the composition according to the present invention is composed of one or two kinds of polymers, preferably one kind of polymer, with Mw distribution and polymerization variation being allowed.

[0029] The content of the polymer (A) is preferably from 10 to 40 mass %, more preferably from 12 to 38 mass %, and further preferably from 15 to 36 mass %, based on the composition. The composition according to the present invention may contain a polymer other than the polymer (A), but a preferred embodiment is one in which the composition does not contain any polymer other than the polymer (A).

[0030] Photoacid generator (B) The composition according to the present invention comprises a photoacid generator (B). Here, the photoacid generator (B) releases an acid upon irradiation with light. Preferably, the acid derived from the photoacid generator (B) acts on the polymer (A) to increase the solubility of the polymer (A) in an alkaline aqueous solution. For example, when the polymer (A) has an acid group protected by a protecting group, the protecting group is removed by the acid. The photoacid generator (B) used in the composition according to the present invention can be selected from conventionally known ones.

[0031] Upon exposure to light, the photoacid generator (B) changes its acid dissociation constant pKa (H 2 O) preferably releases an acid of from -20 to 1.4; more preferably from -16 to 1.4; even more preferably from -16 to 1.2; and even more preferably from -16 to 1.1.

[0032] The photoacid generator (B) is preferably represented by formula (B-1). B n+ Cation B n- Anion (B-1) where B n+ The cation is a cation represented by formula (BC1), a cation represented by formula (BC2), or a cation represented by formula (BC3); preferably a cation represented by formula (BC1) or (BC2); more preferably a cation represented by formula (BC1). n+ The cation as a whole has a valency of n, where n is 1 to 3. B n- The anion is a sulfonate anion, preferably an anion represented by formula (BA1), an anion represented by formula (BA2), an anion represented by formula (BA3), or an anion represented by formula (BA4); more preferably an anion represented by formula (BA3). B n- The anion as a whole has a valency of n. n is preferably 1 or 2; more preferably 1. Without being bound by theory, it is believed that by using the above-mentioned photoacid generator (B), it is possible to control the amount of photoacid generator (B) present near the bottom surface during resist film formation, and to control the pattern shape to be rectangular. In a positive resist, the exposed area is solubilized, but the amount of light reaching the area decreases as it approaches the bottom surface of the resist film, so it is effective to control the pattern shape by the amount of photoacid generator (B) present.

[0033] Equation (BC1) is as follows: [ka] Where: R b1 are each independently 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, or C 6-12 Aryloxy; preferably methyl, ethyl, t-butyl, methoxy, ethoxy, phenylthio, or phenyloxy; more preferably t-butyl, methoxy, ethoxy, phenylthio, or phenyloxy. Each nb1 is independently 0, 1, 2 or 3; preferably 0 or 1, and more preferably 0.

[0034] Specific examples of formula (BC1) include the following. [ka]

[0035] Equation (BC2) is as follows. [ka] Where: R b2 are each independently 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 aryl; preferably C 4-6 Each R in the formula is an alkyl having a branched structure. b2 may be the same or different, and it is more preferable that they are the same. b2 is more preferably t-butyl or 1,1-dimethylpropyl; even more preferably t-butyl. Each nb2 is independently 0, 1, 2 or 3; preferably 1.

[0036] Specific examples of formula (BC2) include the following. [ka]

[0037] Equation (BC3) is as follows: [ka] Where: R b3 are each independently hydroxy, C 1-6 Alkyl, C 1-6 Alkoxy, or C 6-12 It is aryl; preferably methyl, ethyl, methoxy, or ethoxy; more preferably methyl or methoxy. R b4 are each independently 1-6 is preferably methyl, ethyl, propyl, or butyl. b4 may be bonded to each other to form a ring structure, and in the case of ring formation, it is preferable to form a 5- or 6-membered alicyclic ring. Each nb3 is independently 0, 1, 2 or 3; preferably 1, 2 or 3; and more preferably 1 or 3.

[0038] Specific examples of formula (BC3) include the following. [ka]

[0039] Equation (BA1) is as follows: [ka] Here, R b5 are each independently 1-6 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, or C 1-6 It is an alkyl group. For example, -CF 3 is methyl (C 1 In the present invention, fluorine substitution means that some or all of the hydrogen atoms present in the alkyl moiety are substituted with fluorine atoms, and more preferably all of the hydrogen atoms are substituted with fluorine atoms. R b5 The alkyl portion of is preferably methyl, ethyl or t-butyl, more preferably methyl. R b5 is preferably a fluorine-substituted alkyl; more preferably -CF 3 It is.

[0040] Specific examples of formula (BA1) include the following. [ka]

[0041] Equation (BA2) is as follows: [ka] Here, R b6 is C 1-10 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, C 6-12 Fluorine-substituted aryl, C 2-12 Fluorine-substituted acyl, or C 6-12 fluorine-substituted alkoxyaryl; preferably C 1-10 R is a fluorine-substituted alkyl. b6 The alkyl portion of R is preferably linear or cyclic. b6 is preferably C 1-6 Fluorine-substituted alkyl; more preferably C 2-6 It is a fluorine-substituted alkyl.

[0042] Specific examples of formula (BA2) include the following. [ka]

[0043] Equation (BA3) is as follows: [ka] (where: R b7 are each independently 1-6Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, C 6-12 Fluorine-substituted aryl, C 2-12 Fluorine-substituted acyl, or C 6-12 fluorine-substituted alkoxyaryl; preferably C 2-6 Fluorine-substituted alkyl. Two R b7 may be bonded to each other to form a fluorine-substituted heterocyclic structure. The heterocyclic structure is preferably a saturated ring. The heterocyclic structure is preferably a monocyclic structure having 5 to 8 rings including N and S; more preferably a 5-membered or 6-membered ring; and even more preferably a 6-membered ring.

[0044] Specific examples of formula (BA3) include the following. [ka]

[0045] Equation (BA4) is as follows: [ka] Where: R b8 is hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy, or hydroxy; preferably hydrogen, methyl, ethyl, methoxy, or hydroxy; more preferably hydrogen or hydroxy. L b is methylene, ethylene, carbonyl, oxy or carbonyloxy; preferably ethylene or carbonyl. Y b are each independently hydrogen or fluorine; preferably one or more are fluorine. nb4 is an integer of 0 to 10; preferably 0, 1 or 2. nb5 is an integer of 0 to 21; preferably 4, 5 or 6.

[0046] Specific examples of formula (BA4) include the following. [ka]

[0047] The molecular weight of the photoacid generator (B) is preferably 300 to 1,200; more preferably 400 to 900.

[0048] The content of the photoacid generator (B) is preferably 0.3 to 4 parts by mass, more preferably 0.4 to 2 parts by mass, and even more preferably 0.5 to 2 parts by mass, relative to 100 parts by mass of the polymer (A). Without being bound by theory, it is believed that a resist pattern with better resolution can be formed when the content of the photoacid generator (B) is within the above range.

[0049] The composition according to the present invention may contain a photoacid generator other than the photoacid generator (B), for example, a photoacid generator (B') represented by the following formula (B'-1). In the present invention, the photoacid generator (B') is different from the photoacid generator (B). In a preferred embodiment of the present invention, the acid that acts directly on the polymer (A) is not the photoacid generator (B') but is an acid released from the photoacid generator (B).

[0050] In a preferred embodiment of the present invention, the cation derived from the photoacid generator (B') reacts with the anion moiety derived from the photoacid generator (B) and functions as a quencher. In this case, the photoacid generator (B') functions as a quencher to suppress the diffusion of the acid derived from the photoacid generator (B) generated in the exposed area.

[0051] The photoacid generator (B') is represented by formula (B'-1). B' m+ Cation B' m- Anion (B-1) Where: B' m+ The cation is a cation represented by the above formula (BC1) or a cation represented by the above formula (BC2). The preferred form is also the same as above. B' m+ The cation as a whole has a valency of m, where m is 1-3. B'm- The anion is an anion represented by the formula (B'A1) or an anion represented by the formula (B'A2). m- The anion as a whole has a valency of m. m is preferably 1 or 2; more preferably 1.

[0052] The formula (B'A1) is as follows. [ka] Where: X 1 is C 1-20 is a hydrocarbon or a single bond; R b’1 are each independently hydrogen, hydroxy, C 1-6 Alkyl, or C 6-10 is aryl, nb'1 is 1, 2 or 3, and nb'2 is 0, 1 or 2.

[0053] X 1 When C is a hydrocarbon, it may be linear, branched, or cyclic, but is preferably linear or cyclic. 1-4 It is preferable that 1-2 ), preferably has one double bond in the chain or is saturated. If it is cyclic, it may be an aromatic monocyclic ring, or a saturated monocyclic or polycyclic ring, if it is a monocyclic ring, it is preferably a six-membered ring, and if it is a polycyclic ring, it is preferably an adamantane ring. X 1 is preferably methyl, ethyl, propyl, butyl, ethane, phenyl, cyclohexane, adamantane or a single bond; more preferably, methyl, phenyl, cyclohexane or a single bond; even more preferably, phenyl or a single bond; and even more preferably, phenyl. nb'1 is preferably 1 or 2; more preferably 1. nb'2 is preferably 0 or 1; more preferably 1. Rb'1 is preferably hydroxy, methyl, ethyl, 1-propyl, 2-propyl, t-butyl, or phenyl; more preferably hydroxy.

[0054] X 1 is a single bond, R b’1 is preferably hydrogen. 1 is a single bond, R b’1 is hydrogen, nb'1=nb'2=1 (B'A1) is H-COO - represents an anion.

[0055] Specific examples of formula (B'A1) are as follows. [ka]

[0056] The formula (B'A2) is as follows. [ka] Where: R b’2 is C 1-20 Alkyl (wherein a part or the whole of the alkyl may form a ring, and -CH 2 - may be replaced by -C(=O)-. b’2 is preferably C 3-13 alkyl; more preferably C 5-12 alkyl; more preferably C 8-12 alkyl; even more preferably C 10 It is an alkyl group. b’2 The alkyl in R preferably forms a ring in part or in whole; more preferably forms a ring in part. b’2 One or more (more preferably one) -CH 2 - is replaced by -C(=O)-.

[0057] Specific examples of formula (B'A2) are as follows. [ka]

[0058] Upon exposure to light, the photoacid generator (B') has an acid dissociation constant pKa (H 2 O) preferably releases 1.5 to 8; more preferably 1.5 to 5 acids.

[0059] The molecular weight of the photoacid generator (B') is preferably 300 to 1,400; more preferably 300 to 1,200.

[0060] The content of the photoacid generator (B') is preferably 0.01 to 5 mass% based on the polymer (A), more preferably 0.03 to 1 mass%, still more preferably 0.05 to 1 mass%, and still more preferably 0.5 to 1 mass%. A preferred embodiment of the present invention is one in which the photoacid generator (B') is not contained.

[0061] Solvent (C) The composition according to the present invention contains a solvent (C). There are no particular limitations on the solvent as long as it can dissolve each of the components to be blended. Specific examples of the solvent include water, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene, methanol, ethanol, n-Propanol, i-Propanol, n-Butanol, i-Butanol, sec-Butanol, t-Butanol, n-Pentanol, i-Pentanol, 2-Methylbutanol, sec-Pentanol, t-Pentanol, 3-Methoxybutanol, n-Hexanol, 2-Methylpentanol, sec-Hexanol, 2-Ethylbutanol, sec-Heptanol, Heptanol-3, n-Octanol, 2-Ethylhexanol, sec-Octanol, n-Nonylalcohol, 2,6-Dimethylheptanol-4, n-Decanol, sec-U nonyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol All-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol,Acetophenone, Fenchone, Ethyl Ether, i-Propyl Ether, n-Butyl Ether (Di-n-Butyl Ether, DBE), n-Hexyl Ether, 2-Ethylhexyl Ether, Ethylene Oxide, 1,2-Propylene Oxide, Dioxolane, 4-Methyldioxolane, Dioxane, Dimethyldioxane, Ethylene Glycol Monomethyl Ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Diethyl Ether, Ethylene Glycol Mono-n-Butyl Ether, Ethylene Glycol Mono-n-Hexyl Ether, Ethylene Glycol Monophenyl Ether, Ethylene Glycol Mono-2-Ethylbutyl Ether, Ethylene Glycol Dibutyl Ether, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Diethyl Ether, Diethylene Glycol Mono-n-Butyl Ether, Diethylene Glycol Di-n-Butyl Ether, Diethylene Glycol Mono-n-Hexyl Ether, Ethoxytriglycol, Tetraethylene Glycol Di-n-Butyl Ether, Propylene Glycol Monomethyl Ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl carbonate, methyl acetate, ethyl acetate, gamma-butyrolactone, gamma-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate (normal butyl acetate, nBA), i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate,Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate (EL), γ-butyrolactone, n-butyl lactate, Examples of the solvent include n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents can be used alone or in combination of two or more. The solvent (C) is preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, n-butyl acetate, n-butyl ether, 2-heptanone, cyclohexanone, or any combination thereof; more preferably PGME, EL, nBA, DBE, or any mixture thereof; even more preferably PGME, EL, or a mixture thereof; and even more preferably a mixture of PGME and EL. When two types are mixed, the mass ratio of the first solvent to the second solvent is preferably 95:5 to 5:95 (more preferably 90:10 to 10:90, and even more preferably 80:20 to 20:80).

[0062] In relation to other layers or films, the solvent (C) may not substantially contain water. For example, the amount of water in the entire solvent (C) is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and even more preferably 0.001% by mass or less. In another preferred embodiment, the solvent (C) does not contain water (0% by mass).

[0063] The content of the solvent (C) is preferably 50 to 90 mass %, more preferably 60 to 88 mass %, and further preferably 65 to 85 mass %, based on the composition. By increasing or decreasing the amount of the solvent in the entire composition, the film thickness after formation can be controlled.

[0064] Base Compound (D) The composition according to the present invention may further contain a basic compound (D). The basic compound has the effect of suppressing the diffusion of the acid generated in the exposed area and the effect of suppressing the deactivation of the acid on the resist film surface due to amine components contained in the air.

[0065] The basic compound (D) is preferably ammonia, C 1-16 Primary aliphatic amines, C 2-32 Secondary aliphatic amines, C 3-48 Tertiary aliphatic amines, C 6-30 Aromatic amines, C 5-30 and their derivatives.

[0066] Specific examples of the basic compound (D) include ammonia, ethylamine, n-octylamine, n-heptylamine, ethylenediamine, triethylamine, tri-n-octylamine, diethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene-5, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0067] The base dissociation constant pKb(H 2O) is preferably −12 to 5, and more preferably 1 to 4.

[0068] The molecular weight of the basic compound (D) is preferably 17-500, more preferably 60-400.

[0069] The content of the basic compound (D) is preferably from 0.01 to 5 parts by mass, and more preferably from 0.05 to 2 parts by mass, based on 100 parts by mass of the polymer (A).

[0070] Surfactant (E) The composition according to the present invention may further include a surfactant (E). By including a surfactant, the coating property may be improved. Examples of surfactants that can be used in the present invention include (I) anionic surfactants, (II) cationic surfactants, and (III) nonionic surfactants, and more specifically, (I) alkylsulfonates, alkylbenzenesulfonic acids, and alkylbenzenesulfonates, (II) laurylpyridinium chloride, and laurylmethylammonium chloride, and (III) polyoxyethylene octyl ethers, polyoxyethylene lauryl ethers, polyoxyethylene acetylenic glycol ethers, fluorine-containing surfactants (e.g., Fluorad (3M), Megafac (DIC), Sulfuron (Asahi Glass), and organic siloxane surfactants (e.g., KF-53, KP341 (Shin-Etsu Chemical)).

[0071] These surfactants can be used alone or in combination of two or more. The content of the surfactant (E) is preferably 0.005 to 1 part by mass, more preferably 0.01 to 0.2 part by mass, based on 100 parts by mass of the polymer (A).

[0072] Dye (F) The composition according to the present invention may further contain a dye (F). By containing the dye (F), the pattern shape can be improved. The content of the dye (F) is preferably 0 to 0.5 parts by mass, more preferably 0 to 0.2 parts by mass, and even more preferably 0 to 0.1 parts by mass, based on 100 parts by mass of the polymer (A). Since the resist film of the present invention preferably has high transmittance, it is preferable that the resist film does not substantially contain a dye. In a more preferred embodiment of the present invention, the composition according to the present invention does not contain the dye (F) (0 part by mass).

[0073] Additives (G) The composition according to the present invention may further contain an additive (G) other than the above-mentioned components. The additive (G) is preferably a surface smoothing agent, a plasticizer, a contrast enhancing agent, an acid, a radical generator, a substrate adhesion enhancing agent, an antifoaming agent, or any combination thereof. The content of additive (G) (when there are multiple additives, the sum of the content) is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass, and further preferably 0 to 1 part by mass, based on 100 parts by mass of polymer (A). In one embodiment of the present invention, the composition according to the present invention does not contain additive (G) (0 part by mass).

[0074] The acid can be used to adjust the pH value of the composition or to improve the solubility of the additive components. The acid to be used is not particularly limited, but examples thereof include formic acid, acetic acid, propionic acid, benzoic acid, phthalic acid, salicylic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aconitic acid, glutaric acid, adipic acid, and combinations thereof. In the present invention, the content of salicylic acid is preferably 0 to 0.005 parts by mass, more preferably 0 to 0.001 parts by mass, based on 100 parts by mass of the polymer (A). In one embodiment of the present invention, the composition according to the present invention does not contain salicylic acid (0 part by mass).

[0075] <Method of manufacturing processed substrate> The method for producing a processed substrate according to the present invention comprises the following steps. Producing a resist pattern using the composition according to the present invention; and Ion implantation is performed using a resist pattern as a mask, or 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.

[0076] An embodiment of the manufacturing method according to the present invention will now be described. The composition according to the present invention is applied above a substrate (e.g., silicon / silicon dioxide-coated substrate, silicon nitride substrate, silicon wafer substrate, glass substrate, ITO substrate, etc.) by a suitable method. Here, in the present invention, above includes the case where it is formed directly above and the case where it is formed via another layer. For example, a planarizing film or a resist underlayer film may be formed directly above the substrate, and the composition according to the present invention may be applied directly above it. An example of the resist underlayer film is a BARC layer. The application method is not particularly limited, and examples include a method of coating with a spinner or coater. After coating, the film according to the present invention is formed by heating. This heating is performed, for example, by a hot plate. The heating temperature is preferably 100 to 250°C; more preferably 100 to 200°C; and even more preferably 100 to 160°C. The temperature here is the heating atmosphere, for example the heating surface temperature of a hot plate. The heating time is preferably 30 to 300 seconds; more preferably 30 to 120 seconds; and even more preferably 45 to 90 seconds. The heating is preferably performed in air or nitrogen gas atmosphere.

[0077] The resist film formed by the present invention has high transmittance. When the film thickness is 5 μm, the transmittance at a wavelength of 248 nm is preferably 15 to 50%, and more preferably 17 to 40%. With such transmittance, even when the film is thick, the exposure light can reach the lower part of the film, and a resist pattern with high rectangularity can be formed.

[0078] 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 expose with light having a wavelength of 13.5 to 248 nm. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), extreme ultraviolet ray (wavelength 13.5 nm), etc. can be used, and KrF excimer laser is preferable. These wavelengths allow a range of ±1%. After exposure, post exposure bake (PEB) can be performed as necessary. The PEB temperature is preferably 80 to 160°C; more preferably 100 to 150°C, and the heating time is 0.3 to 5 minutes; preferably 0.5 to 2 minutes.

[0079] The exposed resist film is developed using a developer. 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, water washing or rinsing treatment can be performed as necessary. When a positive resist composition is used, the exposed portion is removed by development to form a resist pattern. This resist pattern can also be further fined by using, for example, a shrink material.

[0080] When the composition according to the present invention is used, a resist pattern can be formed that has a high resolution, i.e., a high aspect ratio, even though it is a thick film. When the thickness of the resist film is 3 μm, the resolution is preferably 150 to 220 nm, and more preferably 160 to 200 nm.

[0081] When the composition according to the present invention is used, a resist pattern with high rectangularity can be formed. When the composition according to the present invention is a positive resist pattern forming composition, the width of the top of the resist pattern is Wt and the width of the bottom is Wb, and Wt / Wb (hereinafter sometimes referred to as Pr) is preferably 0.6 to 1.7, more preferably 0.7 to 1.0, and further preferably 0.8 to 1.0. It is preferable to measure under conditions for comparing these values ​​that are as consistent as possible with those in the examples described below. For example, it is preferable to form a film with a thickness of 3.0 μm, and form a trench pattern with a line width of 0.8 μm and a space width of 0.2 μm, and then compare the results.

[0082] The resist pattern thus formed has high heat resistance. When a trench pattern having a film thickness of 3 μm, a line width of 0.8 μm, and a space width of 0.2 μm is heated at 50° C. for 60 seconds, the change in line width at the top of the pattern before and after heating is preferably 50 nm or less, more preferably 35 nm or less.

[0083] Ion implantation is performed using the formed resist pattern as a mask, or the formed resist pattern is used as a mask to process a layer below the resist pattern, a lower layer pattern is formed, and ion implantation is performed using the lower layer pattern as a mask; An engineered substrate is formed. Ion implantation can be performed 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 the impurity diffusion layer is usually performed in two stages: introduction of impurities and diffusion. 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 the support. As the ion acceleration energy during ion implantation, an energy load of 10 to 200 keV is generally applied to the resist pattern, which may destroy the resist pattern. The resist pattern formed by the present invention is a thick film, has high rectangularity, and has high heat resistance, and therefore can be suitably used for ion implantation applications in which ions are implanted at high energy. The ion source (impurity element) may be ions of boron, phosphorus, arsenic, argon, etc. The thin film on the substrate may be silicon, silicon dioxide, silicon nitride, aluminum, etc.

[0084] Thereafter, if necessary, further processing such as forming wiring on the processed substrate is performed to form a device. For these further processing, known methods can be applied. 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 element. EXAMPLES

[0085] The present invention will be described below with reference to various examples. However, the present invention is not limited to these examples.

[0086] Preparation of Composition 1 100 parts by mass of polymer 1, 1.00 parts by mass of photoacid generator 1, 0.15 parts by mass of base compound 1, and 0.06 parts by mass of surfactant 1 are added to a mixed solvent with a mass ratio of PGME:EL=70:30 so that the solid content ratio is 25.0% by mass. This is stirred at room temperature for 30 minutes. It is visually confirmed that the added materials are dissolved. This is filtered through a 0.05 μm filter. As a result, composition 1 is obtained. [ka] (Polymer 1) Hydroxystyrene:styrene:t-butyl acrylate copolymer, molar ratio 6:2:2, respectively, Mw approximately 9,000 The above ratio indicates the ratio of the number of constituent units of each repeating unit, and the same applies below. [ka] (Photoacid generator 1) Base compound 1: Tris[2-(2-methoxyethoxy)ethyl]amine Surfactant 1: Megafac R-40, DIC Corporation

[0087] Preparation of Compositions 2 to 11 and Comparative Composition 1 Compositions 2 to 11 and Comparative Composition 1 were obtained in the same manner as in the preparation of Composition 1, except that the composition was changed as shown in Table 1, the solvent was the same as in Composition 1, and the solid content ratio was the same as in Composition 1. In the table, the numerical values ​​for each composition indicate parts by mass. [Table 1] In the table, Polymer 2 [ka] Hydroxystyrene:styrene:t-butyl acrylate copolymer, molar ratio 6:2:2, respectively, Mw approx. 12,000 Polymer 3 [ka] Hydroxystyrene:styrene:t-butyl acrylate copolymer, molar ratio 6:2:2 respectively, Mw approx. 15,000 Polymer 4 [ka] Hydroxystyrene:styrene:t-butyl acrylate copolymer, molar ratio 6:2:2 respectively, Mw approx. 18,000 Polymer 5 (comparison polymer) [ka] Hydroxystyrene:styrene:t-butyl acrylate copolymer, molar ratio 6:2:2 respectively, Mw approx. 24,000 Polymer 6 [ka] Hydroxystyrene:styrene:ethylcyclopentyl acrylate copolymer, molar ratio 6:2:2 respectively, Mw approx. 12,000 Polymer 7 [ka] Hydroxystyrene:cyclohexyl acrylate:t-butyl acrylate copolymer, molar ratio 6:2:2, respectively, Mw approx. 12,000 Polymer 8 [ka] Hydroxystyrene:styrene:t-butyl acrylate copolymer, molar ratio 6:1:3, respectively, Mw approx. 12,000 Polymer 9 [ka] Anthracenemethanol methacrylate, acetoacetoxyethyl methacrylate 2-Hydroxypropyl methacrylate / t-butyl methacrylate copolymer, molar ratio 1:1:0.3:0.5, Mw approx. 15,000 Photoacid generator 2 [ka]

[0088] Example of resist pattern formation Using a coater developer Mark8 (Tokyo Electron), the composition prepared above is dropped onto an 8 cm Si wafer and spin-coated. This wafer is heated at 140°C for 90 seconds using a hot plate under atmospheric conditions to form a resist film. The thickness of the resist film at this point is measured using an optical interference film thickness measuring device M-1210 (SCREEN) to be 3.0 μm. The resist film is exposed using a KrF stepper FPA3000-EX5 (Canon). The exposed wafer is heated (PEB) at 120°C for 90 seconds using a hot plate under atmospheric conditions. The resist film is then paddle developed in a 2.38% by mass TMAH aqueous solution for 60 seconds, washed with DIW, and spin-dried at 1,000 rpm. This forms a trench pattern with a line width of 0.8 μm and a space width of 0.2 μm. The line width and space width are measured at the bottom of the pattern. Figure 1 shows a schematic diagram of the vertical cross-sectional shape of this pattern. A trench pattern 2 is formed on a substrate 1. The exposure dose at which a trench pattern with a line width of 0.8 μm and a space width of 0.2 μm is formed is defined as the optimum exposure dose, and the resolution, which will be described later, is evaluated at this optimum exposure dose.

[0089] Pattern rectangularity evaluation A slice of the sample created in the "Example of Resist Pattern Formation" above is prepared, and the vertical cross section of the pattern is observed with a scanning electron microscope (SEM). The ratio of the width at the top of the pattern to the width at the bottom of the pattern is evaluated. Figure 2 shows a schematic of the vertical cross section, with a trench pattern 2 formed on a substrate 1. The width at the top of the pattern is Wt, and the width at the bottom of the pattern is Wb. This ratio Pr is defined as Pr=Wt / Wb, and is used as an index for evaluating the rectangularity of the pattern. The evaluation criteria are as follows: A:Pr is 0.8 to 1.0 B:Pr is 0.7 to 0.8 C:Pr is 1.0 or more or 0.7 or less The evaluation results are shown in Table 2.

[0090] Resolution evaluation A mask pattern with a space size of 0.25 to 0.16 μm was used, and exposure was performed at the optimum exposure dose using the above-mentioned pattern formation method. The minimum dimension (μm) of the resist pattern resolved when exposed at the optimum exposure dose was taken as the resolution. For those where a pattern of 0.20 μm could not be formed, the minimum dimension that could be formed was taken as the resolution. The evaluation results are shown in Table 2.

[0091] Transmittance evaluation Each composition is dropped onto a quartz substrate and spin-coated. The wafer is heated at 140°C for 90 seconds using a hot plate under atmospheric conditions to form a resist film with a thickness of 5.0 μm. The transmission spectrum of this film is measured using a UV-Vis spectrometer (Thermo Fisher Scientific). The transmittance at 248 nm at this time is the transmittance for evaluation. The reference is a quartz substrate on which no resist film is formed.

[0092] Heat resistance evaluation The substrate on which the pattern was formed in the above "Example of Resist Pattern Formation" is heated at 150°C for 60 seconds using a hot plate. After that, the change in the pattern shape is observed from the vertical cross section using a SEM. The evaluation criteria are as follows. A: No change in shape was observed B: There is a change at the top of the resist pattern, and the amount of deformation is 50 nm or less. C: The deformation amount of the top of the resist pattern is more than 50 nm. [Table 2]

[0093] Evaluation of Composition 11 Composition 11 is used to carry out the following evaluations. When the resolution was evaluated in the same manner as above, the resolution was 180 nm and rated A. When the heat resistance was evaluated in the same manner as above, the deformation amount was 0 nm and rated A. [Explanation of symbols]

[0094] 1. Substrate 2.Trench pattern

Claims

1. An ion implantation thick-film resist composition comprising a polymer (A), a photoacid generator (B), and a solvent (C), The thickness of the resist film formed from the composition is 1.0 to 50 μm; The weight average molecular weight of the polymer (A) is 5,000 to 19,000; and A composition, wherein the polymer (A) comprises at least one of repeating units represented by formulas (A-1), (A-2), (A-3) and (A-4). 【Chemistry 1】 (where, R １１ , R ２１ , R ４１ and R ４５ are each independently C １－５ alkyl, wherein methylene in the alkyl may be replaced by oxy; R １２ , R １３ , R １４ , R ２２ , R ２３ , R ２４ , R ３２ , R ３３ , R ３４ , R ４２ , R ４３ , and R ４４ are each independently hydrogen, C １－５ Alkyl, C １－５ alkoxy, or —COOH; p11 is 0 to 4, p15 is 1 to 2, and p11 + p15 ≦ 5; p21 is 0 to 5, p41 is 0 to 4, p45 is 1 to 2, and p41 + p45 ≦ 5; P ３１ is C ４－２０ alkyl (wherein part or all of the alkyl may form a ring, part or all of the H in the alkyl may be substituted with halogen, and methylene in the alkyl may be substituted with oxy or carbonyl)

2. 2. The composition according to claim 1, wherein the resist film has a transmittance of 15 to 50% at a wavelength of 248 nm when the film thickness is 5 μm.

3. The number of repeating units n of the repeating units (A-1), (A-2), (A-3) and (A-4) in the polymer (A) Ａ－１ , n Ａ－２ , n Ａ－３ , and n Ａ－４ but, n Ａ－１ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ )=40~80%、 n Ａ－２ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ )=0~40%、 n Ａ－３ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ ) = 10 to 50%, or n Ａ－４ / (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ 3. The composition according to claim 1 or 2, wherein: Preferably, the total number n of all repeating units contained in the polymer (A) is ｔｏｔａｌ Then, (n Ａ－１ +n Ａ－２ +n Ａ－３ +n Ａ－４ ) / n ｔｏｔａｌ = Meets 80 to 100%.

4. 3. The composition according to claim 1, wherein the resist film has a resolution of 150 to 220 nm when the film thickness is 3 μm.

5. When a trench pattern having a film thickness of 3 μm, a line width of 0.8 μm, and a space width of 0.2 μm formed from the resist film is heated at 50° C. for 60 seconds, the change in line width at the top of the pattern before and after heating is 50 nm or less, and When the width of the top of the trench pattern is Wt and the width of the bottom of the pattern is Wb, the following relationship holds: 0.6≦Wt / Wb≦1.7 The composition according to claim 1 or 2, which satisfies the above.

6. 3. The composition according to claim 1, wherein the photoacid generator (B) is represented by formula (B-1): B ｎ＋ Cation B ｎ－ Anion (B-1) (where, B ｎ＋ The cation is a cation represented by formula (BC1), a cation represented by formula (BC2), or a cation represented by formula (BC3), and B ｎ＋ the cation as a whole is n-valent, n being 1 to 3; B ｎ－ The anion is an anion represented by formula (BA1), an anion represented by formula (BA2), an anion represented by formula (BA3), or an anion represented by formula (BA4), and B ｎ－ The anion as a whole has a valency of n. 【Chemistry 2】 (where, R ｂ１ are each independently C １－６ Alkyl, C １－６ Alkoxy, C ６－１２ Aryl, C ６－１２ arylthio, or C ６－１２ is aryloxy, nb1 is independently 0, 1, 2 or 3. 【Transformation 3】 (where, R ｂ２ are each independently C １－６ Alkyl, C １－６ Alkoxy, or C ６－１２ is aryl, nb2 is independently 0, 1, 2 or 3. 【Chemistry 4】 (where, R ｂ３ are each independently hydroxy, C １－６ Alkyl, C １－６ Alkoxy, or C ６－１２ is aryl, R ｂ４ are each independently C １－６ alkyl, provided that two R ｂ４ may be bonded to each other to form a ring structure, nb3 is independently 0, 1, 2 or 3. 【Transformation 5】 (where R ｂ５ are each independently C １－６ Fluorine-substituted alkyl, C １－６ fluorine-substituted alkoxy, or C １－６ alkyl) 【Transformation 6】 (where R ｂ６ is C １－１０ Fluorine-substituted alkyl, C １－６ Fluorine-substituted alkoxy, C ６－１２ Fluorine-substituted aryl, C ２－１２ Fluorine-substituted acyl, or C ６－１２ fluorine-substituted alkoxyaryl) 【Transformation 7】 (where, R ｂ７ are each independently C １－６ Fluorine-substituted alkyl, C １－６ Fluorine-substituted alkoxy, C ６－１２ Fluorine-substituted aryl, C ２－１２ Fluorine-substituted acyl, or C ６－１２ fluorine-substituted alkoxyaryl, wherein two R ｂ７ may be bonded to each other to form a fluorine-substituted heterocyclic structure) 【Transformation 8】 (where, R ｂ８ is hydrogen, C １－６ Alkyl, C １－６ alkoxy, or hydroxy; ｂ is methylene, ethylene, carbonyl, oxy or carbonyloxy; Y ｂ are each independently hydrogen or fluorine, nb4 is an integer from 0 to 10, and nb5 is an integer from 0 to 21.

7. 3. The composition according to claim 1 or 2, wherein the solvent (C) is propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, n-butyl acetate, n-butyl ether, 2-heptanone, cyclohexanone, or any combination thereof.

8. The composition according to claim 1 or 2, further comprising a basic compound (D): Preferably, the basic compound (D) is ammonia, C １－１６ Primary aliphatic amine compounds, C ２－３２ Secondary aliphatic amine compounds, C ３－４８ Tertiary aliphatic amine compounds, C ６－３０ Aromatic amine compounds, C ５－３０ a heterocyclic amine compound, or any combination thereof; or Preferably, the content of the basic compound (D) is 0.01 to 5 parts by mass based on 100 parts by mass of the polymer (A).

9. The composition according to claim 1 or 2, further comprising a surfactant (E): Preferably, the content of the surfactant (E) is 0.005 to 1 part by mass per 100 parts by mass of the polymer (A).

10. The composition according to claim 1 or 2, further comprising a dye (F): Preferably, the content of the dye (F) is 0 to 0.5 parts by mass based on 100 parts by mass of the polymer (A).

11. The composition according to claim 1 or 2, further comprising an additive (G): Preferably, the additive (G) is a surface smoothing agent, a plasticizer, a contrast enhancing agent, an acid, a radical generator, a substrate adhesion enhancing agent, an antifoaming agent, or any combination thereof; or Preferably, the content of the additive (G) is 0 to 5 parts by mass based on 100 parts by mass of the polymer (A).

12. The composition according to claim 1 or 2, wherein the polymer (A) comprises further repeating units other than the repeating units represented by formulas (A-1) to (A-4): Preferably, the content of the further repeating unit contained in the polymer (A) is 0 to 10 parts by mass per 100 parts by mass of the polymer (A); or Preferably, the further repeat unit comprises an arylcarbonyl.

13. 3. The composition according to claim 1, wherein the content of salicylic acid is 0 to 0.005 parts by mass based on 100 parts by mass of the polymer (A).

14. The content of the polymer (A) is 10 to 40 mass% based on the composition, The content of the photoacid generator (B) is 0.3 to 4 parts by mass, preferably 0.4 to 2 parts by mass, based on 100 parts by mass of the polymer (A), and The composition according to claim 1 or 2, wherein the content of the solvent (C) is 50 to 90 mass% based on the composition.

15. A method for producing a processed substrate, comprising the steps of: A method for producing a resist pattern using the composition according to claim 1 or 2; and performing ion implantation using the resist pattern as a mask; or 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.

16. A method for manufacturing a device comprising the method of claim 15: Preferably, the method further comprises forming wiring on the processed substrate.

Images