Resist compositions and methods of using the same to prepare resist films

Abstract

Provided is a resist composition with improved rectangularity. A resist composition comprising: a polymer containing an acid dissociation group (A) and a compound represented by formula (I) (B).

Description

Technical Field

[0001] This invention relates to a photoresist composition for manufacturing semiconductor devices, semiconductor integrated circuits, etc., and a method for manufacturing a photoresist film using the photoresist composition. Background Technology

[0002] In the manufacturing process of semiconductors and other devices, photolithography is typically used to perform microfabrication using photoresist compositions. In recent years, the demand for higher integration levels in LSIs (Large-Scale Integration) has been increasing. Higher integration levels enable smaller sizes and faster speeds, significantly improving the performance of electronic devices such as computers, smartphones, and network equipment.

[0003] To achieve higher integration, finer resist patterns are required. Photolithography processes using KrF excimer lasers, ArF excimer lasers, extreme ultraviolet light, X-rays, electron beams, etc., fall under the category of microscopy. To obtain finer resist patterns, photosensitive resist compositions are needed to form resist patterns that are closer to rectangles.

[0004] To prevent halos and obtain a good resist pattern shape, it is recommended to add anthracene derivatives with specific structures to the resist composition (Patent Document 1).

[0005] [List of cited references]

[0006] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2004-310121 Summary of the Invention

[0008] [Technical Issues]

[0009] When forming high-rectangularity patterns, the irradiated light may be reflected and diffused at the interface between the substrate and the resist. For example, with positive resists, an undercut may occur, where the lower part of the resist is scraped into a recessed shape, making it impossible to obtain a high-rectangularity pattern. Although forming a bottom anti-reflective coating (BARC) on the substrate can suppress undercut, the inventors are concerned with developing a technique to reduce undercut and obtain high-rectangularity patterns without using BARC in order to increase yield per unit time and reduce production costs.

[0010] The inventors believe that one or more problems still exist regarding the resist compositions and their applications, requiring improvement. These problems include: inability to obtain sufficiently rectangular resist patterns; lateral etching between the resist pattern and the substrate surface; footing at the resist pattern-substrate interface; insufficient etch resistance of the resist pattern in subsequent steps (e.g., insufficient dry etching resistance); poor coating performance of the resist composition; insufficient resist pattern resolution; insufficient LWR (linewidth roughness) of the resist pattern; excessive optimal exposure; insufficient etch resistance of the resist pattern; large variation in the pattern width of the resist pattern; low aspect ratio of the resist pattern; narrow process window; and low manufacturing yield.

[0011] Based on the above-mentioned technical background, the present invention provides a photoresist composition and a method for preparing a photoresist film using the photoresist composition.

[0012] [Solution to the problem]

[0013] The resist composition according to the present invention comprises: a polymer (A) containing an acid-dissociating group and a compound (B) represented by formula (I).

[0014] [C1]

[0015]

[0016] in:

[0017] X 1 To X 10 Each is independently H, OH, NH2, halogen, C 1-10 Alkyl, C 1-10 Alkyl group or R represented by formula (II);

[0018] When X 1 To X 10 When each is an alkyl group independently, one or more non-adjacent methylene (-CH2-) groups of the alkyl group may be independently replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, or -C≡C-; and

[0019] X 1 To X 10 At least one of them is R;

[0020] [C2]

[0021]

[0022] in:

[0023] Y 1 To Y 5Each is independently H, OH, NH2, halogen, C 1-10 Alkyl or C 1-10 Alkoxy;

[0024] When Y 1 To Y 5 When each is an alkyl group independently, one or more non-adjacent methylene (-CH2-) groups of the alkyl group may be independently replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH- or -C≡C-.

[0025] When Y 1 To Y 5 When each is an alkyl group independently, one or more H atoms of the alkyl group may be replaced by OH, NH2 or halogen;

[0026] Y 1 To Y 5 At least one of them is OH or contains OH;

[0027] L 1 For single bond or C 1-10 Alkylene; and;

[0028] When L 1 When it is an alkylene group, L 1 One or more non-adjacent methylene (-CH2-) groups can be independently replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH- or -C≡C-.

[0029] The method for preparing a resist film according to the present invention includes the step of coating the above-described resist composition onto a substrate to form a coating film.

[0030] The method for preparing resist patterns according to the present invention includes the following steps:

[0031] The resist film was prepared using the method described above.

[0032] Expose the resist film to light; and

[0033] Develop the resist film.

[0034] The method for manufacturing a processed substrate according to the present invention includes the following steps:

[0035] The resist pattern was prepared using the above method; and

[0036] The process involves using the resist pattern as a mask.

[0037] The method for manufacturing a device according to the present invention includes the method described above.

[0038] This invention relates to the use of the above-described resist composition for forming a resist film on a substrate.

[0039] [Advantages of the Invention]

[0040] According to the present invention, one or more of the following effects can be expected:

[0041] It can achieve resist patterns with improved rectangularity; it can suppress lateral etching between the resist pattern and the substrate surface; it can suppress the appearance of footings at the interface between the resist pattern and the substrate; the resist pattern has sufficient resistance in subsequent steps (e.g., resistance to dry etching); the resist composition has good coatability; the resist pattern has sufficient resolution; the resist pattern has a sufficiently low LWR; the optimal exposure is small enough; the resist pattern has sufficient etch resistance; it can suppress variations in the pattern width of the resist pattern; the resist pattern has a sufficiently high aspect ratio; the process window is wide enough; and it improves manufacturing yield. Detailed Implementation

[0042] [definition]

[0043] Unless otherwise specified, the definitions or examples set forth in this paragraph shall apply in this specification.

[0044] The singular form should include the plural form, and "a" or "the" means "at least one". An element in a concept can be expressed in multiple types, and when describing its quantity (e.g., mass% or mole%), the quantity refers to the sum of the multiple types.

[0045] "And / or" includes all combinations of elements, as well as cases where elements are used individually.

[0046] When using "~ / to" or "-" to represent a numerical range, it includes both endpoints and the units are the same. For example, 5 to 25 mol% means more than 5 mol% and less than 25 mol%.

[0047] Such as "C" x-y “C” x -C y "and "C x Descriptions like "" refer to the number of carbon atoms in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain containing 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl).

[0048] Groups such as alkyl, alkylene, or alkoxy can have linear, branched, or cyclic structures. An alkyl group is a group obtained by removing one hydrogen atom from a saturated hydrocarbon, while an alkylene group is a group obtained by removing two hydrogen atoms from a saturated hydrocarbon.

[0049] When a polymer contains multiple repeating units, these repeating units form a copolymer. Copolymers can be alternating copolymers, random copolymers, block copolymers, graft copolymers, or a mixture thereof. When a polymer or resin is represented by a structural formula, the 'n', 'm', etc., outside the parentheses indicate the number of repeating units.

[0050] Temperature is measured in Celsius (degrees Celsius). For example, 20 degrees means 20 degrees Celsius.

[0051] Additives refer to compounds that have a specific function (e.g., a base-generating agent is a compound capable of generating a base). An embodiment may also exist in which the compound is dissolved or dispersed in a solvent and added to the composition. As an embodiment of the invention, preferably, the solvent is included as solvent (G) or as another component in the composition according to the invention.

[0052] The embodiments of the present invention will now be described in detail.

[0053] <Resistant Composition>

[0054] The resist composition according to the invention (hereinafter referred to as the composition in some cases) comprises: a polymer (A) containing an acid-dissociating group and a compound (B) represented by formula (I).

[0055] The resist composition according to the present invention is preferably a thin-film chemically amplified resist composition.

[0056] In this context, a thin film refers to a film with a thickness of 1200 nm or less, preferably 50 to 1100 nm, and more preferably 80 to 1000 nm. The kinematic viscosity of the composition according to the invention is preferably 0.5 to 5 mm. 2 / s, more preferably 1.5 to 4 mm 2 / s. In this respect, viscosity was measured using a capillary viscometer at 25°C.

[0057] As a preferred embodiment, the composition according to the present invention is a thin-film KrF chemically amplified resist composition. As another embodiment, the composition according to the present invention is preferably a positive resist composition, more preferably a thin-film positive chemically amplified resist composition, and even more preferably a thin-film KrF positive chemically amplified resist composition.

[0058] Polymer (A) containing acid-dissociating groups

[0059] The polymer (A) containing acid-dissociating groups used in this invention (hereinafter referred to as component (A) in some cases, and other components may also be applicable) reacts with acids to increase its solubility in alkaline aqueous solutions. Such polymers, for example, have acid groups protected by protective groups, which are removed when acid is added from the outside, thereby increasing their solubility in alkaline aqueous solutions.

[0060] In a preferred embodiment, component (A) comprises:

[0061] The repeating unit represented by equation (A-1); and

[0062] At least one repeating unit is selected from the group of repeating units represented by equations (A-2) to (A-4).

[0063] Equation (A-1) is as follows.

[0064] [C3]

[0065]

[0066] in:

[0067] Group R 11 Each independently is C 1-5 Alkyl group (wherein the -CH2- of the alkyl group may be replaced by -O-), preferably methyl or ethyl, more preferably methyl.

[0068] R 12 R 13 and R 14 Each independently represents H and C. 1-5 Alkyl, C 1-5 Alkyl or -COOH, preferably H or methyl, more preferably H.

[0069] p11 is 0 to 4, preferably 0 or 1, more preferably 0.

[0070] p15 is 1 to 2, preferably 0 or 1, more preferably 1.

[0071] p11+p15≤5.

[0072] Component (A) may contain multiple types of units represented by equation (A-1). For example, component (A) may have one unit with p15=1 and one unit with p15=2 in a ratio of 1:1.

[0073] In this case, p15 is equal to 1.5. Hereinafter, unless otherwise stated, the numbers representing resins or polymers in this invention apply.

[0074] Specific examples of equation (A-1) include the following.

[0075] [C4]

[0076]

[0077] Equation (A-2) is as follows.

[0078] [C5]

[0079]

[0080] in:

[0081] Group R 21 Each independently is C 1-5 Alkyl group (wherein the -CH2- of the alkyl group may be replaced by -O-), preferably methyl, ethyl, tert-butyl or tert-butoxy, more preferably methyl or ethyl, and even more preferably methyl.

[0082] R 22 R 23 and R 24 Each independently represents H and C. 1-5 Alkyl, C 1-5 Alkyl or -COOH, preferably H or methyl, more preferably H.

[0083] p21 is 0 to 5, preferably 0, 1, 2, 3, 4 or 5, more preferably 0 or 1, and even more preferably 0.

[0084] Specific examples of equation (A-2) include the following.

[0085] [C6]

[0086]

[0087] Equation (A-3) is as follows.

[0088] [C7]

[0089]

[0090] in:

[0091] R 32 R 33 and R 34 Each independently represents H and C. 1-5 Alkyl, C 1-5 Alkoxy or -COOH, preferably H, methyl, ethyl, tert-butyl, methoxy, tert-butoxy or -COOH, more preferably H or methyl, and even more preferably H.

[0092] P 31 C 4-20Alkyl group. In this respect, the alkyl group may partially or completely form a ring, and some or all of the H atoms in the alkyl group may be substituted with halogens. P 31 The alkyl portion is preferably branched or cyclic. If P 31 C 4-20 If the hydrogen atom on the alkyl group is replaced by a halogen, preferably all hydrogen atoms are substituted, and the substituted halogen is preferably F or Cl; more preferably F. No halogen substitution is used for P. 31 C 4-20 The H on the alkyl group is a preferred embodiment of the present invention. P 31 Preferably, it is methyl, isopropyl, tert-butyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, adamantyl, methyl adamantyl, or ethyl adamantyl; more preferably, it is tert-butyl, ethylcyclopentyl, ethylcyclohexyl, or ethyl adamantyl; even more preferably, it is tert-butyl, ethylcyclopentyl, or ethyl adamantyl; and even more preferably, it is tert-butyl.

[0093] Specific examples of equation (A-3) include the following.

[0094] [C8]

[0095]

[0096] Equation (A-4) is as follows.

[0097] [C9]

[0098]

[0099] in:

[0100] R 41 and R 45 Each independently is C 1-5 Alkyl group (where the -CH2- of the alkyl group can be replaced by -O-). R 45 Preferably, it is methyl, tert-butyl, or -CH(CH3)-O-CH2CH3. 41 Preferably, it is methyl, ethyl, or tert-butyl, more preferably methyl.

[0101] R 42 R 43 and R 44 Each independently represents H and C. 1-5 Alkyl, C 1-5 Alkyl or -COOH, preferably H or methyl, more preferably H.

[0102] p41 is 0 to 4, p45 is 1 to 2, and p41 + p45 ≤ 5. p41 is preferably 0, 1, 2, 3 or 4, more preferably 0 or 1, and even more preferably 0. p45 is preferably 1 or 2, more preferably 1.

[0103] Specific examples of equation (A-4) are as follows.

[0104] [C10]

[0105]

[0106] The number of repeating units n in component (A) of repeating units (A-1), (A-2), (A-3), and (A-4) A-1 n A-2 n A-3 and n A-4 The description is as follows.

[0107] n A-1 / (n A-1 +n A-2 +n A-3 +n A-4 The content is preferably 40% to 80%; more preferably 50% to 80%; even more preferably 55% to 75%; and even more preferably 60% to 70%.

[0108] n A-2 / (n A-1 +n A-2 +n A-3 +n A-4 The preferred percentage is 0% to 40%; more preferably 5% to 35%; even more preferably 5% to 25%; and still more preferably 10% to 20%.

[0109] n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 The preferred percentage is 0% to 40%; more preferably 10% to 35%; even more preferably 15% to 35%; and still more preferably 20% to 30%.

[0110] n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 The preferred percentage is 0% to 40%; more preferably 10% to 35%; even more preferably 15% to 35%; and still more preferably 20% to 30%.

[0111] Preferred implementation schemes include n A-1 / (n A-1 +n A-2 +n A-3 +n A-4 ) = 40% to 80%, n A-2 / (n A-1 +n A-2 +nA-3 +n A-4 ) = 0% to 40%, n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) = 0% to 40%, and n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 =0% to 40%.

[0112] As one embodiment of the present invention, n is preferred. A-3 >0 and n A-4 =0, or n A-3 =0 and n A-4 >0, and more preferably n A-3 >0 and n A-4 =0.

[0113] Component (A) may also contain repeating units other than those represented by (A-1), (A-2), (A-3), and (A-4). The total number of repeating units contained in component (A) is defined as n. total At that time, (n A-1 +n A-2 +n A-3 +n A-4 ) / n total Preferably 80% to 100%; more preferably 90% to 100%; even more preferably 95% to 100%; and even more preferably 100%.

[0114] More specifically, it is also a preferred embodiment of the invention that does not include any other units besides the repeating units represented by (A-1), (A-2), (A-3) and (A-4).

[0115] The mass-average molecular weight (hereinafter referred to as Mw) of component (A) is preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, even more preferably from 5,000 to 20,000, and even more preferably from 8,000 to 15,000.

[0116] The number-average molecular weight (hereinafter referred to as Mn in some cases) of component (A) is preferably from 1,000 to 50,000; more preferably from 2,000 to 30,000.

[0117] In this invention, Mw and Mn can be measured by gel permeation chromatography (GPC).

[0118] For measurements, a preferred example is to use a GPC column at 40°C, with tetrahydrofuran as the elution solvent, a flow rate of 0.6 mL / min, and monodisperse polystyrene as the standard.

[0119] For illustrative purposes, the following description is provided. In the compositions according to the invention, two or more components (A) may be used, provided that these components (A) conform to the structure of the above formula. For example, a composition comprising two polymers as component (A) is also an embodiment of the invention.

[0120] [C11]

[0121]

[0122] Component (A) preferably contains one or two polymers, more preferably two polymers. The Mw distribution and degree of polymerization may vary.

[0123] Based on the total mass of the composition, the content of component (A) is preferably 1 to 15% by mass, more preferably 1.5 to 12% by mass, and even more preferably 2 to 10% by mass.

[0124] The composition according to the invention may contain polymers other than component (A). Based on the total mass of component (A), the content of polymers other than component (A) (or the sum of them if there are more than one) is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, even more preferably 0 to 5% by mass, and even more preferably, the composition according to the invention does not contain any polymers other than component (A) (0% by mass).

[0125] Compound (B) is represented by formula (I).

[0126] The composition according to the invention comprises compound (B) represented by formula (I).

[0127] Including component (B) can yield a resist pattern with sufficient rectangularity. While this is not determined by any theory, it is generally believed that the reason is as follows.

[0128] For example, when the resist composition is positive, component (B) absorbs excess light reaching the vicinity of the substrate during exposure, thus preventing the resist pattern from lateral etching due to light reflection. Furthermore, because component (B) has good solubility in the developer, even with poor development, the resist pattern will not develop a base after development, thereby preventing the resist pattern from becoming conical.

[0129] Equation (I) is as follows.

[0130] [C12]

[0131]

[0132] in:

[0133] X 1 To X 10 Each is independently H, OH, NH2, halogen, C 1-10 Alkyl, C 1-10 Alkyl group or R represented by formula (II);

[0134] When X 1 To X 10 When each is an alkyl group independently, one or more non-adjacent methylene (-CH2-) groups of the alkyl group may be independently replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, or -C≡C-; and

[0135] X 1 To X 10 At least one of them is R;

[0136] [C13]

[0137]

[0138] in:

[0139] Y 1 To Y 5 Each is independently H, OH, NH2, halogen, C 1-10 Alkyl or C 1-10 Alkoxy groups, preferably H, OH, or C. 1-10 Alkyl or C 1-10 Alkoxy groups, more preferably H, OH or C 1-5 alkyl.

[0140] When Y 1 To Y 5 When each is an alkyl group independently, one or more non-adjacent methylene (-CH2-) groups of the alkyl group may be independently replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH- or -C≡C-, preferably unsubstituted.

[0141] When Y 1 To Y 5 When each is an alkyl group independently, one or more H atoms of the alkyl group may be replaced by OH, NH2 or halogen, preferably unsubstituted.

[0142] Y 1 To Y 5At least one of them is OH or contains OH, preferably, at least one of them is OH. The number of OH on each aromatic ring is preferably 3 or less, more preferably 2 or less, and even more preferably 1. Although not limited by any theory, it is believed that the number of OH on each aromatic ring as described above can more effectively suppress the progress of crosslinking reactions and the interactions between compounds.

[0143] L 1 For single bond or C 1-10 Alkylene, preferably a single bond, methylene (-CH2-) or ethylene (-CH2-CH2-), more preferably a single bond or methylene.

[0144] When L 1 When it is an alkylene group, L 1 One or more non-adjacent methylene (-CH2-) groups may be independently replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH- or -C≡C-, preferably unsubstituted.

[0145] In a preferred embodiment, component (B) is represented by formula (Ia).

[0146] [C14]

[0147]

[0148] in:

[0149] n1 is 1, 2, 3, 4 or 5, preferably 1, 2 or 3, more preferably 1 or 2, and even more preferably 1.

[0150] n2 is 1, 2, 3, 4 or 5, preferably 1, 2 or 3, more preferably 1 or 2, and even more preferably 1.

[0151] R a1 R a2 and R a3 Each independently constitutes a halogen, C 1-10 Alkyl or C 1-10 Alkoxy, preferably C 1-5 Alkyl or C 1-5 Alkyl group.

[0152] n3, n4 and n5 are each independently 0, 1, 2, 3 or 4, preferably 0 or 1, more preferably 0.

[0153] L a1 and L a2 Each is independently a single bond or C 1-10 Alkylene, preferably a single bond, methylene (-CH2-) or ethylene (-CH2-CH2-), more preferably a single bond or methylene.

[0154] Specific examples of component (B) include the following.

[0155] [C15]

[0156]

[0157] Based on the total mass of the composition, the content of component (B) is preferably 0.01 to 0.1% by mass, more preferably 0.02 to 0.09% by mass, and even more preferably 0.03 to 0.08% by mass.

[0158] The following describes in detail some specific examples of compounds that can be read from formulas (I) and (II).

[0159] The following compounds can be read from formula (I) and formula (II).

[0160] In equation (I), X 1 To X 8 For H, X 9 and X 10 Let R be the value.

[0161] In equation (II), for the corresponding X 9 R, L 1 For a single bond, Y 1 Y 2 Y 4 and Y 5 For H, Y 3 It is OH.

[0162] For the corresponding X 10 R, L 1 It is a C1 alkylene group, i.e., methylene, Y 1 Y 2 Y 4 and Y 5 For H, Y 3 It is OH.

[0163] [C16]

[0164]

[0165] The following compounds can also be read from formulas (I) and (II).

[0166] In equation (I), X 1 To X 8 For H, X 9 and X 10 Let R be the value.

[0167] In equation (II), for the corresponding X 9 R, L 1 For a single bond, Y 1and Y 5 For H, Y 2 and Y 4 It is a C1 alkyl group, in which one H is replaced by OH, i.e., hydroxymethyl, Y 3 It is OH.

[0168] For the corresponding X 10 R, L 1 It is a C1 alkylene group, i.e., methylene, Y 1 and Y 5 For H, Y 2 and Y 4 It is a C1 alkyl group, in which one H is replaced by OH, i.e., hydroxymethyl, Y 3 It is OH.

[0169] [C17]

[0170]

[0171] As shown in the two examples mentioned above, when multiple X's in equation (I) 1 To X 10 When the group is R, L in formula (II) 1 and Y 1 To Y 5 The R groups may be different from or the same as each other.

[0172] First acid generator (C)

[0173] The composition according to the invention preferably further comprises a first acid generating agent (C). The first acid generating agent (C) has a -SO2- structure.

[0174] Component (C) is preferably a photoacid generator that releases acid upon light irradiation. Preferably, the acid derived from component (C) acts on component (A) to increase the solubility of component (A) in an alkaline aqueous solution. For example, component (A) causes its acid dissociation groups to be eliminated along with the acid. Component (C) used in the compositions according to the invention may be selected from conventionally known components.

[0175] Component (C) releases acid when exposed to light, and its acid dissociation constant pKa(H2O) is preferably -20 to 1.4; more preferably -16 to 1.4; even more preferably -16 to 1.2; and even more preferably -16 to 1.1.

[0176] Component (C) is preferably represented by the following formula (C-1) or formula (C-2).

[0177] Equation (C-1) is as follows.

[0178] [C18]

[0179]

[0180] in:

[0181] Group R c1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Aryl thiols or C 6-12 The aryloxy group is preferably methyl, ethyl, tert-butyl, methoxy, ethoxy, phenylthio, or phenoxy, and more preferably tert-butyl, methoxy, ethoxy, phenylthio, or phenoxy.

[0182] Each digit nc1 is independently 0, 1, 2, or 3. A preferred embodiment is that all digits nc1 are 1. Another preferred embodiment is that all digits nc1 are equal. Yet another preferred embodiment is that all digits nc1 are 0. Still another preferred embodiment is that one digit nb1 is 3, while the other two digits nc1 are 0.

[0183] A - It is a monovalent anion.

[0184] Specific examples of cations of formula (C-1) include the following.

[0185] [C19]

[0186]

[0187] A - Examples include halide ions, hexafluoroantimonate ions, hexafluorophosphate ions, and ions represented by the following formulas (CA1) to (CA4), and A - The preferred ions are hexafluoroantimonate ions, ions represented by formula (CA1), or ions represented by formula (CA2).

[0188] Equation (CA1) is as follows.

[0189] [C20]

[0190]

[0191] Among them, R c5 Each group is independently C 1-6 Fluorinated alkyl groups, C 1-6 Fluorine-substituted alkoxy or C 1-6 Alkyl group. For example, -CF3 represents a methyl group (C1) in which all hydrogen atoms are substituted with fluorine. In this invention, fluorine substitution means that some or all of the hydrogen atoms in the alkyl or alkoxy group are substituted with fluorine, more preferably, the hydrogen atoms are completely substituted with fluorine.

[0192] R c5Preferably, it is a fluorinated or unsubstituted methyl, ethyl, tert-butyl, methoxy, ethoxy, or tert-butoxy compound, more preferably a fluorinated or unsubstituted methyl compound.

[0193] R c5 Preferably, it is a fluorine-substituted alkyl group; more preferably, it is -CF3.

[0194] Specific examples of formula (CA1) are as follows.

[0195] [C21]

[0196]

[0197] Equation (CA2) is as follows.

[0198] [C22]

[0199]

[0200] Among them, R c6 C 1-10 Fluorinated alkyl groups, C 1-6 Fluorinated alkoxy groups, C 6-12 Fluorinated aryl, C 2-12 Fluorinated acyl groups, C 6-12 Fluorine-substituted alkoxyaryl or C 6-12 Alkyl-substituted aryl; preferably C 1-10 Fluorinated alkyl groups, C 6-12 Fluorine-substituted aryl or C 6-12 Alkyl-substituted aryl, more preferably C 1-6 Fluorinated alkyl or C 6-10 Fluorine-substituted aryl group. R c6 The alkyl or alkyl moiety is preferably straight-chain or cyclic.

[0201] Specific examples of formula (CA2) are as follows.

[0202] [C23]

[0203]

[0204] Equation (CA3) is as follows.

[0205] [C24]

[0206]

[0207] in:

[0208] Group R c7 Each independently is C 1-6 Fluorinated alkyl groups, C 1-6 Fluorinated alkoxy groups, C 6-12 Fluorinated aryl, C 2-12Fluorine-substituted acyl groups or C 6-12 Fluorine-substituted alkoxyaryl group; preferably C 2-6 Fluorine-substituted alkyl group. Two groups R c7 They can be interconnected to form a fluorine-substituted heterocyclic structure. This heterocyclic structure is preferably a saturated ring. The heterocyclic structure is preferably a five- to eight-membered monocyclic structure containing N and S; more preferably a five-membered or six-membered ring; even more preferably a six-membered ring.

[0209] Specific examples of formula (CA3) are as follows.

[0210] [C25]

[0211]

[0212] Equation (CA4) is as follows.

[0213] [C26]

[0214]

[0215] in:

[0216] R c8 For H, C 1-6 Alkyl, C 1-6 Alkyl or OH; preferably H, methyl, ethyl, methoxy or OH; more preferably H or OH.

[0217] L c It can be methylene, ethylene, carbonyl, oxygen, or carbonyloxy; preferably ethylene or carbonyl.

[0218] Group Y c Each is independently H or fluorine; preferably, one or more of them are fluorine.

[0219] nc4 is an integer from 0 to 10; preferably 0, 1 or 2.

[0220] nc5 is an integer from 0 to 21; preferably 4, 5 or 6.

[0221] Specific examples of formula (CA4) are as follows.

[0222] [C27]

[0223]

[0224] Equation (C-2) is as follows.

[0225] [C28]

[0226]

[0227] in:

[0228] R11 C 1-10 Alkyl or C 6-12 Aryl, preferably tolyl, C 1-6 Alkyl or C 6-10 Aryl, more preferably p-tolyl.

[0229] Specific examples of equation (C-2) include the following.

[0230] [C29]

[0231]

[0232] The molecular weight of component (C) is preferably from 400 to 2500, more preferably from 400 to 1500.

[0233] Component (C) may have one, two or more components, preferably two or more components, more preferably three or more components, and even more preferably three components.

[0234] Based on the total mass of component (A), the content of component (C) is preferably 1 to 15% by mass, more preferably 1.5 to 10% by mass, and even more preferably 2 to 6% by mass.

[0235] Second acid generator (D)

[0236] The composition according to the invention preferably further comprises a second acid generating agent (D). Component (D) is different from component (C).

[0237] Component (D) is preferably a photoacid generator that can generate acid using light.

[0238] In a preferred embodiment of the invention, the cations derived from component (D) partially react with the anions derived from component (C) and act as quenchers. In this case, component (D) can act as a quencher to suppress the diffusion of acid derived from component (C) generated at the exposed site. Although not limited to any particular theory, the mechanism is considered to be as follows: When exposure causes acid to be released from component (C), and this acid diffuses to the unexposed site, salt exchange with component (D) occurs. More specifically, the anions of component (C) and the cations of component (D) form a salt. Therefore, the diffusion of acid is suppressed. In this case, although the anions of component (D) are released, these anions are weak acids and cannot deprotect the polymer, so the unexposed sites are unaffected.

[0239] Furthermore, component (D) serves to prevent the acid on the resist film surface from being deactivated by components such as amines present in the air. While not limited to any single theory, the mechanism is believed to be as follows: At the exposure site, acid (a weak acid originating from component (D) and an acid originating from component (C)) is generated through exposure. Amines in the air penetrate to the resist film surface, thereby neutralizing the acid present therein. However, the presence of the weak acid released by component (D) reduces the frequency of neutralization of the acid released by component (C). It is believed that increasing the acid concentration at the exposure site, as described above, can prevent acid deactivation.

[0240] Component (D) is preferably represented by formula (D-1).

[0241] D m+ Cation D m- Anion (D-1)

[0242] in:

[0243] D m+ The cation is a cation represented by formula (DC1) or a cation represented by formula (DC2); preferably, it is a cation represented by formula (DC1).

[0244] D m+ The cation as a whole has a valence of m, where m ranges from 1 to 3.

[0245] D m- The anion is an anion represented by formula (DA1) or an anion represented by formula (DA2); preferably, it is an anion represented by formula (DA1). m- The anions are generally in the m valence.

[0246] m is preferably 1 or 2; more preferably 1.

[0247] Equation (DC1) is as follows.

[0248] [C30]

[0249]

[0250] in:

[0251] Group R d1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl;

[0252] Each number nd1 is independently 0, 1, 2, or 3.

[0253] R d1 Preferably, it is methyl, ethyl, tert-butyl, methoxy, ethoxy, phenylthio, or phenoxy; more preferably, it is tert-butyl, methoxy, ethoxy, phenylthio, or phenoxy; even more preferably, it is tert-butyl or methoxy.

[0254] nd1 is preferably 0 or 1; more preferably 0.

[0255] Another preferred embodiment is that all digits nd1 are 1, and all groups R d1 They are all the same.

[0256] Specific examples of formula (DC1) include the following.

[0257] [C31]

[0258]

[0259] Equation (DC2) is as follows.

[0260] [C32]

[0261]

[0262] in:

[0263] Group R d2 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl;

[0264] Each number nd2 is independently 0, 1, 2, or 3.

[0265] Rd2 is preferably C 4-6 Branched alkyl groups. Each R in the formula d2 They can be the same or different, but the same is preferred. R d2 More preferably, it is tert-butyl or 1,1-dimethylpropyl; even more preferably, it is tert-butyl.

[0266] Each nd2 is preferably 1.

[0267] Specific examples of formula (DC2) include the following.

[0268] [C33]

[0269]

[0270] Equation (DA1) is as follows.

[0271] [C34]

[0272]

[0273] in:

[0274] X is C 1-20 Hydrocarbon group or single bond;

[0275] Group Rd3 Each is independently H, OH, C 1-6 Alkyl or C 6-10 Aryl;

[0276] nd3 is 1, 2, or 3; and

[0277] nd4 can be 0, 1, or 2.

[0278] When X is a hydrocarbon group, X can be straight-chain, branched, or cyclic, preferably straight-chain or cyclic. When X is straight-chain, X is preferably C. 1-4 (More preferably C) 1-2 The chain preferably contains a double bond or is a saturated hydrocarbon. When X is a cyclic hydrocarbon, X can be a monocyclic aromatic ring, or a saturated monocyclic or polycyclic ring; when X is a monocyclic ring, the ring is preferably a six-membered ring; when X is a polycyclic ring, the ring is preferably an adamantane ring.

[0279] X 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.

[0280] nd3 is preferably 1 or 2; more preferably 1.

[0281] nd4 is preferably 0 or 1; more preferably 1.

[0282] R d3 Preferably, it is OH, methyl, ethyl, 1-propyl, 2-propyl, tert-butyl, or phenyl; more preferably, it is OH.

[0283] When X is a single bond, R d3 H is preferred. X represents a single bond, R d3 Represents H, and in (DA1) nd3=nd4=1 represents H-COO - The anion.

[0284] Specific examples of formula (DA1) include the following.

[0285] [C35]

[0286]

[0287] Equation (DA2) is as follows.

[0288] [C36]

[0289]

[0290] in:

[0291] R d4 C 1-15Alkyl group (wherein the alkyl group may partially or completely form a ring, and the -CH2- of the alkyl group may be replaced by -C(=O)-). R d4 C is preferred 3-13 Alkyl; more preferably C 5-12 Alkyl; more preferably C 8-12 Alkyl; or even more preferably C 10 Alkyl group. R d4 The alkyl group preferably forms a ring, either partially or entirely; more preferably, it forms a ring. Preferably, R... d4 One or more (more preferably one) -CH2- groups of the alkyl group are replaced by -C(=O)-.

[0292] Specific examples of formula (DA2) are as follows.

[0293] [C37]

[0294]

[0295] When exposed to light, component (D) releases an acid, and its acid dissociation constant pKa(H2O) is preferably 1.5 to 8, more preferably 1.5 to 5.

[0296] The molecular weight of component (D) is preferably 300 to 1400; more preferably 300 to 1200.

[0297] Component (D) may have one, two or more components.

[0298] Based on the total mass of component (A), the content of component (D) is preferably 0.005 to 0.3% by mass, more preferably 0.01 to 0.2% by mass, and even more preferably 0.03 to 1% by mass.

[0299] Photoalkali generator (E)

[0300] The composition according to the invention preferably further comprises a photoalkali generator (E). Component (E) can act as a quencher to inhibit the diffusion of acid originating from component (C) in the exposed area.

[0301] Examples of component (E) include light-generating agents based on cobaltamine complexes, oxime carboxylates, carbamates, or quaternary ammonium salts. Specific examples include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyl oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropyl Alkane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2'-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine.

[0302] Component (E) may have one, two or more components.

[0303] Based on the total mass of component (A), the content of component (E) is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, and even more preferably 0.3 to 4% by mass.

[0304] Amine compounds (F)

[0305] The composition according to the invention preferably further comprises an amine compound (F). Component (F) has the effect of inhibiting the diffusion of acid generated at the exposure site and can prevent the acid on the surface of the resist film from being deactivated by the amine component present in the air.

[0306] Examples of component (F) preferably include C. 1-16 aliphatic primary amine compounds, C 2-32 fatty secondary amine compounds, C 3-48 fatty tertiary amine compounds, C 6-30 Aromatic amine compounds or C 5-30 Heterocyclic amine compounds.

[0307] Examples of component (F) include ethylamine, n-octylamine, n-heptylamine, ethylenediamine, triethylamine, tri-n-octylamine, diethylamine, triethanolamine, tris[2-(2-methoxyethoxy)ethyl]amine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, 7-methyl-1,5,7-trizabicyclo[4.4.0]dec-5-ene, and 1,5,7-trizabicyclo[4.4.0]dec-5-ene.

[0308] The base dissociation constant pKb(H2O) of component (F) is preferably -12 to 5, more preferably 1 to 4.

[0309] The molecular weight of component (F) is preferably 17 to 500; more preferably 60 to 400.

[0310] Component (F) may have one, two or more components.

[0311] Based on the total mass of component (A), the content of component (F) is preferably 0.1 to 10% by mass, more preferably 0.15 to 7% by mass, and even more preferably 0.2 to 4% by mass.

[0312] Solvent (G)

[0313] The composition according to the invention preferably further comprises a solvent (G). The solvent is not particularly limited, as long as it can dissolve the components to be blended. Component (G) is preferably water, a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or any combination of the above solvents.

[0314] Examples of solvents include water, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, trimethylbenzene, methanol, ethanol, n-propanol, isopropanol, etc. Butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethylhept-4-ol, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecylol, sec-heptadecylol, phenol, cyclohexane Alcohols, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, benzyl methanol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methylpentane-2,4-diol, 2,5-hexanediol, 2,4-heptanediol, 2-ethylhexane-1,3-diol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, acetone, methyl ethyl ketone, methyl n- Propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, cyclopentanone, methyl cyclohexanone, 2,4-pentanedione, acetone-acetone, diacetone alcohol, acetophenone, fenestrate, diethyl ether, isopropyl ether, n-butyl ether (di-n-butyl ether, DBE), n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-Epoxypropane, 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, ethoxytriethylene glycol, 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 ether, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate (n-butyl acetate, nBA), isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methylamyl 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 (PGMEA), 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, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate Esters, isopentyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate (EL), n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, 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-propanesulfonyl lactone. These solvents can be used alone or in mixtures of two or more solvents.

[0315] Component (G) is preferably PGME, PGMEA, EL, nBA, DBE or a mixture of these solvents; more preferably PGME, PGMEA, EL, nBA, DBE or a mixture of these solvents; even more preferably PGME, PGMEA, EL or a mixture thereof; and even more preferably a mixture of PGME, PGMEA and EL.

[0316] Another embodiment is that component (G) is substantially water-free relative to the other layers and membranes. For example, the water content in the entire component (G) 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. Another preferred embodiment is that the solvent (G) is water-free (0% by mass).

[0317] Based on the total mass of the composition, the content of (G) is preferably 50 to 99% by mass, more preferably 70 to 98% by mass, and even more preferably 80 to 95% by mass.

[0318] Surfactant (H)

[0319] The compositions according to the invention preferably contain a surfactant (H). Adding a surfactant improves coatability. Surfactants that can be used in this invention include: (I) anionic surfactants, (II) cationic surfactants, or (III) nonionic surfactants, more specifically including: (I) alkyl sulfonates, alkylbenzene sulfonic acids, and alkylbenzene sulfonates; (II) laurylpyridine chloride and lauryl methyl ammonium chloride; and (III) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene acetylenic glycol ether, fluorinated surfactants (e.g., Fluorad (3M), MEGAFACE (DIC), Surflon (AGC Inc.), and organosiloxane surfactants (e.g., KF-53 and KP341 (Shin-Etsu Chemical Co., Ltd.)).

[0320] Component (H) may have one, two or more components.

[0321] Based on the total mass of the composition, the content of component (H) is preferably 0.0005 to 0.01% by mass, more preferably 0.001 to 0.009% by mass, and even more preferably 0.002 to 0.007% by mass.

[0322] Additive (I)

[0323] In addition to the components described above, the composition according to the invention may also contain additive (I). Component (I) is preferably selected from at least one of the following components: surface smoother, plasticizer, dye, contrast enhancer, acid, free radical generator, substrate adhesion enhancer, and defoamer.

[0324] The total mass of component (A) and the content of component (I) (the sum of them if there is more than one) are preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass. Another embodiment of the invention is wherein the composition according to the invention does not contain component (I) (0% by mass).

[0325] Acids can be used to adjust the pH of the composition or to improve the solubility of additive components. There are no particular limitations on the acids used, such as 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, p-toluenesulfonic acid, camphorsulfonic acid, any hydrates of the above acids, and combinations thereof. Based on the total mass of the composition, the acid content is preferably 0.005 to 0.1% by mass (more preferably 0.01 to 0.1% by mass).

[0326] <Methods for preparing resist films>

[0327] The method for preparing a resist film according to the present invention includes:

[0328] The above-described resist composition is coated onto the substrate to form a coating.

[0329] An embodiment of the preparation method according to the present invention will now be described.

[0330] The compositions according to the invention can be coated onto a substrate (e.g., a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, etc.) by suitable methods. In this context, the term "on" includes both direct formation onto the substrate and formation via an intermediate layer. For example, a planarization film or a resist underlayer can be formed directly on the substrate, and the compositions of the invention can be directly coated onto the planarization film or resist underlayer. Preferably, no anti-reflective coating is formed as the resist underlayer. The coating method is not particularly limited; for example, it can be performed using a spin coater or a coating machine. After coating, the film according to the invention is formed by heating. It is preferable to heat the coated film, for example, by using a heating plate. The heating temperature is preferably 30 to 200°C, more preferably 50 to 150°C. The temperature referred to herein is the temperature in a heating atmosphere, for example, the heating surface temperature of the heating plate. The heating time is preferably 30 to 300 seconds, more preferably 30 to 120 seconds. Heating is preferably performed in an air or nitrogen atmosphere.

[0331] The thickness of the resist film is selected according to the application. When using the composition according to the invention, a pattern with a better shape can be formed when forming the coating film. The thickness of the resist film is preferably 1200 nm or thinner, more preferably 50 to 1100 nm, and even more preferably 80 to 1000 nm.

[0332] The method for preparing resist patterns according to the present invention includes the following steps:

[0333] The resist film was prepared using the method described above.

[0334] Expose the resist film to light; and

[0335] Develop the resist film.

[0336] The photoresist film is exposed through a pre-set mask. There are no particular limitations on the wavelength of the light used for exposure. Exposure is preferably performed using light with a wavelength of 13.5 to 248 nm. Specifically, KrF excimer lasers (wavelength: 248 nm), ArF excimer lasers (wavelength: 193 nm), extreme ultraviolet light (wavelength: 13.5 nm), etc., can be used, with KrF excimer lasers being preferred. Deviations in these wavelengths are allowed within ±1%. After exposure, post-exposure baking (PEB) can be performed if 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.

[0337] The exposed photoresist film is developed using a developing solution. The developing method can employ conventional methods for developing photoresist, such as pull-dip development, immersion development, or swing-dip development. An aqueous solution is used as the developing solution, containing an inorganic base (such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium silicate) and ammonia; an organic amine, such as ethylamine, propylamine, diethylamine, diethylaminoethanol, or triethylamine; a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH); and 2.38% by mass of an aqueous TMAH solution. A surfactant may also be added to the developing solution. The temperature of the developing solution is preferably 5 to 50°C, more preferably 25 to 40°C, and the developing time is preferably 10 to 300 seconds. After development, washing or rinsing with water may be performed if necessary. When using a positive photoresist composition, the developing process removes the exposed portion, thereby forming a photoresist pattern. This photoresist pattern can be further refined by using, for example, a shrinkage material.

[0338] The method for preparing the processed substrate according to the present invention includes the following steps:

[0339] The resist pattern was prepared using the method described above.

[0340] The resist pattern is used as a mask for processing.

[0341] The resulting resist pattern is preferably used to process the underlying film or substrate (more preferably the substrate). Specifically, using the resist pattern as a mask, various substrates used as substrates can be processed by methods such as dry etching, wet etching, ion implantation, and metal plating.

[0342] Subsequently, if necessary, the substrate is further processed to form a device. These further processing steps can be performed using known methods, preferably including forming wiring on the processed substrate. Subsequently, if necessary, the substrate is diced into wafers, connected to a lead frame, and encapsulated in resin. In this invention, such encapsulated product is referred to as a device. Examples of devices include semiconductor elements, liquid crystal display elements, organic electroluminescent display elements, plasma display elements, and solar cell elements. The device is preferably a semiconductor element.

[0343] This invention relates to the use of a resist composition for forming a resist film on a substrate. Preferably, the resist film is used as a mask in an ion implantation step into the substrate; more preferably, the ion implantation step is intended to fabricate logic gates.

[0344] [Example]

[0345] The present invention is described through the following embodiments. It should be noted that the embodiments of the present invention are not limited to these embodiments.

[0346] [Preparation of the composition of Example 1]

[0347] The components listed in Table 1 were mixed according to the mass parts listed in Table 1, and the container containing the mixture was stirred overnight. A homogeneously dissolved composition was thus obtained. This was then filtered through a 0.05 μm filter membrane. The composition of Example 1 was thus obtained. Each component was weighed using an analytical balance with an accuracy of 0.1 mg.

[0348] [Table 1]

[0349]

[0350] [Example 2, Preparation of compositions of Comparative Examples 1 to 6]

[0351] Examples 2 and 6 were prepared in the same manner as the compositions of Example 1, except that component (B) was replaced with a compound listed in Table 2. Comparative Example 6 did not contain component (B).

[0352] [Table 2]

[0353]

[0354] <Formation of resist patterns>

[0355] An 8-inch silicon wafer was pretreated with hexamethyldisilazane. The prepared composition was then added dropwise onto the silicon wafer. The silicon wafer was spin-coated at approximately 1200 rpm and then heated on a hot plate at 90°C (pre-baking) for 35 seconds to form a resist film. The film thickness at this point was 310 nm. An anti-reflective coating (TARC) with a thickness of 43 nm was then formed on the resist film.

[0356] A KrF stepper lithography machine (FPA300-EX5, CANON, numerical aperture 0.63, σ value 0.65) was used to expose the resist film. The exposure dose at the wafer center was 190 J / nm. 2 As the wafer mask pattern, a dense line pattern with an L:S ratio of 1:1 and a linewidth of 180nm is adopted.

[0357] The wafer was then baked on a hot plate at 135°C (PEB) for 90 seconds. After that, it was immersion-developed with a 2.38% by mass TMAH aqueous solution for 30 seconds to obtain the resist pattern.

[0358] [Evaluation of Coating Performance]

[0359] During the formation of the resist film, the coatability of the composition was evaluated according to the following criteria, and the results are listed in Table 2.

[0360] A: It has good coating properties and can form a resist film.

[0361] B: The coating is defective and cannot form a resist film.

[0362] Based on Comparative Examples 1 and 2, no resist film could be formed, therefore no further evaluation was conducted.

[0363] [Rectangularity evaluation]

[0364] The cross-section of the resist pattern formed above was observed using a SEM device (SU8230, Hitachi High-Tech Corporation), and evaluated according to the following criteria. The results are listed in Table 2.

[0365] A: The resist pattern is rectangular or substantially rectangular.

[0366] B: The resist pattern is rectangular or substantially rectangular, but with slight slag inclusions. The quality of the resist pattern is within acceptable limits.

[0367] C: The interface between the resist pattern and the substrate has feet, and the resist pattern is conical.

[0368] D: The resist pattern is inverted cone shape.

Claims

1. A resist composition comprising: Polymers containing acid-dissociating groups (A); and Compound (B) represented by formula (I): ［C1］ in: X 1 To X 10 Each is independently H, OH, NH2, halogen, C 1-10 Alkyl, C 1-10 Alkyl group or R represented by formula (II); When X 1 To X 10 When each is an alkyl group independently, one or more non-adjacent methylene (-CH2-) groups of the alkyl group may be independently replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, or -C≡C-; and X 1 To X 10 At least one of them is R; ［C2］ in: Y 1 To Y 5 Each is independently H, OH, NH2, halogen, C 1-10 Alkyl or C 1-10 Alkoxy; When Y 1 To Y 5 When each is an alkyl group independently, one or more non-adjacent methylene (-CH2-) groups of the alkyl group may be independently replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH- or -C≡C-. When Y 1 To Y 5 When each is an alkyl group independently, one or more H atoms of the alkyl group may be replaced by OH, NH2 or halogen; Y 1 To Y 5 At least one of them is OH or contains OH; L 1 For single bond or C 1-10 Alkylene; and; When L 1 When it is an alkylene group, L 1 One or more non-adjacent methylene (-CH2-) groups can be independently replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH- or -C≡C-.

2. The resist composition according to claim 1, wherein the polymer (A) comprises: The repeating unit represented by equation (A-1); and At least one repeating unit is selected from the group of repeating units represented by equations (A-2) to (A-4). ［C3］ in: R 11 R 21 R 41 and R 45 Each independently is C 1-5 Alkyl group, wherein the -CH2- of the alkyl group can be replaced by -O-; and 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 Each independently represents H and C. 1-5 Alkyl, C 1-5 Alkyl groups or -COOH; p11 is 0 to 4, p15 is 1 to 2, and p11+p15≤5; p21 is 0 to 5; p41 ranges from 0 to 4, p45 ranges from 1 to 2, and p41 + p45 ≤ 5; and P 31 C 4-20 Alkyl groups, wherein the alkyl group may partially or completely form a ring, and some or all of the H atoms in the alkyl group may be replaced by halogens.

3. The resist composition according to claim 1 or 2 further comprises a first acid generator (C), wherein the first acid generator (C) has a -SO2- structure.

4. The resist composition according to claim 3, wherein, The first acid generator (C) is a photoacid generator.

5. The resist composition according to any one of claims 1 to 4 further comprises a solvent (G).

6. The resist composition according to any one of claims 1 to 5, wherein, Based on the total mass of the resist composition, the content of the polymer (A) containing acid-dissociating groups is 1 to 15% by mass, and Based on the total mass of the resist composition, the content of compound (B) represented by formula (I) is 0.01 to 0.1 by mass.

7. The resist composition according to any one of claims 1 to 6, wherein, This resist composition is a positive resist composition.

8. A method for preparing a resist film, comprising the following steps: The resist composition according to any one of claims 1 to 7 is coated over a substrate to form a coating film; as well as Preferably, no anti-reflective coating is formed on the substrate before the coating film is formed; or Optionally, the coating film can be heated.

9. A resist film prepared by the method of claim 8, wherein the film thickness is 1200 nm or less.

10. A method for preparing a resist pattern, comprising the following steps: A resist film is prepared by the method of claim 8; Expose the resist film to light; Optionally, the resist film is heated after exposure; and The exposed resist film is developed.

11. A method for manufacturing a processed substrate, comprising the following steps: The resist pattern is prepared by the method of claim 10; and The resist pattern is used as a mask for processing.

12. A method of manufacturing a device, comprising the method according to claim 11; Preferably, the method further includes the step of forming wiring on the processed substrate; and Preferably, the device is a semiconductor device.

13. Use of the resist composition according to claim 1 for forming a resist film on a substrate.

14. The use according to claim 13, wherein the resist film serves as a mask in the step of ion implantation into the substrate, and Preferably, the ion implantation step is intended to fabricate logic gates.

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