Chemically amplified positive resist composition for thick film and method for manufacturing resist film using the same

Abstract

The invention provides a thick film chemically amplified positive resist composition. A thick film chemically amplified positive resist composition containing an alkali-soluble resin (A) having a specific structure, a photoacid generator (B), and a solvent (C).

Description

Technical Field

[0001] The present invention relates to a thick-film chemically amplified positive resist composition used in the manufacture of semiconductor devices and / or semiconductor integrated circuits, and a method for producing a resist film using the same. Background Art

[0002] Microfabrication using photolithography techniques using resists is commonly performed during the manufacturing process of semiconductor devices. The microfabrication process involves forming a thin resist layer on a semiconductor substrate such as a silicon wafer, covering this layer with a mask pattern corresponding to the target device pattern, exposing the layer to active light such as ultraviolet light through the mask pattern, developing the exposed layer to obtain a resist pattern, and etching the substrate using the resulting resist pattern as a protective film, thereby forming fine concave and convex surfaces corresponding to the pattern.

[0003] Patent Document 1 discloses a positive resist composition comprising a resin soluble in an alkaline developer having a specific structure. Examples of groups in the resin that decompose and dissociate under the action of an acid include tert-butyl groups, tert-amyl groups, and hydrocarbon groups with an alicyclic structure. This resist composition is preferably used in thin films, and the examples disclose the formation of a 0.3 μm resist film.

[0004] [Prior art literature]

[0005] [Patent Document]

[0006] [Patent Document 1]: Japanese Patent Application Laid-Open No. 2009-244829 Summary of the Invention

[0007] [Problems to be solved by the invention]

[0008] The inventors of the present invention have the following considerations. While miniaturization of resist patterns is desired, thicker resist patterns with higher aspect ratios are also required to cope with high-energy ion implantation and other processes. Since the performance and process conditions required for forming thick resist patterns differ from those for thin films, simply adjusting the viscosity of a thin resist composition to achieve thicker films presents unique difficulties, as it is impossible to achieve the desired shape.

[0009] The present inventors have determined that there are still one or more problems that need to be improved in thick film chemically amplified positive resist compositions and their use. Examples of these problems include the following.

[0010] If the film thickness is increased, the depression at the top of the resist pattern wall becomes larger. The transmittance of the resist film decreases, and the sensitivity decreases. The resolution is low. The process margin of the process is narrow. The rectangularity of the resist pattern is low. The development contrast is low. Shape abnormalities appear after development. The resistance of the resist pattern to post-development processes (such as etching) is low. The film thickness loss caused by development is large. The etching selectivity is low. In the case of a thick resist film, light cannot fully reach the bottom. The energy of exposing the resist film becomes large. The deviation in the amount of acid generated and diffused at the top and bottom of the resist film is large.

[0011] [Methods used to solve the problem]

[0012] The thick-film chemically amplified positive resist composition of the present invention comprises an alkali-soluble resin (A), a photoacid generator (B) and a solvent (C).

[0013] in,

[0014] The resist film formed by the thick-film chemically amplified positive resist composition has a thickness of 5.0 to 50.0 μm;

[0015] The alkali-soluble resin (A) comprises at least one of the following repeating units:

[0016]

[0017] in,

[0018] R 11 、R 21 、R 41 and R 45 Each independently is C 1-5 Alkyl, wherein -CH2- in the alkyl may also be replaced by -O-,

[0019] 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 independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy or -COOH;

[0020] p11 is 0 to 4; p15 is 1 to 2; p11+p15≦5;

[0021] p21 is 0 to 4;

[0022] n21 is 0 to 1;

[0023] p41 is 0 to 4; p45 is 1 to 2; p41+p45≦5;

[0024] P 31 C 4-20 Alkyl, wherein the alkyl group does not form a ring, and part or all of the H groups in the alkyl group may be substituted with halogen; and

[0025] The number n of repeating units of the repeating units (A-1), (A-2), (A-3) and (A-4) in the alkali-soluble resin (A) A-1 、n A-2 、n A-3 and n A-4 satisfy:

[0026] n A-1 / (n A-1 +n A-2 +n A-3 +n A-4 )=0~80%、

[0027] n A-2 / (n A-1 +n A-2 +n A-3 +n A-4 )=1~40%、

[0028] n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) = 0-40%, or

[0029] n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 )=0~40%;

[0030] Among them, n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) and n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 ) is greater than 0%.

[0031] The method for manufacturing a resist film of the present invention comprises the following steps:

[0032] (1) applying the composition above a substrate;

[0033] (2) The composition is heated to form a resist film.

[0034] [Effects of the Invention]

[0035] By using the thick-film chemically amplified positive resist composition of the present invention, one or more of the following effects can be expected.

[0036] The depression at the top of the resist pattern wall is suppressed. Good sensitivity can be obtained even with a thick resist film. The resolution is sufficient. The process margin is wide. The rectangularity of the resist pattern is sufficient. The development contrast is sufficient. Shape abnormalities after development are less likely to occur. The film thickness loss caused by development is suppressed. A resist pattern with sufficient resistance in the process after development (such as etching) can be obtained. The etching selectivity is sufficient. Even with a resist film of 5 to 50 μm thick, light can fully reach the bottom. The energy of exposing the resist film can be suppressed. The deviation in the amount of acid generated and diffused at the top and bottom of the resist film can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 (a) and (b) are conceptual diagrams showing the cross-sectional shapes of the resist pattern.

[0038] [ Figure 2 ] is a conceptual diagram showing the top of the wall of the resist pattern. DETAILED DESCRIPTION

[0039] [definition]

[0040] In this specification, unless otherwise specified, the definitions and / or examples described in this paragraph shall apply.

[0041] The singular includes the plural, and “one” and / or “the” means “at least one.” A certain concept may be expressed in multiple forms, and when the amount (for example, mass % and / or mol %) is described, the amount refers to the total of the multiple forms.

[0042] "And / or" includes all combinations of elements and also includes individual uses.

[0043] When "to" or "to / -" is used to express a numerical range, both endpoints are included and the unit is the same. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

[0044] “C x-y ”, “C x -C y ” and “C x " etc. refers to the number of carbon atoms in a molecule or a substituent. For example, C 1-6The alkyl group refers to an alkyl chain having 1 or more and 6 or less carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl).

[0045] When a polymer has multiple repeating units, these repeating units are copolymerized. These copolymerizations may be alternating copolymerizations, random copolymerizations, block copolymerizations, graft copolymerizations, or mixtures thereof. When a polymer and / or resin is represented by a structural formula, n, m, etc. listed after the parentheses represent the number of repeating units.

[0046] The unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius.

[0047] The additive refers to the compound itself having the function (for example, in the case of a base generator, the compound itself that generates a base). Alternatively, the compound may be dissolved or dispersed in a solvent and added to the composition. As one aspect of the present invention, such a solvent is preferably included in the composition of the present invention as a solvent (C) or other component.

[0048] Hereinafter, embodiments of the present invention will be described in detail.

[0049] [Thick film chemically amplified positive resist composition]

[0050] The thick-film chemically amplified positive resist composition of the present invention (hereinafter sometimes referred to as the composition) comprises an alkali-soluble resin (A), a photoacid generator (B), and a solvent (C).

[0051] The thick film resist composition is a resist composition capable of forming a thick resist film. In the present invention, the resist film formed from the thick film resist composition has a thickness of 5.0 μm to 50 μm (preferably 11.0 μm to 30 μm; more preferably 11.0 μm to 25 μm; further preferably 11 μm to 20 μm).

[0052] The solid content concentration of the composition of the present invention is preferably greater than 0% by mass and less than 80% by mass, more preferably 30% to 50% by mass, and even more preferably 35% to 45% by mass. The solid content concentration is the concentration of all components other than the solvent component, based on the composition.

[0053] The viscosity is preferably 100 cP to 3,000 cP, more preferably 150 cP to 2,500 cP, and even more preferably 200 cP to 2,000 cP. The viscosity is measured at 25°C using a capillary viscometer.

[0054] The composition of the present invention is preferably a thick-film chemically amplified positive-type KrF resist composition. Here, the term KrF used in the preferred embodiment means that a KrF excimer laser is used when exposing a resist film formed from the resist composition.

[0055] (A) Alkali-soluble resin

[0056] The composition of the present invention includes an alkali-soluble resin (A) (hereinafter sometimes referred to as component (A). The same applies to other components). Component (A) includes repeating units represented by the following formulas (A-1), (A-2), (A-3), and (A-4), and includes at least the repeating unit represented by (A-2). Component (A) is a component that reacts with an acid to increase its solubility in an alkaline aqueous solution. Such an alkali-soluble resin, for example, has an acid group protected by a protecting group. When an acid is added from the outside, the protecting group is detached, and the solubility in an alkaline aqueous solution is increased.

[0057] In a preferred embodiment, the repeating unit represented by (A-2) is not an acid-dissociable unit that removes a protecting group.

[0058] When forming a resist pattern, it has been found that as the film thickness increases, scooping tends to occur at the top of the resist pattern wall. One of the characteristics of the present invention is that component (A) contains a repeating unit represented by formula (A-2) having an alicyclic structure, thereby improving the shape of the scooping. While not being bound by theory, it is believed that the following occurs.

[0059] Since the amount of light reaching the bottom decreases when the resist film thickness becomes thicker, it is considered necessary to increase the exposure energy. When the exposure energy is high, the upper part of the resist film where the amount of light reaching is large becomes easy to diffuse due to the large amount of acid generated by the photoacid generator. Therefore, it is believed that the acid from the photoacid generator will penetrate and diffuse from the exposed part to the top of the unexposed part of the film, causing the part to dissolve significantly during development and become a concave shape. It is believed that the present invention contains a repeating unit represented by formula (A-2), which will have the necessary characteristics as a resist resin while suppressing light absorption, thereby improving the transmittance of the entire resist film of 5 to 50 μm thickness. Therefore, it is believed that the exposure energy can be suppressed, the difference in the amount of light between the top and bottom of the film can be suppressed, and the diffusion of acid to the top of the unexposed part of the film can be suppressed, making it difficult to form a concave shape.

[0060] Formula (A-1) is as follows:

[0061]

[0062] in,

[0063] R 11 Each independently is C 1-5Alkyl group (wherein -CH2- in the alkyl group may be replaced by -O-); preferably methyl or ethyl; more preferably methyl. In the present invention, the expression "-CH2- in the alkyl group may be replaced by -O-" means that an oxy group may be present between carbon atoms in the alkyl group, but does not mean that the terminal carbon in the alkyl group becomes an oxy group, that is, it does not mean that the alkyl group has an alkoxy group or a hydroxyl group.

[0064] R 12 、R 13 , and R 14 are independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy or -COOH; preferably hydrogen or methyl; more preferably hydrogen.

[0065] p11 is 0 to 4; preferably 0 or 1; more preferably 0.

[0066] p15 is 1 to 2, preferably 1.

[0067] p11+p15≦5.

[0068] Formula (A-2) is as follows:

[0069]

[0070] in,

[0071] R 21 Each independently is C 1-5 Alkyl (wherein the methylene group in the alkyl group may be replaced by an oxy group); preferably methyl, ethyl, tert-butyl or tert-butoxy; more preferably methyl or ethyl; more preferably methyl.

[0072] R 22 、R 23 , and R 24 are independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy or -COOH; preferably hydrogen or methyl; more preferably hydrogen.

[0073] p21 is 0 to 1; preferably 0 or 1; more preferably 0.

[0074] n21 is 0 to 1, preferably 0 or 1, and more preferably 1. When n21=0, it is a 5-membered ring, and when n=22, it is a 6-membered ring.

[0075] Specific examples of formula (A-2) include the following.

[0076]

[0077] Formula (A-3) is as follows:

[0078]

[0079] in,

[0080] R 32 、R 33 and R 34 are independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy or -COOH; preferably hydrogen, methyl, ethyl, tert-butyl, methoxy, tert-butoxy or -COOH; more preferably hydrogen or methyl; further preferably hydrogen.

[0081] P 31 C 4-20 Alkyl groups, alkyl groups do not form a ring, and part or all of the H groups in the alkyl group may be substituted with halogen. 31 The alkyl portion of P is preferably branched. 31 C 4-20 When the alkyl group is substituted with halogen, all of them are preferably substituted, and the substituted halogen is preferably F or Cl; more preferably F. 31 C 4-20 It is a preferred embodiment of the present invention that the H of the alkyl group is not substituted by halogen. 31 Preferred are methyl, isopropyl and tert-butyl; more preferred is tert-butyl.

[0082] Specific examples of the formula (A-3) include the following.

[0083]

[0084] Formula (A-4) is as follows:

[0085]

[0086] in,

[0087] R 41 Each independently is C 1-5 Alkyl group (wherein the methylene group in the alkyl group may be replaced by an oxy group); preferably methyl group, ethyl group or tert-butyl group; more preferably methyl group.

[0088] R 45 Each independently is C 1-5 Alkyl (wherein the methylene group in the alkyl group may also be replaced by an oxy group); preferably methyl, tert-butyl or -CH(CH3)-O-CH2CH3.

[0089] R 42 、R 43 and R 44 are independently hydrogen, C 1-5 Alkyl, C 1-5Alkoxy or -COOH; preferably hydrogen or methyl; more preferably hydrogen.

[0090] p41 is 0 to 4; more preferably 0 or 1; further preferably 0.

[0091] p45 is 1 to 2; more preferably 1.

[0092] Satisfies p41+p45≤5.

[0093] Specific examples of the formula (A-4) include the following.

[0094]

[0095] The alkali-soluble resin (A) may contain multiple repeating units represented by formula (A-1), (A-2), (A-3), or (A-4). For example, a structural unit with p15 = 1 and a structural unit with p15 = 2 may be present in a ratio of 1:1. In this case, p15 = 1.5 overall. The same applies to the number of polymers in the present invention unless otherwise specified.

[0096] In a preferred embodiment of the present invention, the alkali-soluble resin (A) contains, in addition to the repeating unit represented by formula (A-2), a repeating unit represented by formula (A-1) and a repeating unit represented by formula (A-3).

[0097] These structural units can be appropriately blended depending on the intended purpose. In a preferred embodiment, an acid is blended to appropriately increase the solubility in an alkaline aqueous solution.

[0098] The number n of repeating units (A-1), (A-2), (A-3) and (A-4) in the alkali-soluble resin (A) A-1 、n A-2 、n A-3 and n A-4 Instructions are as follows.

[0099] n A-1 / (n A-1 +n A-2 +n A-3 +n A-4 ) is 0 to 80% by mass; preferably 40% to 80%; more preferably 45% to 75%; further preferably 50% to 70%; further preferably 55% to 65%.

[0100] n A-2 / (n A-1 +n A-2 +n A-3 +n A-4) is preferably 1% to 40%; more preferably 0% to 35%; further preferably 5% to 35%; further preferably 15% to 25%.

[0101] n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) is preferably 0% to 40%; more preferably 10% to 40%; further preferably 15% to 30%; further preferably 15% to 25%.

[0102] 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%; further preferably 0% to 10%; further preferably 0% to 5%.

[0103] Among them, n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) and n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 ) is greater than 0%. n A-4 A value of 0 is also a preferred embodiment of the present invention.

[0104] As one embodiment of the present invention, n A-3 >0 and n A-4 =0.

[0105] The alkali-soluble resin (A) may contain other repeating units other than the repeating units represented by (A-1), (A-2), (A-3), and (A-4).

[0106] When the total number of all repeating units contained in the alkali-soluble resin (A) is set to n total When:

[0107] (n A-1 +n A-2 +n A-3 +n A-4 ) / n total It is preferably 80% to 100%, more preferably 90% to 100%, and even more preferably 95% to 100%. It is also a preferred embodiment of the alkali-soluble resin (A) that does not contain other repeating units.

[0108] Specific examples of the alkali-soluble resin (A) include the following:

[0109]

[0110] The mass average molecular weight (hereinafter sometimes referred to as Mw) of the alkali-soluble resin (A) is 10,000 to 50,000, more preferably 18,000 to 40,000, and even more preferably 20,000 to 35,000.

[0111] In the present invention, Mw can be measured by gel permeation chromatography (GPC). In a preferred example of this measurement, the GPC column is set at 40 degrees Celsius, the eluent is tetrahydrofuran at 0.6 mL / min, and monodisperse polystyrene is used as a standard.

[0112] The content of component (A) is preferably greater than 0% by mass and less than 50% by mass, 15 to 50% by mass, more preferably 20 to 45% by mass, and even more preferably 30 to 40% by mass, based on the composition.

[0113] (B) Photoacid generator

[0114] The composition of the present invention comprises a photoacid generator (B). Component (B) releases an acid upon exposure to light. Preferably, the acid derived from component (B) acts on component (A), thereby increasing the solubility of component (A) in alkaline aqueous solution. For example, when component (A) has an acid group protected by a protecting group, the protecting group is removed by the acid. Component (B) used in the composition of the present invention can be selected from conventionally known components.

[0115] The component (B) releases an acid having an acid dissociation constant pKa (H 2 O) of preferably -20 to 1.4, more preferably -16 to 1.4, further preferably -16 to 1.2, and even further preferably -16 to 1.1 upon exposure.

[0116] The component (B) is preferably represented by formula (B-1) or formula (B-2).

[0117] Formula (B-1) is as follows.

[0118] B n+ Cation B n- Anion (B-1)

[0119] in,

[0120] B n+ The cation is a cation represented by formula (BC1), a cation represented by formula (BC2), or a cation represented by formula (BC3), B n+ The cations are generally n-valent, where n is 1 to 3, preferably 1 or 2, more preferably 1, and

[0121] 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- Anions generally have a valence of n.

[0122] Formula (BC1) is as follows:

[0123]

[0124] in,

[0125] R b1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, or C 6-12 Aryloxy; preferably methyl, ethyl, tert-butyl, methoxy, ethoxy, phenylthio or phenoxy; more preferably tert-butyl, methoxy, ethoxy, phenylthio or phenoxy.

[0126] nb1 is independently 0, 1, 2 or 3. All nb1 are 1, all R b1 The same is also a preferred embodiment. In addition, nb1 being 0 is also a preferred embodiment.

[0127] Specific examples of formula (BC1) are as follows.

[0128]

[0129] Formula (BC2) is as follows:

[0130]

[0131] in,

[0132] R b2 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl; preferably having C 4-6 An alkyl group having a branched structure; more preferably a tert-butyl group or a 1,1-dimethylpropyl group; further preferably a tert-butyl group.

[0133] nb2 are each independently 0, 1, 2 or 3; preferably 1.

[0134] Specific examples of formula (BC2) are as follows.

[0135]

[0136] Formula (BC3) is as follows.

[0137]

[0138] in,

[0139] R b3 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl; preferably methyl, ethyl, methoxy or ethoxy; more preferably methyl or methoxy.

[0140] R b4 Each independently is C 1-6 Alkyl; preferably methyl or ethyl; more preferably methyl.

[0141] nb3 are each independently 0, 1, 2 or 3; more preferably 3.

[0142] Specific examples of formula (BC3) are as follows.

[0143]

[0144] B n+ It is preferred that the cation be selected from the group consisting of cations represented by formula (BC1) or (BC2) because a better effect is exhibited.

[0145] Formula (BA1) is as follows:

[0146]

[0147] Among them, R b5 Each independently is C 1-6 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy or C 1-6 Alkyl. For example, -CF3 means that the hydrogen of methyl (C1) is replaced by fluorine. 1-6 All hydrogens present in the fluorine-substituted alkyl group are replaced by fluorine. b5 The alkyl portion of is preferably methyl, ethyl or tert-butyl (more preferably methyl). b5 It is preferably a fluorine-substituted alkyl group, more preferably -CF3.

[0148] Specific examples of formula (BA1) are as follows.

[0149]

[0150] Formula (BA2) is as follows.

[0151]

[0152] in,

[0153] R b6 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; preferably C 2-6 Fluorine-substituted alkyl; more preferably C 2-3 Fluorine-substituted alkyl; more preferably C3 fluorine-substituted alkyl. b6 In the fluorine-substituted alkyl group, an embodiment in which all hydrogen atoms present in the alkyl moiety are replaced by fluorine atoms is preferred. b6 The alkyl portion of R is preferably methyl, ethyl, propyl, butyl or pentyl; more preferably propyl, butyl or pentyl; further preferably butyl. b6 It is preferred that the alkyl portion be straight chain.

[0154] nb4 is 1 or 2; preferably 1.

[0155] When nb4 is 2, R b6 Becomes bivalent, from the above R b6 The hydrogen or fluorine forms a single bond and bonds to the S atom.

[0156] Specific examples of formula (BA2) are as follows.

[0157]

[0158] Formula (BA3) is as follows:

[0159]

[0160] in,

[0161] R b7 Each independently is 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; preferably C 2-6 Fluoro-substituted alkyl. b7 The alkyl portion of R is preferably methyl, ethyl, propyl, butyl or pentyl; more preferably methyl, ethyl or butyl; further preferably butyl. b7 The alkyl portion of is preferably straight chain.

[0162] Among them, the two R b7They may be bonded to each other to form a fluorine-substituted heterocyclic structure. In this case, the heterocyclic ring may be a monocyclic ring or a polycyclic ring, but is preferably a monocyclic structure having 5 to 8 constituent members.

[0163] Specific examples of formula (BA3) are as follows.

[0164]

[0165] Formula (BA4) is as follows:

[0166]

[0167] in,

[0168] R b8 For hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy or hydroxy; preferably hydrogen, methyl, ethyl, methoxy, or hydroxy; more preferably hydrogen or hydroxy.

[0169] L b It is a carbonyl group, an oxy group or a carbonyloxy group; preferably a carbonyl group or a carbonyloxy group; more preferably a carbonyl group.

[0170] Y b Each is independently hydrogen or fluorine; preferably at least one is fluorine.

[0171] nb5 is an integer from 0 to 10, preferably 0.

[0172] nb6 is an integer from 0 to 21; preferably 4, 5 or 6.

[0173] Specific examples of formula (BA4) are as follows.

[0174]

[0175] Formula (B-2) is as follows.

[0176]

[0177] in,

[0178] R b9 C 1-5 Fluorine-substituted alkyl; preferably C 1-4 More preferably, it is an alkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[0179] R b10 Each independently is C 3-10 Alkenyl or alkynyl (wherein CH3- in alkenyl and alkynyl may be replaced by phenyl, and -CH2 in alkenyl and alkynyl may be replaced by at least one of -C(=O)-, -O- or phenylene), C 2-10Sulfanyl, C 5-10 Saturated heterocyclic ring; preferably C 3-12 Alkenyl or alkynyl, C 3-5 sulfanyl, C 5-6 saturated heterocycle; more preferably -C≡C-CH2-CH2-CH2-CH3, -CH=CH-C(=O)-O-tBu, -CH=CH-Ph, -S-CH(CH3)2, -CH=CH-Ph-O-CH(CH3)(CH2CH3) and piperidine. Among them, tBu refers to tert-butyl, and Ph refers to phenylene or phenyl. It should be noted that in the present invention, alkenyl refers to a monovalent group having one or more double bonds (preferably one). Similarly, alkynyl refers to a monovalent group having one or more triple bonds (preferably one).

[0180] nb7 is 0, 1, or 2, preferably 0 or 1, and more preferably 0. Satisfying nb7=1 is also a preferred embodiment.

[0181] Specific examples of formula (B-2) include the following.

[0182]

[0183] The molecular weight of the photoacid generator (B) is preferably 400 to 2,500, and more preferably 400 to 1,500.

[0184] The component (B) may be one kind or two or more kinds.

[0185] Based on the total mass of component (A), the content of component (B) is preferably greater than 0 mass% and less than 20 mass%; 0.05 mass% to 10 mass%; more preferably 0.1 mass% to 5 mass%; and even more preferably 0.5 mass% to 2 mass%.

[0186] (C) Solvent

[0187] The composition of the present invention contains (C) a solvent.

[0188] The solvent (C) preferably contains propylene glycol monomethyl ether (PGME) (C-1). The content of PGME (C-1) is preferably 30% by mass to 100% by mass based on the solvent (C); greater than 50% by mass and less than 100% by mass; preferably 55% by mass to 90% by mass; and more preferably 55% by mass to 80% by mass.

[0189] Solvent (C) more preferably further contains a solvent (C-2) in addition to solvent (C-1). Solvent (C-2) is selected from the group consisting of alcohol solvents (C-2-1) and low-boiling-point solvents (C-2-2). Alcohol solvent (C-2-1) is a compound in which a hydrogen atom of a chain or alicyclic hydrocarbon is substituted with a hydroxyl group. The methylene group in the alcohol solvent may be substituted with an oxy group or a carbonyl group, and the hydrogen atom may be substituted with an aryl group.

[0190] The content of the solvent (C-2) based on the solvent (C) is preferably 0% by mass or more and less than 50% by mass; preferably 5% by mass to 45% by mass; and more preferably 10% by mass to 35% by mass.

[0191] As the alcohol solvent (C-2-1), for example, one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol (isopropyl alcohol, IPA), n-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, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethylheptanol-4, n-decanol, sec-undecanol , trimethyl nonanol, secondary tetradecanol, secondary heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenyl methyl carbinol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mononormal Butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxylated triethylene glycol, 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, 4-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-2-pentanol, 3-methyl -2-butanol, 2-methyl-2-butanol, 4-methyl-2-hexanol, 5-methyl-2-hexanol, 3-methyl-2-hexanol, 2-methyl-2-hexanol, ethyl lactate (EL), propyl lactate, n-butyl lactate, n-pentyl lactate, butyric acid, methyl 2-hydroxyisobutyrate, methyl 2-hydroxybutyrate, methyl 3-hydroxybutyrate, methyl 4-hydroxybutyrate, ethyl 2-hydroxyisobutyrate, ethyl 2-hydroxybutyrate, ethyl 3-hydroxybutyrate and ethyl 4-hydroxybutyrate, preferably IPA and / or EL.

[0192] The boiling point of the low-boiling-point solvent (C-2-2) is preferably 80°C to 130°C, more preferably 80°C to 110°C, and even more preferably 80°C to 100°C at 1 atmosphere.

[0193] As the low-boiling point solvent (C-2-2), for example, one is selected from the group consisting of n-propanol, isopropanol (IPA), n-butanol, isobutanol, sec-butanol, tert-butanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, ethylene glycol monomethyl ether, 2-methyl-2-pentanol, 3-methyl-2-butanol, 2-methyl-2-butanol, propylene glycol dimethyl ether, butyl acetate, methyl ethyl ketone and methyl isobutyl ketone, preferably IPA and / or propylene glycol dimethyl ether.

[0194] The solvent (C) may further contain a solvent (C-3) other than the solvent (C-1) and the solvent (C-2). Examples of the solvent (C-3) include propylene glycol monomethyl ether acetate (PGMEA) and N-methylpyrrolidone.

[0195] The content of solvent (C-3) is less than 50% by mass based on solvent (C); preferably, it is from 0% to 35% by mass; more preferably, it is from 0% to 10% by mass; and even more preferably, it is from 0% to 5% by mass. The absence of solvent (C-3) is also a preferred embodiment of the present invention.

[0196] In a preferred embodiment of the present invention, solvent (C) is PGME, a low-boiling-point solvent. In a more preferred embodiment, solvent (C) further comprises a solvent (C-2) selected from the group consisting of an alcohol solvent (C-2-1) and a low-boiling-point solvent (C-2-2).

[0197] The content of the (C) solvent is preferably 20% by mass or more and less than 100% by mass based on the composition; more preferably 50% by mass to 79% by mass; and even more preferably 55% by mass to 70% by mass.

[0198] (D) Photoreaction quencher

[0199] The composition of the present invention may further contain a photoreaction quencher (D). While photoreaction quenchers release an acid upon exposure to light, this acid does not directly act on the polymer. Because the released acid deprotects the polymer's protective groups, this differs from component (B), which directly acts on the polymer.

[0200] The cation portion of the photoreaction quencher (D) generated by receiving light preferably reacts with the anion portion of the photoacid generator (B) generated by receiving light.

[0201] The photoreaction quencher (D) functions as a quencher by inhibiting the diffusion of the acid generated from component (B) in the exposed area. While not limited by theory, the following mechanism is believed to be responsible. Exposure releases acid from component (B). When this acid diffuses to the unexposed area (unexposed portions), it undergoes salt exchange with component (D). In other words, the anions of component (B) and the cations of component (D) form a salt, thereby inhibiting the diffusion of the acid. At this point, although the anions of component (D) are released, they are weak acids and cannot deprotect the polymer, so it is believed that they have no effect on the unexposed area.

[0202] The photoreaction quencher (D) is preferably represented by formula (D-1).

[0203] D m+ Cation D m- Anion (D-1)

[0204] in,

[0205] D m+ The cation is a cation represented by formula (DC1) or a cation represented by formula (DC2), D m+ The cations are all m-valent.

[0206] m is 1 to 3, and

[0207] D m- The anion is an anion represented by formula (DA1) or an anion represented by formula (DA2), D m- The anions are all m-valent.

[0208] m is preferably 1 or 2; more preferably 1.

[0209] Formula (DC1) is as follows:

[0210]

[0211] in,

[0212] R d1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio, or C 6-12 Aryloxy; preferably methyl, ethyl, tert-butyl, methoxy, ethoxy, phenylthio, or phenoxy; more preferably tert-butyl, methoxy, ethoxy, phenylthio, phenoxy; further preferably tert-butyl or methoxy.

[0213] nd1 is each independently 0, 1, 2 or 3. All nd1 are 1, and all R d1 Similarly, this is also a preferred embodiment.

[0214] Furthermore, nd1 is 0, which is also a preferred embodiment.

[0215] A specific example of formula (DC1) is as follows:

[0216]

[0217] Formula (DC2) is as follows:

[0218]

[0219] in,

[0220] R d2 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl. R d2 Preferably, C 4-6 Alkyl group with branched structure. d2 They may be the same or different, and are more preferably the same. d2 More preferred are tert-butyl and 1,1-dimethylpropyl; further preferred are tert-butyl.

[0221] nd2 are each independently 0, 1, 2 or 3; preferably each is 1.

[0222] A specific example of formula (DC2) is as follows:

[0223]

[0224] Formula (DA1) is as follows:

[0225]

[0226] in,

[0227] X is C 1-20 Hydrocarbon or single bond. When X is a hydrocarbon, it may be any of linear, branched, or cyclic, but is preferably linear or cyclic. Preferably linear or cyclic. When linear, preferably C 1-4 (More preferably C 1-2 ); preferably, one double bond in the chain or saturation. If cyclic, it may be a monocyclic aromatic ring, a saturated monocyclic ring, or a polycyclic ring. If monocyclic, a 6-membered ring is preferred; if polycyclic, an adamantane ring is preferred. X is preferably a methyl group, an ethyl group, a propyl group, a butyl group, an ethane group, a phenyl group, a cyclohexane group, an adamantane group, or a single bond; more preferably, a methyl group, a phenyl group, a cyclohexane group, or a single bond; and even more preferably, a phenyl group.

[0228] R d3 are independently hydrogen, hydroxyl, C1-6 Alkyl, or C 6-10 Aryl; preferably hydroxy, methyl, ethyl, 1-propyl, 2-propyl, tert-butyl, or phenyl; more preferably hydroxy.

[0229] nd3 is 1, 2 or 3; preferably 1 or 2; more preferably 1.

[0230] nd4 is 0, 1 or 2; preferably 0 or 1; more preferably 1.

[0231] When X is a single bond, R d3 Preferably, hydrogen. X is a single bond, R d3 (DA1) where nd3=nd4=1 means: H-COO - anions.

[0232] Specific examples of formula (DA1) are as follows.

[0233]

[0234] Formula (DA2) is as follows:

[0235]

[0236] in,

[0237] R d4 C 1-15 Alkyl, wherein a part or all of the alkyl may form a ring, and -CH2- in the alkyl may be replaced by -C(=O)-. d4 Preferably C 3-13 Alkyl; more preferably C 5-12 Alkyl; more preferably C 8-17 Alkyl; more preferably C 10 Alkyl. R d4 The alkyl group of is preferably partially or entirely formed into a ring; more preferably partially formed into a ring. d4 One or more (more preferably one) -CH2- in the alkyl group is replaced by -C(=O)-.

[0238] Specific examples of the formula (DA2) include the following.

[0239]

[0240] The photoreaction quencher (D) releases an acid having an acid dissociation constant pKa (H 2 O) of preferably 1.5 to 8 (more preferably 1.5 to 5) upon exposure to light.

[0241] The molecular weight of the photoreaction quencher (D) is preferably 300 to 1,400, and more preferably 300 to 1,200.

[0242] The content of the photoreaction quencher (D) is preferably 0.01 to 5% by mass, more preferably 0.03 to 1% by mass, and even more preferably 0.05 to 1% by mass, based on the component (A).

[0243] (E) Surfactant

[0244] The composition of the present invention may further contain a surfactant (E). Component (E) can improve the coating properties of the composition. Examples of component (E) include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0245] Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether, and / or polyoxyethylene fatty acid diesters, polyoxyethylene fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers, acetylenic alcohols, acetylenic diols, polyethoxylated acetylenic alcohols, and polyethoxylated acetylenic diols; fluorine-containing surfactants such as Fluorad (trade name, 3M Japan), MEGAFACE (trade name, DIC), and Surflon (trade name, AGC); and organosiloxane surfactants such as KF-53 (trade name, Shin-Etsu Chemical) and BYK-333 (trade name, BYK). Examples of the acetylene glycol include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyn-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0246] Examples of the anionic surfactant include ammonium salts or organic amine salts of alkyldiphenylether disulfonic acid, ammonium salts or organic amine salts of alkyldiphenylether sulfonic acid, ammonium salts or organic amine salts of alkylbenzenesulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfate, and ammonium salts or organic amine salts of alkyl sulfate.

[0247] Furthermore, examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and lauramide propyl hydroxysulfobetaine.

[0248] The component (E) may be one kind or two or more kinds.

[0249] The content of the component (E) is preferably 0.0001 to 1% by mass, more preferably 0.001 to 1% by mass, and even more preferably 0.05 to 0.5% by mass, based on the component (A).

[0250] (F) Plasticizer

[0251] The composition of the present invention may further contain a plasticizer (F). By containing the component (F), film breakage during thick film formation can be suppressed.

[0252] Examples of component (F) include alkali-soluble vinyl polymers and / or vinyl polymers containing acid-dissociable groups. More specifically, examples include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoate, polyvinyl ether, polyvinyl butyral, polyvinyl alcohol, polyether ester, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylate, maleic acid polyimide, polyacrylamide, polyacrylonitrile, polyvinylphenol, novolac, and copolymers thereof, with polyvinyl ether, polyvinyl butyral, and polyether ester being more preferred.

[0253] The content of component (F) is preferably 0% to 3% by mass, more preferably 0% to 1% by mass, based on the composition. A preferred embodiment of the present invention is one in which the composition does not contain component (F).

[0254] (G) Additives

[0255] The composition of the present invention may contain an additive (G) in addition to (A) to (F). Component (G) may be at least one selected from the group consisting of a surface smoothing agent, a pigment, a contrast enhancer, an alkali, an acid, a radical generator, a substrate adhesion enhancer, and a defoaming agent.

[0256] The content of component (G) (or the sum of the content of component (G) in the case of multiple components) is preferably 0.0001% to 10% by mass, more preferably 0.01% to 2% by mass, based on component (A). Excluding component (G) (0% by mass) is also a preferred embodiment of the present invention.

[0257] The following effects of the base can be expected: the effect of suppressing the diffusion of acid generated in the exposed area and the effect of suppressing the deactivation of acid on the film surface due to amine components contained in the air. As the base, ammonia, C 1-16 Aliphatic primary amine compounds, C 2-32 Aliphatic secondary amine compounds, C 3-48 Aliphatic tertiary amine compounds, C 6-30 Aromatic amine compounds, or C 5-30 Heterocyclic amine compounds.

[0258] As C 1-16 Examples of the aliphatic primary amine compound include methylamine, ethylamine, isopropylamine, tert-butylamine, cyclohexylamine, ethylenediamine, and tetraethylenediamine.

[0259] As C2-32 Examples of the aliphatic secondary amine compound include dimethylamine, diethylamine, methylethylamine, dicyclohexylamine, and N,N-dimethylmethylenediamine.

[0260] As C 3-48 Examples of the aliphatic tertiary amine compound include trimethylamine, triethylamine, dimethylethylamine, triisobutylamine, triethanolamine, tri-n-octylamine, tricyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, tris[2-(dimethylamino)ethyl]amine, and tris[2-(2-methoxyethoxy)ethyl]amine.

[0261] As C 6-30 Examples of the aromatic amine compound include aniline, benzylamine, naphthylamine, N-methylaniline, 2-methylaniline, 4-aminobenzoic acid, and phenylalanine.

[0262] As C 5-30 Examples of the heterocyclic amine compound include pyrrole, oxazole, thiazole, imidazole, 4-methylimidazole, pyridine, picoline, butylpyridine, and 1,4-diazabicyclo[2.2.2]octane.

[0263] [Method of Manufacturing Resist Film]

[0264] The method for manufacturing a resist film of the present invention comprises the following steps:

[0265] (1) applying the composition of the present invention on a substrate;

[0266] (2) The composition is heated to form a resist film.

[0267] Hereinafter, one embodiment of the production method of the present invention will be described.

[0268] Process (1)

[0269] Above a substrate (e.g., a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, and an ITO substrate, etc.), the composition of the present invention is applied by an appropriate method. Here, in the present invention, "above" includes the case where it is formed directly thereon and the case where it is formed across other layers. For example, a planarization film and / or a resist underlayer film can be formed directly on the substrate, and the composition of the present invention can be applied directly thereon. An embodiment in which the composition of the present invention is directly applied to a substrate (without across other layers) is more preferred. The application method is not particularly limited, but a method in which, for example, coating is performed by a spinner or a coater can be cited.

[0270] Process (2)

[0271] After applying the composition, the resist film is formed by heating (prebaking). The heating in (2) is performed, for example, by a hot plate. The heating temperature is preferably 100°C to 250°C (more preferably 100°C to 200°C; further preferably 100°C to 160°C). The temperature here refers to the heating atmosphere, for example, the heating surface temperature of the hot plate. The heating time is preferably 30 seconds to 300 seconds (more preferably 60 seconds to 240 seconds). The heating is preferably performed in air or nitrogen atmosphere.

[0272] The thickness of the resist film is selected according to the intended purpose. However, when the composition of the present invention is used, a thicker coating film can be formed, resulting in a pattern with a more excellent shape. Therefore, the thickness of the resist film is preferably thick, preferably 5.0 μm to 50.0 μm, more preferably 11.0 μm to 30.0 μm, even more preferably 11.0 μm to 25.0 μm, and even more preferably 11.0 μm to 20.0 μm.

[0273] Furthermore, the resist pattern can be produced by a method comprising the following steps:

[0274] (3) exposing the resist film;

[0275] (4) Developing the resist film.

[0276] For the sake of clarity, steps (1) and (2) are performed before step (3). The numbers in parentheses indicate the order of the steps. The same applies to the following.

[0277] Process (3)

[0278] The resist film is exposed through a specific mask. The wavelength of the light used for exposure is not particularly limited, but it is preferably exposed with light with a wavelength of 13.5nm to 248nm. Specifically, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm) and extreme ultraviolet (wavelength 13.5nm) etc. can be used, preferably KrF excimer laser. These wavelengths allow a range of ±1%. After exposure, post-exposure heating (PEB) can also be performed as needed. The temperature of post-exposure heating is preferably 80°C to 150°C, more preferably 100°C to 140°C, and the heating time is 0.3 minute to 5 minutes, preferably 0.5 minute to 3 minutes.

[0279] Process (4)

[0280] The exposed resist film is developed using a developer. As a developing method, methods used in the development of conventional photoresists such as spin immersion developing, immersion developing, and shaking immersion developing can be used. In addition, as a developer, an aqueous solution of an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, an organic amine such as ammonia, ethylamine, propylamine, diethylamine, diethylamine ethanol, triethylamine, or a quaternary amine such as tetramethylammonium hydroxide (TMAH) can be used, preferably a 2.38% by mass TMAH aqueous solution. A surfactant may also be further added to the developer. The temperature of the developer is preferably 5°C to 50°C, more preferably 25°C to 40°C, and the developing time is preferably 10 seconds to 300 seconds, more preferably 30 seconds to 60 seconds. After development, water washing or rinsing may also be performed as needed. When a positive resist composition is used, the exposed portion is removed by development to form a resist pattern. In the resist pattern, further miniaturization may also be performed using, for example, a shrinking material.

[0281] When a thick film resist pattern is formed using a chemically amplified resist, particularly when the aspect ratio is high, depressions may occur at the top of the resist pattern wall (details of the depressions are described in the examples using drawings).

[0282] In a preferred embodiment, the ratio of the distance between the endpoint of the top of the resist pattern and the perpendicular to the substrate to the most concave point on the side of the resist pattern and the perpendicular to the substrate (hereinafter sometimes referred to as the bite width) to the resist film thickness is 0.023 or less, preferably 0 to 0.022, and more preferably 0 to 0.021. The present invention can suppress concavity. This suppression of concavity is advantageous in enhancing the durability of the pattern in subsequent steps.

[0283] Furthermore, the processed substrate can be manufactured by a method comprising the following steps:

[0284] (5) Processing is performed using the resist pattern as a mask.

[0285] Process (5)

[0286] The formed resist pattern is preferably used for processing the underlying film or substrate (more preferably a substrate). Specifically, the resist pattern can be used as a mask to process various substrates as a base using dry etching, wet etching, ion implantation, or metal plating. Using the resist pattern of the present invention as a mask and etching the substrate using a dry etching method is a more preferred embodiment. Since the resist pattern of the present invention can obtain a thicker film thickness, it can also be used for substrate processing using an ion implantation method.

[0287] When the underlying film is processed using a resist pattern, the processing can be performed in stages. For example, the BARC layer can be processed using a resist pattern, the SOC film can be processed using a BARC pattern, and the substrate can be processed using an SOC pattern.

[0288] An example of a processing method includes the following steps:

[0289] (5a) etching the resist pattern;

[0290] (5b) Etching the substrate.

[0291] wherein the combination of steps (5a) and (5b) is repeated at least twice; and

[0292] The substrate is formed by stacking a plurality of Si-containing layers, at least one Si-containing layer has electrical conductivity, and at least one Si-containing layer has electrical insulation.

[0293] It is preferable that the Si-containing layer having conductivity and the Si-containing layer having electrical insulation properties are alternately stacked.

[0294] The resist pattern of the present invention can also be used for ion implantation.

[0295] Therefore, the method of manufacturing a processed substrate of the present invention includes the following steps.

[0296] Manufacturing a resist pattern by the method according to claim 11; and

[0297] Ion implantation is performed using the resist pattern as a mask, or

[0298] The lower layer of the resist pattern is processed using the resist pattern as a mask to form a lower layer pattern, and ion implantation is performed using the lower layer pattern as a mask.

[0299] Ion implantation can be performed using a known ion implantation apparatus and a known method. In the manufacture of semiconductor devices and / or liquid crystal display devices, an impurity diffusion layer is formed on the surface of the substrate. The formation of the impurity diffusion layer is usually carried out in two stages: the introduction and diffusion of impurities. As one of the introduction methods, there is an ion implantation method, which ionizes impurities such as phosphorus and boron in a vacuum and accelerates them with a high electric field to penetrate 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, and the resist pattern is sometimes destroyed.

[0300] The resist pattern formed by the present invention is a thick film with high rectangularity and high heat resistance, and therefore can be suitably used for ion implantation in which ions are implanted at high energy.

[0301] Examples of the ion source (impurity element) include boron, phosphorus, arsenic, argon, etc. Examples of the thin film on the substrate include silicon, silicon dioxide, silicon nitride, aluminum, etc.

[0302] Then, the substrate can be further processed as needed, preferably by forming a wiring process on the processed substrate to manufacture the device. These processes can be applied to well-known methods. As needed, the substrate is cut into bare chips (chips), connected to a lead frame, and encapsulated with a resin. In the present invention, the encapsulated product is referred to as a device (device). As the device, semiconductor devices, liquid crystal display devices, organic EL display devices, plasma display devices, solar cell devices can be listed, preferably semiconductor devices.

[0303] [Example]

[0304] The present invention will be described below by various examples. However, it should be noted that the embodiments of the present invention are not limited to these examples.

[0305] Preparation of Resist Composition I

[0306] PGME, PGMEA, and MMPOM (propylene glycol dimethyl ether) were mixed at a mass ratio of 60:20:20 (PGME:PGMEA:MMPOM) to form a mixed solvent. Alkali-soluble resin A1, photoacid generator B1, photoreaction quencher D1, and surfactant E1 were added to this mixed solvent to form a mixed solution. The solids concentration was 36.5% by mass. The mass ratios of A1:B1:D1:E1 were 100:1.44:0.10:0.15.

[0307] In the following examples, components other than the solvent are referred to as solid content, and the concentration of the sum of components other than the solvent in the entire composition is referred to as solid content concentration.

[0308] The mixed solution was stirred at room temperature for 30 minutes to obtain a solution. Complete dissolution of each component was visually confirmed. The obtained solution was filtered through a 0.05 μm filter to obtain a resist composition I.

[0309] Alkali-soluble resin A1: p-Hydroxystyrene / cyclohexyl acrylate / tert-butyl acrylate copolymer (Mw=27,000, random copolymer)

[0310]

[0311] Photoacid generator B1: the following compound (Heraeus, DTBPIO-C1)

[0312]

[0313] Photoreaction quencher D1: the following compound (Sumitomo Pharma Food & Chemical Co., Ltd., ZK-1741)

[0314]

[0315] Surfactant E1: Organosiloxane surfactant (BYK, BYK-333)

[0316] Preparation of Comparative Resist Composition II

[0317] A comparative resist composition II was obtained in the same manner as in the preparation of the resist composition I except that the alkali-soluble resin A1 was changed to the alkali-soluble resin A2.

[0318] Alkali-soluble resin A2: p-Hydroxystyrene / styrene / tert-butyl acrylate copolymer (Mw=27,000, random copolymer)

[0319]

[0320] <Formation of Resist Film>

[0321] An 8-inch silicon wafer was treated with HMDS at 90°C for 60 seconds. Using Coater Developer Mark8 (Tokyo Electron), the prepared resist solution was dripped onto the 8-inch silicon wafer and spin-coated. The speed was changed from 1,000 rpm to 3,500 rpm depending on the target film thickness. The resist film was then baked on a hot plate at 140°C for 120 seconds. The thickness of the resulting resist film was measured using an optical interferometer film thickness measurement device (M-1210, SCREEN).

[0322] The resist film obtained by spin coating at 1,000 rpm using the resist composition I (solid content concentration 36.5% by mass) had a thickness of 18.0 μm. In the following examples, the spin coating rotation speed was adjusted according to the target film thickness to obtain the desired film thickness.

[0323] When forming a resist film with a thickness of 10 to 18 μm, use Composition 1 with a solids concentration of 36.5% by mass. The spin coating speed is 1,000 rpm for a film thickness of 18 μm and 3,000 rpm for a film thickness of 10 μm. The resulting film thickness can be gradually reduced by gradually increasing the spin speed.

[0324] Table 1 shows the results when the resist composition I or the comparative resist composition II was used and the film thickness was 18 μm (Example 101 and Comparative Example 101).

[0325] Table 2 shows the results when the resist composition I or the comparative resist composition II was used and the film thickness was 10 μm (Example 201 and Comparative Example 201).

[0326] Table 3 shows the results when the resist composition I was used and the film thickness was 12, 14, and 16 μm (Examples 301 to 303).

[0327]

[0328] <Formation of Resist Pattern>

[0329] In Example 101 and Comparative Example 101, the 18 μm-thick resist film obtained in the above-described resist film formation example was exposed using a KrF stepper (FPA3000-EX5, Canon). PEB (post-exposure baking) was then performed on a hot plate at 110°C for 120 seconds. The film was developed with a 2.38% by mass TMAH aqueous solution for 90 seconds to form a groove pattern with a line:space ratio of 3:1 and a gap width of 10 μm. The cross-sectional shape of the resulting pattern was confirmed using a scanning electron microscope (S9200, Hitachi).

[0330] When a resist film having a thickness of 18 μm was formed using the resist composition I as in the above resist pattern formation example, a resist pattern having a pattern wall top width of 7 μm was obtained. The exposure amount at this time was defined as the sensitivity.

[0331] When forming a resist pattern from a resist film having another film thickness, exposure is performed under the same conditions as those for the resist film having a film thickness of 18 μm to obtain a resist pattern.

[0332] use Figure 1 Describe the shape of the pattern formed. Figure 1 (a) shows a resist pattern 12 formed on a substrate 11, with a line width 13, a space width 14, and a top width 15 of 15 μm, 5 μm, and 7 μm, respectively. The top 16 of the pattern wall is the end point of the top, and a depression may occur in this portion. Figure 1 The resist film thickness of (a) is 18 μm. Figure 1 (b) is a schematic diagram when the inclination of the resist pattern is not changed and the film thickness is set to 10 μm.

[0333] In the evaluation of changing the film thickness, the pattern was produced without changing the inclination as described above.

[0334] <Bite width>

[0335] The formed resist pattern was observed and the degree of depression from the top of the pattern toward the inside (bite width) was evaluated. Figure 2 Specific instructions. Figure 2 Schematically Figure 1 (a) and (b) of the wall top 21. Draw a line perpendicular to the substrate from the endpoint of the pattern top. Draw a line perpendicular to the substrate from the most concave point on the side of the pattern. The distance between these lines is the bite width (nm).

[0336] <Rectangularity>

[0337] The width of the top gap of the formed resist pattern is set as S t , set the width of the gap at the bottom of the resist pattern to S b When , the following formula is used to calculate:

[0338] Rectangularity = S t / S b .

[0339] S t The measurement is made at the top of the part above where the depression occurs.

[0340] Exposure Margin (EL)

[0341] The exposure amount described above was defined as the optimum exposure amount (Eop), and the exposure amounts (Emax, Emin) at which the width of the pattern wall top was ±0.5% were measured.

[0342] EL is calculated using the following formula:

[0343] EL=((Emax-Emin) / Eop)×100(%).

[0344] Depth of Focus (DoF)

[0345] When the focus position of the exposure machine is moved from the optimal value (Dop), the focus position (Dmax, Dmin) at which the width of the top of the resist pattern wall is ±0.5% is measured.

[0346] The DoF is calculated as follows:

[0347] DoF=((Dmax-Dmin) / Dop)×100(%).

[0348] <Film thickness loss>

[0349] The film thickness before and after development was measured, and the following was calculated: film thickness loss = film thickness before development - film thickness after development.

[0350] <Etching rate>

[0351] The resist pattern obtained above was subjected to O2 etching or CF4 etching, and the etching rate was measured.

[0352] For etching, an etching apparatus NE-5000N (ULVAC) was used.

[0353] During O2 etching, the chamber pressure is set to 10Pa, the power is 500W, the bias power (Bias) is 100W, the gas flow rates are O2 (30sccm), N2 (5sccm), and He (266sccm), and the time is 30 seconds to perform dry etching on each film on the wafer.

[0354] During CF4 etching, the chamber pressure is set to 10 Pa, the power is 500 W, the bias power is 100 W, the gas flow rate is CF4 (45 sccm), He (266 sccm), and the time is 30 seconds, and each film on the wafer is dry-etched.

[0355] The film thickness was measured using an optical interference film thickness measuring device (M-1210, SCREEN).

[0356] The film thickness before etching and the film thickness after etching were measured, and the difference between the former and the latter was obtained to calculate the etching rate per unit time (nm / min).

[0357] [Explanation of symbols]

[0358] 11: Substrate

[0359] 12: Resist pattern

[0360] 13: Line width

[0361] 14: Gap width

[0362] 15: Top width

[0363] 16: Top of pattern wall

[0364] 21: Top of wall

[0365] 22: Bite width.

Claims

1. A thick film chemically amplified positive resist composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a solvent (C): in, The resist film formed by the thick-film chemically amplified positive resist composition has a thickness of 5.0 to 50.0 μm; The alkali-soluble resin (A) comprises the following repeating units: in, R 11 、R 21 、R 41 and R 45 Each independently is C 1-5 Alkyl, wherein -CH2- in the alkyl may also be replaced by -O-, 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 independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy or -COOH, p11 is 0 to 4; p15 is 1 to 2; p11+p15≦5, p21 is 0 to 4, n21 is 0 to 1, p41 is 0 to 4, p45 is 1 to 2, p41+p45≦5, P 31 C 4-20 Alkyl, wherein the alkyl group does not form a ring, and part or all of the H groups in the alkyl group may be substituted with halogen; and The number n of repeating units of the repeating units (A-1), (A-2), (A-3) and (A-4) in the alkali-soluble resin (A) A-1 、n A-2 、n A-3 and n A-4 satisfy: n A-1 / (n A-1 +n A-2 +n A-3 +n A-4 )=0~80%、 n A-2 / (n A-1 +n A-2 +n A-3 +n A-4 )=1~40%、 n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) = 0-40%, or n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 )=0~40%; Among them, n A-3 / (n A-1 +n A-2 +n A-3 +n A-4 ) and n A-4 / (n A-1 +n A-2 +n A-3 +n A-4 ) is greater than 0%; Alternatively, when the total number of all repeating units contained in the alkali-soluble resin (A) is set to n total When it satisfies: (n A-1 +n A-2 +n A-3 +n A-4 ) / n total =80~100%。 2. The composition according to claim 1, wherein The solvent (C) comprises propylene glycol monomethyl ether (PGME) (C-1), Optionally, the content of PGME (C-1) is 30 to 100% by mass based on the solvent (C); Optionally, the solvent (C) further comprises a solvent (C-2); Alternatively, the content of solvent (C-2) is 0% by mass or more and less than 50% by mass based on solvent (C); or Alternatively, the solvent (C-2) is selected from the group consisting of alcohol solvents (C-2-1) and low-boiling-point solvents (C-2-2).

3. The composition according to claim 1 or 2, wherein The mass average molecular weight of the alkali-soluble resin (A) is 10,000 to 50,000.

4. The composition according to one or more of claims 1 to 3, wherein The photoacid generator (B) is represented by formula (B-1) or formula (B-2), B n+ Cation B n- Anion (B-1) Among them, B n+ The cation is a cation represented by formula (BC1), a cation represented by formula (BC2), or a cation represented by formula (BC3), B n+ The cation is generally n-valent, where n is 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 is generally n-valent; in, R b1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio or C 6-12 aryloxy, nb1 are each independently 0, 1, 2 or 3; in, R b2 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, nb2 are each independently 0, 1, 2 or 3; in, R b3 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, R b4 Each independently is C 1-6 alkyl, nb3 are each independently 0, 1, 2 or 3; in, R b5 Each independently is C 1-6 Fluorine-substituted alkyl, C 1-6 Fluorine-substituted alkoxy, or C 1-6 alkyl; in, R b6 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 a fluorine-substituted alkoxyaryl group, and nb4 is 1 or 2; in, R b7 Each independently is 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 Can bond with each other to form a fluorine-substituted heterocyclic structure; in, R b8 For hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy or hydroxyl groups, L b is a carbonyl group, an oxy group or a carbonyloxy group, Y b are each independently hydrogen or fluorine, nb5 is an integer from 0 to 10, and nb6 is an integer from 0 to 21; in, R b9 C 1-5 Fluoro-substituted alkyl, R b10 Each independently is C 3-10 Alkenyl or alkynyl, C 2-10 Sulfanyl, C 5-10 a saturated heterocycle, wherein the CH3- in the alkenyl and alkynyl groups may be substituted by a phenyl group, and the -CH2- in the alkenyl and alkynyl groups may be replaced by at least one of -C(=O)-, -O-, or a phenylene group, nb7 is 0, 1, or 2.

5. The composition according to claim 1 or 2, further comprising a photoreaction quencher (D), wherein The photoreaction quencher (D) is represented by formula (D-1), D m+ Cation D m- Anion (D-1) in, D m+ The cation is a cation represented by formula (DC1) or a cation represented by formula (DC2), D m+ The cations are all m-valent, where m is 1 to 3, and D m- The anion is an anion represented by formula (DA1) or an anion represented by formula (DA2), D m- The anion is generally m-valent; in, R d1 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, C 6-12 Aryl, C 6-12 Arylthio or C 6-12 aryloxy, nd1 is each independently 0, 1, 2 or 3; in, R d2 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, nd2 are each independently 0, 1, 2 or 3; in, X is C 1-20 hydrocarbons or single bonds, R d3 are independently hydrogen, hydroxyl, C 1-6 Alkyl or C 6-10 Aryl, nd3 is 1, 2, or 3, nd4 is 0, 1, or 2; in, R d4 C 1-15 Alkyl, wherein a part or all of the alkyl group may form a ring, and -CH2- in the alkyl group may be replaced by -C(=O)-; Alternatively, the photoreaction quencher (D) is a quencher in which a cation portion generated by receiving light reacts with an anion portion generated by the photoacid generator (B) by receiving light.

6. The composition according to one or more of claims 1 to 5, further comprising a surfactant (E), Optionally, further comprising a plasticizer (F); or Optionally, the composition further contains an additive (G), which is at least one selected from the group consisting of a surface smoothing agent, a pigment, a contrast enhancer, an alkali, an acid, a radical generator, a substrate adhesion enhancer, and a defoaming agent.

7. A composition according to one or more of claims 1 to 6, wherein The content of the alkali-soluble resin (A) is greater than 0% by mass and less than 50% by mass based on the composition. The content of the photoacid generator (B) is greater than 0% by mass and less than 20% by mass based on the alkali-soluble resin (A), and The content of the solvent (C) is 20% by mass or more and less than 100% by mass based on the composition. Optionally, the content of the photoreaction quencher (D) is 0.01 to 5% by mass based on the alkali-soluble resin (A); Optionally, the content of the surfactant (E) is 0.0001 to 1% by mass based on the alkali-soluble resin (A); Optionally, based on the composition, the content of the plasticizer (F) is 0 to 3% by mass; or Alternatively, the content of the additive (G) is 0.00001 to 10% by mass based on the alkali-soluble resin (A).

8. The composition according to one or more of claims 1 to 7, which is a thick film chemically amplified positive KrF resist composition.

9. A method for manufacturing a resist film, comprising the steps of: (1) applying a composition according to one or more of claims 1 to 8 onto a substrate; and (2) heating the composition to form a resist film; Optionally, the resist film has a thickness of 5.0 μm to 50 μm; Optionally, the heating in (2) is performed at 100 to 250° C. and / or for 30 to 300 seconds; or Optionally, the heating in (2) is performed in air or nitrogen atmosphere.

10. A method for manufacturing a resist pattern, comprising the steps of: forming a resist film by the method according to claim 9; (3) exposing the resist film to light; and (4) The resist film is developed.

11. The method for producing a resist pattern according to claim 10, wherein The ratio of the distance from the end point of the top of the resist pattern to the perpendicular line of the substrate and the distance from the most depressed point of the side surface of the resist pattern to the perpendicular line of the substrate to the resist film thickness is 0.023 or less.

12. A method for manufacturing a processed substrate, comprising the steps of: forming a resist pattern by the method according to claim 10; and (5) Processing using the resist pattern as a mask: Optionally, the underlying film or substrate is processed in (5).

13. A method for manufacturing a processed substrate, comprising the steps of: forming a resist pattern by the method according to claim 10; (5a) etching the resist pattern; and (5b) etching the substrate; in, The combination of steps (5a) and (5b) is repeated at least twice; and The substrate is formed by stacking a plurality of layers containing Si, at least one layer containing Si is conductive, and at least one layer containing Si is electrically insulating; Alternatively, layers containing Si having electrical conductivity and layers containing Si having electrical insulation are alternately stacked.

14. A method for manufacturing a processed substrate, comprising the steps of: Manufacturing a resist pattern by the method according to claim 11; as well as Ion implantation is performed using the resist pattern as a mask, or The resist pattern is used as a mask to process a lower layer of the resist pattern to form a lower layer pattern, and ion implantation is performed using the lower layer pattern as a mask.

15. A method for manufacturing a device comprising the method according to one or more of claims 12 to 14; Optionally, the method further comprises forming wiring on the processed substrate; or Optionally, the device is a semiconductor device.

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