Negative-type peel resist composition comprising alkali-soluble resin and photo-acid generator and method of manufacturing metal film pattern on substrate

Abstract

The object of this invention is to provide a resist composition that can form and retain fine resist patterns. Another object is to provide a resist layer with good sensitivity and / or resolution. Yet another object is to provide a negative stripping resist composition from which resist patterns are well removable. [Solution] This invention provides a negative stripping resist composition comprising an alkali-soluble resin and a photoacid-generating agent. This invention provides a method for fabricating a metal film pattern on a substrate. This invention provides a method for manufacturing a device comprising a method for fabricating a metal film pattern.

Description

Technical Field

[0001] This invention relates to a negative stripping resist composition comprising an alkali-soluble resin and a photoacid-generating agent. This invention also relates to a method for fabricating a metal film pattern on a substrate. Furthermore, this invention relates to a method for manufacturing a device comprising a metal film pattern. Background Technology

[0002] Because of the trend towards smaller and higher-performance devices, finer patterning is required in devices (e.g., semiconductor devices, FPD devices). Photolithography, which uses photoresist (hereinafter referred to as "resist"), is commonly used for fine processing. For example... Figure 1 The example illustrates a known stripping step for manufacturing electrodes, characterized by removing unwanted electrode portions from a patterned resist layer. In contrast, a typical electrode etching step uses the resist pattern as a mask to remove (typically by dry etching) the electrode beneath the resist pattern to obtain the desired electrode pattern.

[0003] In this case, a specific negative photoresist composition for forming a stripping pattern was studied, which was coated on the substrate and developed simultaneously with the substrate (Patent Document 1).

[0004] To achieve high photosensitivity through a good inverted conical profile, a negative photoresist composition was studied, comprising: an alkali-soluble binder resin; a halogen-containing first photoacid generator; a triazine-based second photoacid generator; a crosslinking agent having an alkoxy structure; and a solvent (Patent Document 2).

[0005] To achieve storage stability, high sensitivity, and a film retention rate of over 95% (after development) to form a fully undercut strip resist pattern, a strip resist composition comprising an alkali-soluble cellulose resin, but which is a positive resist (Patent Document 3).

[0006] [Existing technical documents]

[0007] [Patent Literature]

[0008] Patent Document 1: JP2005-37414A

[0009] Patent Document 2: US2011 / 0274853A

[0010] Patent Document 3: US2012 / 0129106A Summary of the Invention

[0011] [The problem the invention aims to solve]

[0012] The inventors have identified one or more important issues that still require improvement, as listed below: insufficient coatability; insufficient solute solubility; difficulty in obtaining well-shaped developable resist patterns and / or detecting defects when the pattern size is small; insufficient removability of resist patterns when the pattern size is small; insufficient yield; insufficient sensitivity and / or resolution of the resist layer; and difficulty in obtaining an inverted conical profile.

[0013] The inventors then discovered that the following invention solved at least one of these problems.

[0014] [Methods used to solve problems]

[0015] This invention provides a negative stripping resist composition comprising one or more (A) alkali-soluble resins and one or more (B) photoacid-generating agents; wherein

[0016] (A) Alkali-soluble resins include (A1) resins and / or (A2) resins;

[0017] (B) Photoacid generators contain (B1) onium salts and / or (B2) sulfonyl compounds;

[0018] The conditions are (i) when the negative stripping resist composition contains one (A) alkali-soluble resin, the negative stripping resist composition contains a variety of (B) photoacid-generating agents, and (ii) when the negative stripping resist composition contains one (B) photoacid-generating agent, the negative stripping resist composition contains a variety of (A) alkali-soluble resins.

[0019] (A1) Resin is represented by the following formula (A1);

[0020]

[0021] R 11 R 12 R 14 R 15 R 17 and R 18 Each independently is hydrogen, C 1-6 Alkyl, carboxyl, halogen, or cyano groups

[0022] R 13 and R 16 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, halogen, or cyano groups,

[0023] R 19 C 1-15 Alkyl or C 1-15 Alkoxy, where R 19 The alkyl moiety can form saturated and / or unsaturated rings.

[0024] m 11 n is a number between 0 and 4. 11 m is a number from 1 to 3. 11 +n 11 ≤5,m 12 Numbers between 0 and 5

[0025] p A1 q A1 and r A1 For the number of repetitions, [p A1 / (p A1 +q A1 +r A1 The percentage is 30-98%, [q] A1 / (p A1 +q A1 +r A1 The percentage is 0-70%, [r] A1 / (p A1 +q A1 +r A1) The percentage ranges from 0% to 70%.

[0026] (A2) The resin is represented by the following formula (A2);

[0027]

[0028] R 21 R 22 R 24 and R 25 Each independently is hydrogen, C 1-6 Alkyl, carboxyl, halogen, or cyano groups

[0029] R 23 C 1-6 Alkyl, C 1-6 Alkoxy, halogen, or cyano groups,

[0030] R 26 C 1-15 Alkyl or C 1-15 Alkoxy, where R 26 The alkyl moiety can form saturated and / or unsaturated rings.

[0031] m 21 n is a number between 0 and 4. 21 m is a number from 1 to 3. 21 +n 21 ≤5,

[0032] p A2 and r A2 For the number of repetitions, [p] A2 / (p A2 +rA2 The percentage is 30-100%, [r] A2 / (p A2 +r A2 The percentage ranges from 0% to 70%.

[0033] (B1) Onium salts are represented by the following formula (B1);

[0034] [B m+ [Cation][B] m- [Anion] (B1),

[0035] B m+ The cation is represented by the following formula (B1)-C1 and / or formula (B1)-C2, and the whole has an m valence, where m = 1 to 3;

[0036]

[0037] R 31 R 32 R 33 R 34 and R 35 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl,

[0038] m 31 m 32 m 33 m 34 and m 35 Each number is independently between 0 and 3;

[0039] B m- Anions are represented by the following formulas: (B1)-A1, (B1)-A2 and / or (B1)-A3;

[0040]

[0041] R 41 R 42 and R 43 Each independently is either unreplaced or C 1-6 Alkyl-substituted C 6-12 aryl, unsubstituted or halogenated or carbonyl C 1-12 Alkyl, m 41 =1 or 2;

[0042] (B2) Sulfonyl compounds are represented by the following formula (B2)-1 or (B2-2);

[0043]

[0044] R 51 R52 and R 53 Each independently is hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, R 51 R 52 and R 53 The alkyl moieties can combine with each other to form cycloalkyl or aryl groups.

[0045] m 52 =0 or 1,

[0046] R 54 C is unsubstituted or halogenated 1-6 alkyl,

[0047] R 55 Each is independent as C 5-12 cycloalkyl or C 6-12 Aryl.

[0048] The present invention provides a method for manufacturing a resist pattern, comprising: forming a coating of a negative stripping resist composition on a substrate; baking the resist composition to form a resist layer; exposing the resist layer; and developing the resist layer to form a resist pattern.

[0049] The present invention provides a method for manufacturing a metal film pattern on a substrate, comprising: manufacturing a resist pattern; forming a metal film on the resist pattern; and removing the remaining resist pattern and metal film thereon.

[0050] The present invention provides a method for manufacturing a device, which includes a method for manufacturing a resist pattern or a metal film pattern on a substrate.

[0051] [The effects of the invention]

[0052] The negative stripping resist composition exhibits good coatability. The solute in the composition exhibits good solubility in solvents. Even with small pattern sizes, a good shape of the developing resist pattern made from this composition can be obtained, and / or defects (e.g., pattern collapse) can be reduced. Furthermore, even with small pattern sizes, the resist pattern made from this composition can be easily removed. High throughput can be achieved. The resist layer obtained with the composition of the present invention exhibits good sensitivity. The photoresist layer can have good resolution. Resist patterns with an inverted conical profile can be obtained with the composition of the present invention. These are all beneficial for more finely designed patterns used in the stripping step to create metal film patterns. Attached Figure Description

[0053] Figure 1 This is a schematic diagram of the stripping process.

[0054] Figure 2 This is a schematic diagram of the etching process.

[0055] Figure 3 This is an illustrative diagram for mask design used for resist patterning.

[0056] Figure 4 This is an illustrative diagram for mask design used for resist patterning. Detailed Implementation

[0057] The above description and the following detailed description are for illustrative purposes only and are not intended to limit the scope of the claimed invention.

[0058] definition

[0059] In this specification, unless expressly limited or stated otherwise, the symbols, units, abbreviations and terms defined below have the meanings given in the following definitions, descriptions and examples.

[0060] The use of the singular form includes the plural form, and "a" or "the" means "at least one". Furthermore, the use of the term "comprising" and other forms such as "including" and "containing" is not restrictive. Additionally, terms such as "element" or "component" cover elements or components that contain one unit and elements or components that contain more than one unit.

[0061] The term “and / or” refers to any combination of any of the foregoing elements, including the use of a single element.

[0062] When using "-", "to", or "~" to indicate a range of values, the range includes the two digits before and after the "-", "to", or "~", and the units are shared. For example, 5 to 25 mol% means more than 5 mol% and less than 25 mol%.

[0063] The "C" used in this article x-y “C” x -C y "and "C x Terms such as "" indicate the number of carbons in a molecule or substituent. For example, "C" 1-6 "Alkyl" refers to an alkyl chain having one or more but no more than six carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0064] When the polymer described herein has multiple repeating units, these repeating units are copolymerized. This copolymerization can be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When representing a polymer or resin using a structural formula, n or m, etc., as listed in parentheses, indicates the number of repeating units.

[0065] The temperature unit used in this article is Celsius. For example, 20 degrees means 20 degrees Celsius.

[0066] Negative stripping resist composition

[0067] This invention provides a negative stripping resist composition comprising one or more (A) alkali-soluble resins and one or more (B) photoacid-generating agents. The negative resist composition of this invention can be used in stripping processes, wherein in subsequent steps, the metal film portions (resist pattern walls) formed on the developed resist layer are removed to obtain a metal film pattern. Because the composition of this invention is a negative resist, the resist layer made from this composition has the characteristic that the exposed portions of the layer exhibit increased resistance to dissolution by the developer, while the unexposed portions will be dissolved by the developer.

[0068] The compositions of the present invention satisfy the following conditions: (i) when the negative release resist composition contains one (A) alkali-soluble resin, the negative release resist composition contains multiple (B) photoacid-generating agents; (ii) when the negative release resist composition contains one (B) photoacid-generating agent, the negative release resist composition contains multiple (A) alkali-soluble resins. Acceptably, the compositions of the present invention simultaneously contain multiple (A) alkali-soluble resins and multiple (B) photoacid-generating agents. It can be said that compositions simultaneously satisfying (iii) the alkali-soluble resin in the composition consists of one alkali-soluble resin and (iv) the photoacid-generating agent in the composition consists of one photoacid-generating agent are excluded from the scope of the present invention.

[0069] Alkali-soluble resins

[0070] The compositions of the present invention comprise one or more (A) alkali-soluble resins. The (A) alkali-soluble resins include (A1) resins and / or (A2) resins. The resin is preferably an alkali-soluble adhesive resin. Furthermore, the resin preferably comprises a phenolic varnish polymer or a polyhydroxystyrene polymer. The resins comprised in the compositions of the present invention are preferably random copolymers or block copolymers, more preferably random copolymers.

[0071] For example, (A) alkali-soluble resin may contain multiple (A1) resins but not (A2) resin.

[0072] In one embodiment of the invention, the mass ratio of (A) alkali-soluble resin to the total mass of the negative stripping resist composition is 5 to 50% by mass (preferably 10 to 30% by mass, more preferably 10 to 25% by mass). When the thickness of the coating made from the negative stripping resist composition is equal to or greater than 1.0 μm, the above mass ratio is preferably 15 to 30% by mass (more preferably 15 to 25% by mass, even more preferably 18 to 22% by mass). When the thickness of the coating made from the composition of the present invention is less than 1.0 μm, the above mass ratio is preferably 5 to 15% by mass (more preferably 5 to 14% by mass, even more preferably 10 to 14% by mass). The thickness of the resulting resist coating can be increased by adding more solid components (mainly comprising (A) alkali-soluble resin) to the composition.

[0073] As described above, the compositions of the present invention may contain a variety of (A) alkali-soluble resins. It is not intended to be theoretically restrictive, but it is considered beneficial to include a variety of (A) alkali-soluble resins in the composition, as the alkali processing precision of the resist layer can be appropriately set to exhibit good sensitivity, good resolution, and / or good pattern shape.

[0074] In this application, the weight-average molecular weight (Mw) can be measured by gel permeation chromatography (GPC). In a suitable example of this measurement, the GPC column is set to 40 degrees Celsius; tetrahydrofuran at a flow rate of 0.6 mL / min is used as the elution solvent; and monodisperse polystyrene is used as the standard.

[0075] As one aspect of the present invention, the weight-average molecular weight (Mw) of the alkali-soluble resin in (A) of the composition of the present invention is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, even more preferably 4,000 to 20,000, and even more preferably 5,000 to 15,000.

[0076] (A1) resin

[0077] (A1) resin is represented by the following formula (A1).

[0078]

[0079] R 11 R 12 R 14 R 15 R 17 and R 18 Each independently is hydrogen, C 1-6 Alkyl, carboxyl, halogen, or cyano groups; preferably hydrogen or methyl; more preferably hydrogen. One embodiment of the invention is R. 17 It is a methyl group. R 13 and R 16Each independently is C 1-6 Alkyl, C 1-6 Alkoxy, halogen, or cyano; preferably methyl, ethyl, isopropyl, tert-butyl, or fluorine; more preferably methyl or tert-butyl.

[0080] R 19 It is C 1-15 Alkyl or C 1-15 Alkyl group. R 19 The alkyl moiety can form saturated and / or unsaturated rings. One embodiment of the invention is R. 19 It is C 1-15 Alkyl group. R 19 The alkyl portion is preferably branched or cyclic, more preferably branched. 19 Preferably, it is methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl or ethyladamantyl; more preferably tert-butyl, ethylcyclopentyl, methylcyclohexyl or ethyladamantyl; even more preferably tert-butyl.

[0081] m 11 It is a number from 0 to 4. One embodiment of the present invention may be that (A) the alkali-soluble resin does not contain (A2) resin and contains two (A1) resins, each in equal parts; in one (A1) resin, p... A1 =100%, m 11 =1; in another (A1) resin, p A1 =100%, m 11 =2. In this case, m 11 =1.5. Unless otherwise specified, this will also apply throughout the text.

[0082] m 11 Preferably 0, 1, 2, 3 or 4; more preferably 0, 1 or 2; even more preferably 0.

[0083] n 11 The number is 1 to 3; more preferably 1 or 2; more preferably 1.

[0084] m 11 +n 11 ≤5.

[0085] m 12 The number is between 0 and 5; preferably 0, 1, 2, 3 or 4; more preferably 0, 1 or 2; and even more preferably 0.

[0086] p A1 q A1 and r A1 This is the number of repetitions.

[0087] [p A1 / (p A1+q A1 +r A1 The content of the active ingredient is 30-98%; preferably 50-95%; more preferably 70-95%; and even more preferably 70-90%.

[0088] [q A1 / (p A1 +q A1 +r A1 The content of [ ] is 0-70%; preferably 0-40%; more preferably 5-40%; and even more preferably 10-40%.

[0089] [r A1 / (p A1 +q A1 +r A1 The content of [ ] is 0-70%; preferably 0-40%.

[0090] Preferably, q A1 and r A1 Do not take 0% simultaneously. A preferred embodiment of the present invention is [r A1 / (p A1 +q A1 +r A1 )] = 0%.

[0091] The (A1) resin of the present invention may or may not contain repeating units other than those defined above in formula (A1). In a preferred embodiment, the (A1) resin of the composition of the present invention does not contain repeating units other than those defined above in formula (A1).

[0092] Exemplary embodiments of the (A1) resin are described below, but are for illustrative purposes only.

[0093]

[0094] As one aspect of the present invention, the weight-average molecular weight (Mw) of the (A1) resin in the composition of the present invention is preferably 5,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 5,000 to 20,000, and even more preferably 8,000 to 15,000.

[0095] The mass ratio of (A1) resin to (A) alkali-soluble resin is preferably 30-100% by mass, more preferably 40-100% by mass, and even more preferably 40-80% by mass. In one embodiment of the present invention, (A) alkali-soluble resin does not contain (A2) resin but contains (A1) resin.

[0096] (A2) resin

[0097] (A2) Resin is represented by the following formula (A2).

[0098]

[0099] R 21 R 22 R 24 and R 25 Each independently is hydrogen, C 1-6 Alkyl, carboxyl, halogen, or cyano groups; preferably hydrogen or methyl; more preferably hydrogen. One embodiment of the invention is R. 24 It is a methyl group.

[0100] R 23 C 1-6 Alkyl, C 1-6 Alkoxy, halogen, or cyano; preferably methyl, ethyl, isopropyl, tert-butyl, or fluorine; more preferably methyl or tert-butyl.

[0101] R 26 C 1-15 Alkyl or C 1-15 Alkyl group. R 26 The alkyl moiety can form saturated and / or unsaturated rings. One embodiment of the invention is R. 26 C 1-15 Alkyl group. R 26 The alkyl portion is preferably branched or cyclic, more preferably branched. 26 Preferably, it is methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl or ethyladamantyl; more preferably tert-butyl, ethylcyclopentyl, methylcyclohexyl or ethyladamantyl; even more preferably tert-butyl.

[0102] m 21 It is a number from 0 to 4; preferably 0, 1, 2, 3 or 4; more preferably 0, 1 or 2; and even more preferably 0.

[0103] n 21 It is a number from 1 to 3; more preferably 1 or 2; even more preferably 1.

[0104] m 21 +n 21 ≤5.

[0105] p A2 and r A2 It is a repeating number.

[0106] [p A2 / (p A2 +r A2 The content of [ ] is 30-100%; preferably 50-100%; more preferably 60-100%; and even more preferably 100%.

[0107] [r A2 / (p A2 +r A2 The content of [ ] is 0-70%; more preferably 0-50%; even more preferably 0-40%; and even more preferably 0%.

[0108] The (A2) resin of the present invention may or may not contain repeating units other than those defined above in formula (A2). In a preferred embodiment, the (A2) resin of the composition of the present invention does not contain repeating units other than those defined above in formula (A2).

[0109] (A2) Exemplary embodiments of the resin are described below, but are for illustrative purposes only.

[0110]

[0111] As one embodiment of the present invention, the weight-average molecular weight (Mw) of the (A2) resin of the composition of the present invention is preferably 2,000 to 20,000; more preferably 4,000 to 20,000; and even more preferably 5,000 to 10,000.

[0112] The mass ratio of (A2) resin to (A) alkali-soluble resin is preferably 10-100% by mass, more preferably 20-100% by mass, and even more preferably 20-50% by mass. In one embodiment of the invention, the (A) alkali-soluble resin does not contain (A1) resin but contains (A2) resin.

[0113] (B) Photoacid generator

[0114] The compositions of the present invention comprise one or more (B) photoacid generators (hereinafter referred to as PAGs). In the irradiated portion of the negative resist composition, the PAG is irradiated and generates acid, which catalyzes the crosslinking reaction of the resin and the crosslinking agent (if present).

[0115] (B) Photoacid generators contain (B1) ononium salts and / or (B2) sulfonyl compounds. For example, (B) PAG may contain multiple (B1) ononium salts and not contain (B2) sulfonyl compounds.

[0116] In one embodiment of the present invention, the mass ratio of (B) photoacid generator to (A) alkali-soluble resin is 1-20% by mass; preferably 1-15% by mass; more preferably 1-10% by mass. For clarity, throughout this application, when the composition of the present invention contains multiple (B) PAGs, the mass ratio of (B) PAGs refers to the sum of the mass ratios of the multiple (B) PAGs. For clarity, throughout this application, when the composition of the present invention contains multiple (A) alkali-soluble resins, the mass ratio of (A) alkali-soluble resins refers to the sum of the mass ratios of the multiple (A) alkali-soluble resins.

[0117] As described above, the compositions of the present invention may contain a plurality of (B)PAGs. It is not intended to be theoretically restrictive, but it is considered desirable to include a plurality of (B)PAGs in the composition, as the resolution and / or pattern shape can be appropriately set.

[0118] (B1) Onion salt

[0119] (B1) Onion salts are represented by the following formula (B1).

[0120] [B m+ [Cation][B] m- [Anion] (B1)

[0121] B m+ The cation is represented by the following formula (B1)-C1 and / or formula (B1)-C2.

[0122] B m+ The cation as a whole has a valence of m.

[0123] m = 1 to 3; preferably 1, 2 or 3; more preferably 1 or 2; even more preferably 1.

[0124]

[0125] R 31 R 32 R 33 R 34 and R 35 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl; preferably methyl, ethyl, tert-butyl, 1,1-dimethylpropyl, methoxy or ethoxy; more preferably methyl, tert-butyl, 1,1-dimethylpropyl or methoxy; even more preferably tert-butyl.

[0126] m 31 m 32 m 33 m 34 and m 35Each number is independently a number from 0 to 3; preferably, each number is independently 0 or 1; more preferably, it is 0. One embodiment of the invention is m. 31 m 32 m 33 m 34 and m 35 Each is independently 1.

[0127] B m+ Exemplary embodiments of cations are described below, but are for illustrative purposes only.

[0128]

[0129] B m- Anions are represented by the following formulas: (B1)-A1, (B1)-A2 and / or (B1)-A3.

[0130]

[0131] R 41 R 42 and R 43 Each independently is either unreplaced or C 1-6 Alkyl-substituted C 6-12 aryl, unsubstituted or halogenated or carbonyl C 1-12 Alkyl group; preferably unsubstituted or halogenated C4. 1-6 Alkyl groups; more preferably, C groups substituted with halogens. 1-4 Alkyl; more preferably C1 or C4 alkyl groups substituted with halogen. The halogen here is preferably fluorine. As one embodiment of the invention, R 41 R 42 Or R 43 The alkyl moieties can be internally bonded or bonded together to form a saturated cyclic hydrocarbon ring. As a preferred embodiment, R... 41 R 42 Or R 43 The alkyl moieties do not internally bond or bond with each other to form a saturated cyclic hydrocarbon ring. The preferred embodiment is C. 1-6 All hydrogen atoms in the alkyl group are replaced by halogens.

[0132] m 41 =1 or 2; 1 is preferred. When m 41 When = 2, R 41 It is a divalent chain linker.

[0133] B m- Exemplary embodiments of anions are described below, but are for illustrative purposes only.

[0134] CF3SO 3- C4F9SO 3- C3F7SO3- ,

[0135] For example, the following ononium salt is an example of formula (B1). B m+ The cation is represented by (B1)-C1, and the whole has a valence of m=2. B m- The anion is represented by formula (B1)-A1, and the whole has a valence of m=2. 41 =2. R 41 It is a C4 alkylene group substituted with fluorine.

[0136]

[0137] (B2) Sulfonyl compounds

[0138] (B2) Sulfonyl compounds are represented by the following formula (B2)-1 or (B2-2).

[0139]

[0140] R 51 R 52 and R 53 Each independently is hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl; C preferred 1-6 Alkyl group. R 51 R 52 and R 53 The alkyl moieties can combine with each other to form cycloalkyl or aryl groups.

[0141] m 52 = 0 or 1; preferably 0. A preferred embodiment of the invention is m 52 =1.

[0142] R 54 It is C that is either unsubstituted or halogenated. 1-6 Alkyl; preferably fluorinated C 1-4 alkyl.

[0143] R 55 Each independently is C 5-12 cycloalkyl or C 6-12 Aryl; C preferred 5-12 Cycloalkyl; more preferably C6 cycloalkyl.

[0144] (B2) Exemplary embodiments of sulfonyl compounds are described below, but are for illustrative purposes only.

[0145]

[0146] (C) Solvent

[0147] The compositions of the present invention may contain (C) solvent.

[0148] One embodiment of the invention is that (C) the solvent includes, for example, water and organic solvents. A preferred embodiment of the invention is that (C) the solvent is selected from aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, monohydric alcohol solvents, polyhydric alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, sulfur-containing solvents, and any combination of these solvents.

[0149] (C) Examples of solvents include: aliphatic hydrocarbon solvents, such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isohexane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents, such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methyl ethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, and isobutylbenzene; and monohydric alcohol solvents, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, 2-ethylhexanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, cyclohexanol, benzyl alcohol, and benzyl alcohol. Methanol, diacetone alcohol, and cresol; polyol solvents, such as ethylene glycol, propylene glycol, 1,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol; ketone solvents, such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, trimethyl nonanone, cyclohexanone, cyclopentanone, methyl cyclohexanone, 2,4-pentanedione, acetone-based acetone, acetophenone, anisole; ether solvents, such as diethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether. Ethylene glycol monoethyl ether, ethylene glycol monohexyl 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, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; ester solvents Examples of solvents include diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-butyl propionate, methyl lactate, ethyl lactate (EL), γ-butyrolactone, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; nitrogen-containing solvents, such as N-methylformamide; and sulfur-containing solvents, such as dimethyl sulfide. Any mixture of these solvents may also be used.

[0150] In particular, regarding the storage stability of the solution, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol 1-monomethyl ether 2-acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate, and any mixture of these solvents are preferred.

[0151] From the perspective of the coating properties and / or solubility of the solute, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, ethyl lactate, and mixtures of any two solvents selected therefrom are preferred. For this purpose, propylene glycol 1-monomethyl ether 2-acetate is more preferred as solvent (C).

[0152] (C) The solvent preferably contains an organic solvent, and the water content in the composition is preferably 0.1% by mass or less, more preferably 0.01% by mass or less. Considering its relationship with another layer or coating, (C) solvent is preferably water-free. As one embodiment of the invention, the water content in the composition is preferably 0.00% by mass.

[0153] In one embodiment of the present invention, (C) the solvent accounts for 30-94% by mass of the total mass of the negative stripping resist composition; preferably 50-94% by mass; more preferably 70-94% by mass; and even more preferably 75-90% by mass.

[0154] (D) Crosslinking agent

[0155] The compositions of the present invention may contain a (D) crosslinking agent (hereinafter referred to as an X-linking group). In negative resists, the resin and the crosslinking agent undergo a crosslinking reaction induced by heat, for example, during post-exposure baking. Furthermore, the solubility of the exposed portions of the resist layer changes.

[0156] One embodiment of the present invention is (D) the crosslinking agent comprising at least one selected from aryl compounds, melamine compounds, guanidine compounds, glycourea compounds, urea compounds, epoxy compounds; thioepoxide compounds, isocyanate compounds, azides and alkenyl compounds; each compound is unsubstituted or substituted by at least one group selected from hydroxyl, hydroxymethyl, alkoxymethyl and acylmethyl.

[0157] The compositions of the present invention may contain one or more (D) crosslinking agents. One aspect of the present invention is that the compositions contain multiple (D) crosslinking agents, for example, two (D) crosslinking agents.

[0158] One embodiment of the present invention is that the mass ratio of (D) crosslinking agent to (A) alkali-soluble resin is 1 to 20% by mass; preferably 3 to 20% by mass; more preferably 5 to 15% by mass.

[0159] The (D) crosslinking agent of the present invention may include (D1) a crosslinking agent represented by formula (D1) and / or (D2) a crosslinking agent represented by formula (D2). In one embodiment of the present invention, the composition comprises one (D2) crosslinking agent and does not contain any other crosslinking agents.

[0160] In addition to the exemplary embodiments represented by formula (D1) or (D2) described below, the compounds described below are other exemplary embodiments, but are for illustrative purposes only.

[0161]

[0162] (D1) Crosslinking agent

[0163] (D1) The crosslinking agent is represented by formula (D1).

[0164]

[0165] R 61 C 2-8 Alkoxyalkyl; preferably C 2-4 Methoxyalkyl; more preferably -CH2-O-CH3.

[0166] R 62 C 2-8 Alkoxyalkyl; preferably C 2-4 Methoxyalkyl, more preferably -CH2-O-CH3.

[0167] R 63 Is it not replaced or by C? 1-6 Alkyl-substituted C 6-10 Aryl, unsubstituted or C 1-6 Alkyl-substituted C 1-8 Alkyl, or -NR 61 R 62 R 63 C 6-10 The aryl group is preferably phenyl or naphthyl, more preferably phenyl. R 63 C 1-8 The alkyl group is preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl, more preferably methyl or butyl. 63 The replacement of C 6-10 Aryl or C 1-8 C of alkyl 1-6 The alkyl group is preferably methyl, ethyl, isopropyl, or butyl, more preferably methyl. Further preferred is R. 63 Unreplaced C 6-10 Aryl and C 1-8 alkyl.

[0168] Even more preferably, R 63 Yes -NR61 R 62 R 61 and R 62 The definitions and preferred implementation schemes are each independently the same as those described above.

[0169] R 64 Is it not replaced or by C? 1-6 Alkyl-substituted C 6-10 Aryl, unsubstituted or C 1-6 Alkyl-substituted C 1-8 Alkyl, or -NR 61 R 62 R 64 C 6-10 The aryl group is preferably phenyl or naphthyl, more preferably phenyl. R 64 C 1-8 The alkyl group is preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl, more preferably methyl or butyl. 64 The replacement of C 6-10 Aryl or C 1-8 C of alkyl 1-6 The alkyl group is preferably methyl, ethyl, isopropyl, or butyl, more preferably methyl. Further preferred is R. 64 Unreplaced C 6-10 Aryl and C 1-8 alkyl.

[0170] Even more preferably, R 64 Yes -NR 61 R 62 R 61 and R 62的 The definitions and preferred implementation schemes are each independently the same as those described above.

[0171] Exemplary embodiments of the (D1) crosslinking agent represented by formula (D1) are described below, but are for illustrative purposes only.

[0172]

[0173]

[0174] As one embodiment of the present invention, the mass ratio of (D1) crosslinking agent to (A) alkali-soluble resin is preferably 0.10 to 8% by mass; more preferably 0.5 to 5% by mass; and even more preferably 0.5 to 3% by mass.

[0175] (D2) Crosslinking agent

[0176] (D2) The crosslinking agent is represented by formula (D2).

[0177]

[0178] R 65 Is it not replaced or by C? 1-6 Alkyl-substituted C 1-20 Alkyl group. R 65 C 1-20 Alkyl groups can be straight-chain alkyl groups or branched alkyl groups. R 65 C 1-20 Alkyl groups are preferably C 1-10 Alkyl, more preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or -C(CH3)2-CH2-C(CH3)3, more preferably -C(CH3)2-CH2-C(CH3)3. R 65 The replacement of C 1-20 C of alkyl 1-6 The alkyl group is preferably methyl, ethyl, isopropyl, or butyl, more preferably methyl. Further preferred is R. 65 Unreplaced C 1-20 alkyl.

[0179] l D2 The value is 1, 2, 3 or 4; preferably 2 or 3; more preferably 2.

[0180] m D2 It can be 0, 1, or 2; preferably 0 or 1; more preferably 1.

[0181] n D2 It can be 0, 1, or 2; 1 is preferred.

[0182] l D2 +m D2 +n D2 ≤6.

[0183] Exemplary embodiments of the (D2) crosslinking agent represented by formula (D2) are described below, but are for illustrative purposes only.

[0184]

[0185] As one embodiment of the present invention, the mass ratio of (D2) crosslinking agent to (A) alkali-soluble resin is preferably 0.50 to 40% by mass; more preferably 1 to 20% by mass; and even more preferably 5 to 15% by mass.

[0186] As one embodiment of the present invention, a resist coating made from the composition of the present invention and any of the above-mentioned crosslinking dosages can exhibit good pattern shape and removability.

[0187] additive

[0188] The compositions of the present invention may also contain another additive. This additive may be selected from quenchers, surfactants, dyes, contrast enhancers, acids, free radical generators, agents for enhancing adhesion to the substrate, alkalis, surface leveling agents, and defoamers.

[0189] As one embodiment of the invention, the mass ratio of other additives to (A) alkali-soluble resin is preferably 0.05 to 10% by mass; more preferably 0.10 to 5% by mass; even more preferably 0.10 to 2% by mass. In one embodiment of the invention, the composition of the invention does not contain (0% by mass) these additives, unless specifically stated below.

[0190] Monomeric dyes and azo dyes can be embodiments of the present invention. The dyes described in WO2001 / 61410 are other embodiments. 9-Anthracene methanol is a preferred embodiment of the present invention as a dye.

[0191] quencher

[0192] Quenchers can be added to the compositions of the present invention to improve properties such as resist pattern shape and long-term stability (post-exposure stability of the latent image formed by patterned exposure of the resist layer). As a quencher, amines are preferred, and more specifically, aliphatic secondary or aliphatic tertiary amines can be used. Here, aliphatic amines refer to C 2-9 Alkyl or C 2-9 Alkyl alcoholamines. One or more alkylene groups in the alkyl moiety may be substituted with one or more ether linkages. More preferably, they have a C... 3-6 Tertiary aliphatic amines of alkyl alcohols.

[0193] Exemplary embodiments of the quencher include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, triisopropylamine, tributylamine, tripentylamine, trioctylamine, diethanolamine, N,N-dicyclohexylmethylamine, triethanolamine, and tris[2-(2-methoxyethoxy)ethyl]amine. More preferably, triethanolamine and tris[2-(2-methoxyethoxy)ethyl]amine are preferred.

[0194] In one embodiment of the present invention, the mass ratio of the quencher to the alkali-soluble resin (A) is preferably 0.05-5% by mass; more preferably 0.10-2% by mass; and even more preferably 0.10-1% by mass.

[0195] surfactants

[0196] The compositions of the present invention may contain surfactants that can be used to reduce pinholes or streaks in the coating and to increase the coatability and / or solubility of the composition.

[0197] In one embodiment of the present invention, the mass ratio of the surfactant to the alkali-soluble resin (A) is preferably 0.01 to 10% by mass; more preferably 0.05 to 5% by mass; and even more preferably 0.05 to 2% by mass.

[0198] Examples of surfactants include: polyoxyethylene alkyl ether compounds, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ether compounds, such as polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc.; polyoxyethylene-polyoxypropylene block copolymer compounds; sorbitol fatty acid ester compounds, such as sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol fatty acid ester compounds, such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, and polyoxyethylene sorbitol tristearate. Other examples of surfactants include: fluorosurfactants such as EFTOP (trade names) EF301, EF303 and EF352 (Tohkem Products Corp.), MEGAFACE (trade names) F171, F173, R-08, R-30 and R-2011 (DIC Corp.), Fluorad FC430 and FC431 (Sumitomo 3M Co., Ltd.), AsahiGuard (trade name) AG710 (Asahi Glass Co., Ltd.), and SURFLON S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (Asahi Glass Co., Ltd.); organosiloxane polymers such as KP341 (Shin-Etsu Chemical Co., Ltd.).

[0199] peeling steps

[0200] An exemplary implementation of the stripping patterning step is as follows: Figure 1 The schematic diagram is shown. As shown in (a), a substrate is prepared, and then a resist composition is applied to the substrate to obtain a resist layer (as shown in (b)). Next, light irradiation exposure is performed through a designed mask, as shown in (c). The resist layer is then developed to form a resist pattern as shown in (d). The resist pattern has walls and trenches.

[0201] For the subsequent removal step, a resist pattern with an inverted conical profile is preferred. For example, the resist pattern can have a good inverted conical profile such that the side surfaces of the substrate and the resist pattern walls preferably form an angle of less than 90 degrees (more preferably equal to or greater than 55 degrees and less than 90 degrees, and even more preferably 55 to 80 degrees). This angle can be measured by SEM cross-sectional photographs.

[0202] Then, metal is applied (preferably deposited) onto the resist pattern to form a metal film, as shown in (e). The metal film is preferably an electrode. The metal film is formed on the walls and trenches of the resist pattern. Preferably, the resist layer has sufficient thickness to form gaps between the metal film on the walls and the trenches, allowing a resist layer remover to penetrate through the gaps.

[0203] And as shown in (f), the resist pattern and the metal film thereon are removed (preferably by means of a resist layer remover solution) to obtain a metal film pattern on the substrate. Here, the metal film formed on the walls of the resist pattern is removed, so that the designed metal film pattern formed on the trenches of the resist pattern is retained.

[0204] For comparison, the following is a brief description. Figure 2 The schematic diagram illustrates the resist etching steps. (a') shows the preparation of the substrate. (b') shows the formation of a metal film (e.g., an electrode), (c') shows the formation of a resist layer on the metal film. (d') shows exposure through a mask, (e') shows development to form a resist pattern. (f') shows dry etching to remove exposed metal film portions, and (g') shows the removal of residual resist patterns from the remaining metal film portions.

[0205] Formation of resist layer

[0206] The composition of the present invention is applied over a substrate. Prior to this, the substrate surface may be pretreated, for example, with a 1,1,1,3,3,3-hexamethyldisilazane solution. The composition of the present invention reacts under irradiation, and its irradiated portion exhibits increased resistance to dissolution by the developer. Coating can be performed using known methods, such as spin coating. The applied resist composition is then baked to remove the solvent from the composition, thereby forming a resist layer. The baking temperature may vary depending on the composition used, but is preferably 70–150°C (more preferably 90–150°C, and even more preferably 100–140°C). The baking time may be 10–180 seconds, preferably 30–90 seconds on a hot plate, or 1–30 minutes in a hot gas atmosphere (e.g., in a clean oven).

[0207] The thickness of the formed resist layer is preferably 0.40 to 5.00 μm (more preferably 0.40 to 3.00 μm, and even more preferably 0.50 to 2.00 μm).

[0208] In the method for manufacturing the resist pattern of the present invention, the underlayer can be located between the substrate and the resist coating, such that the substrate and the resist coating do not directly contact each other. Examples of the underlayer include a bottom anti-reflective coating (BARC layer), an inorganic hard mask underlayer (e.g., a silicon oxide coating, a silicon nitride coating, or a silicon oxynitride coating), and an adhesive coating. The underlayer can consist of a single layer or multiple layers. Because the resist layer of the present invention has good removability, a preferred embodiment is to form the resist coating on a substrate without an underlayer. This reduces the risk of accidental dissolution of the underlayer (e.g., BARC) during resist development, which would otherwise cause difficulties in process control.

[0209] Other layers (such as a top anti-reflective coating, TARC) can be formed on top of the resist coating / resist layer.

[0210] Resist patterning

[0211] The resist layer is exposed through a given mask. There are no particular limitations on the wavelength of the light used for exposure. Exposure is preferably performed with light of wavelengths from 13.5 to 365 nm (preferably 13.5 to 248 nm). KrF excimer laser (248 nm), ArF excimer laser (193 nm), or extreme ultraviolet light (13.5 nm) are preferred embodiments; KrF excimer laser is more preferred. These wavelengths may vary within ±1%. Because the resist pattern made from the composition of the present invention can form a good shape and exhibit good removability, a more finely designed mask can be used. For example, a mask comprising a line space width equal to or less than 1.0 μm can be preferably used, and a line space width less than 1.0 μm can be more preferred.

[0212] If necessary, post-exposure baking can be performed after exposure. The post-exposure baking temperature is selected from the range of 80 to 150°C, preferably 90 to 140°C, and the post-exposure baking time is selected from the range of 0.3 to 5 minutes, preferably 0.5 to 2 minutes.

[0213] Next, development is performed using a developer. The unexposed portions of the resist layer of the present invention are removed by development, resulting in the formation of a resist pattern. A 2.38% by mass aqueous solution of TMAH (accepting concentration variations of ±1%) is preferably used as the developer for developing the resist pattern. Additives such as surfactants can be added to the developer. The temperature of the developer is typically selected from the range of 5 to 50°C, preferably 25 to 40°C, and the development time is typically selected from the range of 10 to 300 seconds, preferably 30 to 90 seconds. Known methods, such as paddle (immersion) development, can be used as the development method. Preferably, the resist layer is effectively removed and does not remain in the groove portions of the resist pattern.

[0214] After development, the resist pattern can be cleaned with water or a cleaning solution, such as using water and / or a cleaning solution instead of the developer. The substrate can then be dried, for example, by a spin-drying method.

[0215] Fabricating metal film patterns on a substrate

[0216] A metal is applied onto a resist pattern to form a metal film. Known methods can be used. Deposition and coating are preferred (vapor deposition is more preferred). In this specification, the metal oxide is included in the metal. Preferably, the metal film has good electrical conductivity. One or more mixed metals can be used. Preferably, the thickness of the formed metal film is significantly less than the thickness of the resist pattern wall (preferably -80% to -20% of the thickness, more preferably -70% to -30% of the thickness) to form gaps through which the resist layer remover can penetrate into the resist pattern wall.

[0217] The resist pattern and the metal film thereon are removed to obtain a metal film pattern on the substrate (this step can be referred to as "stripping" in a narrow sense). The metal film formed on the walls of the resist pattern is removed, thereby retaining the designed metal film pattern formed on the trenches of the resist pattern. Known methods can be used for this removal, such as resist layer removers. One embodiment of a resist layer remover is AZ Remover 700 (Merck Performance Materials Ltd.). The patterned metal film is preferably an electrode on the substrate, which can be used to fabricate devices in subsequent steps.

[0218] Device manufacturing

[0219] Subsequently, the substrate is further processed as needed to form a device. This further processing can be performed using known methods. After the device is formed, the substrate is diced into chips, which are then connected to a lead frame and encapsulated in resin, as needed. Preferably, the device is a semiconductor device, a radio frequency module, a solar cell chip, an organic light-emitting diode, or an inorganic light-emitting diode. A preferred embodiment of the device of the present invention is a semiconductor device. Another preferred embodiment of the device of the present invention is a radio frequency module, which may consist of a transmitter (including an IC chip) and a receiver.

[0220] Example

[0221] The invention will be described below by way of working examples. These examples are given for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise stated, the term "parts" as used in the following description refers to parts by mass.

[0222] Preparation Example 1 of Working Composition 1

[0223] Prepare the following components.

[0224] Polymer A1: Random copolymer p-hydroxystyrene (70) styrene (30) (Mw approximately 9,700; CST 7030, Maruzen Petrochemical)

[0225] Polymer A2: p-hydroxystyrene (Mw approximately 5,000; VP-3500, Nippon Soda)

[0226] Crosslinking agent A1 (DML-POP, Honshu Chemical Industry Co., Ltd.)

[0227] C4F9SO3 - PAG A (TG-NONA, Toyosei Kogyo Co., Ltd.)

[0228] PAG B (MDT sensitizer, Heraeus Precious Metals North America Daychem LLC)

[0229] Quencher 1 (triethanolamine)

[0230] Quencher 2 (tris[2-(2-methoxyethoxy)ethyl]amine)

[0231] Surfactant: MegafacR2011, DIC Corp.

[0232] PGMEA is used as a solvent.

[0233] Each component is added to the solvent. The proportions of crosslinking agent A1, PAG A, PAG B, quencher, and surfactant are 10.66, 3.37, 0.62, 0.39, and 0.10% by mass, respectively, compared to a total of 100% by mass for one or more polymers. This 100% by mass polymer is based on the amount of solids.

[0234] The solution was then stirred and all components were confirmed to be dissolved. The solution was mixed and solvent was added until the total solids concentration reached 23.0% by mass. The resulting solution was filtered through a 0.1 μm capsule filter.

[0235] The resulting working composition is represented by composition 1 in Table 1-1 below.

[0236] Preparation Examples of Working Compositions 2-15

[0237] Except for the changes in components and / or amounts as described in Table 1-1 below, the preparation was carried out in the same manner as in Preparation Example 1.

[0238] Obtain working compositions 2-15.

[0239] Table 1-1

[0240] Polymer A1 Polymer A2 Crosslinking agent A1 PAG A PAG B Quenching Agent 1 Quenching Agent 2 Composition 1 50 50 10.66 3.37 0.62 0.39 - Composition 2 50 50 10.66 3.37 0.93 0.39 - Composition 3 50 50 10.66 3.37 1.86 0.39 - Composition 4 50 50 10.66 2.81 1.55 0.39 - Composition 5 50 50 10.66 2.25 1.24 0.39 - Composition 6 50 50 10.66 3.37 1.86 0.49 - Composition 7 50 50 10.66 3.37 1.86 0.59 - Composition 8 50 50 10.66 1.12 1.24 0.39 - Composition 9 50 50 10.66 1.69 1.24 0.39 - Composition 10 60 40 10.66 1.12 1.24 0.39 - Composition 11 60 40 7.99 1.12 1.24 0.39 - Composition 12 60 40 10.66 3.37 - 0.39 - Composition 13 70 30 10.66 - 1.24 - - Composition 14 70 30 10.66 - 9.31 - - Composition 15 50 50 6.93 1.69 - - 0.49

[0241] In Table 1-1, “composition” refers to a composition, and the same applies to the following tables.

[0242] Example of substrate preparation for evaluating working composition 1

[0243] The substrate used for the following evaluation was prepared as follows: The surface of a silicon substrate (SUMCO Corp., 8-inch) was treated with a 1,1,1,3,3,3-hexamethyldisilazane solution at 90°C for 60 seconds. Working composition 1 was spin-coated onto the substrate and soft-baked at 110°C for 60 seconds to form a resist layer with a thickness of 1.30 μm. This was achieved by exposure using an FPA-3000EX5 (Canon) mask. The mask used had regions comprising multiple 1.0 μm lines with a line-to-space ratio of 1:1 (dense region). Furthermore, the line and space regions within the mask gradually narrowed. The widths of these lines are 1.0μm, 0.9μm, 0.8μm, 0.7μm, 0.6μm, 0.5μm, 0.45μm, 0.40μm, 0.38μm, 0.36μm, 0.34μm, 0.32μm, 0.30μm, 0.28μm, 0.26μm, 0.24μm, 0.22μm, 0.20μm, 0.18μm, 0.16μm, 0.14μm, 0.12μm, and 0.10μm. The mask has multiple lines of equal width, with each line having a 1:1 spatial ratio. For better understanding, Figure 3 The mask design is described herein for illustrative purposes only and is not intended to limit the scope of the invention. For better understanding, Figure 3 An imprecise scaling factor was used.

[0244] Furthermore, the mask used has regions comprising multiple 1.0 μm lines with a line-to-space ratio of 1:5 (separation region). The line and space regions within the mask gradually narrow. The widths of these lines are 1.0 μm, 0.9 μm, 0.8 μm, 0.7 μm, 0.6 μm, 0.5 μm, 0.45 μm, 0.40 μm, 0.38 μm, 0.36 μm, 0.34 μm, 0.32 μm, 0.30 μm, 0.28 μm, 0.26 μm, 0.24 μm, 0.22 μm, 0.20 μm, 0.18 μm, 0.16 μm, 0.14 μm, 0.12 μm, and 0.10 μm. The mask has multiple lines of equal width, each with a line-to-space ratio of 1:5. For better understanding, Figure 4 The mask design is described herein for illustrative purposes only and is not intended to limit the scope of the invention. For better understanding, Figure 4 An imprecise scaling factor was used.

[0245] The substrate was exposed and baked (PEB) at 100°C for 60 seconds. Following this, a 60-second immersion development was performed using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution to resist the substrate. While the immersion developer was forming on the substrate, pure water was introduced to flow onto it. As the substrate rotated, the immersion developer was replaced with pure water. The substrate was then rotated at 2,000 rpm for rotary drying.

[0246] Examples of substrate preparation for evaluating working compositions 2-15

[0247] Except for changing working composition 1 to working compositions 2 to 15, each substrate is prepared in the same manner as described above.

[0248] Evaluation example of resist pattern shape

[0249] The shape of the resist pattern exposed through a 0.5 μm space in a dense area (line:space = 1:1) on each of the aforementioned substrates was evaluated using a SEM instrument SU8230 (Hitachi High Technology Corporation). The evaluation criteria are specified below.

[0250] A: No resist pattern collapse was found.

[0251] B: The resist pattern was found to have collapsed.

[0252] The evaluation results are shown in Table 1-2 below.

[0253] Example of resolution evaluation

[0254] Exposure was performed with an exposure level that could reproduce a 400nm pattern through a 400nm slit (line). Cross-sectional SEM was observed to confirm the pattern shape from the 400nm pattern to narrower patterns. Here, resolution is the spatial width before pattern collapse or gap filling.

[0255] The evaluation criteria are specified as follows.

[0256] X: In dense regions, the resolution is equal to or less than 340nm.

[0257] Y: In dense regions, the resolution is greater than 340nm.

[0258] X: In the separation region, the resolution is equal to or less than 300nm.

[0259] Y: In the separation region, the resolution is greater than 300nm.

[0260] The overall evaluation categories are as follows.

[0261] A: Both the dense area and the separated area are rated X.

[0262] B: At least one of the assessment criteria for dense and separated areas is Y.

[0263] The evaluation results are shown in Table 1-2 below.

[0264] Table 1-2

[0265]

[0266] Preparation Examples 16-20 of Working Compositions 16-20 and Reference Preparation Example 1 of Reference Composition 1

[0267] The preparation was carried out in the same manner as in Preparation Example 1, except that the components and / or amounts were changed as described in Table 2-1 below, and the total solid component concentration reached 13.0% by mass.

[0268] Working compositions 16–20 and reference composition 1 were obtained.

[0269] Crosslinking agent A2 ( 301, Allnex Japan Inc.

[0270] PAGC (TG-TPH, Toyosei Kogyo Co., Ltd.)

[0271] PAGD (WPI-169, Fujifilm and Wako Pure Chemical Industries, Ltd.)

[0272] Table 2-1

[0273]

[0274] Example of substrate preparation for evaluating working composition 16

[0275] The substrates used for the following evaluations are prepared as follows.

[0276] The BARC composition AZ KrF-17B (Merck Performance Materials Ltd., hereinafter referred to as MPMltd.) was spin-coated onto the surface of a silicon substrate (SUMCO Corp., 8 inches) and baked at 180°C for 60 seconds to obtain a BARC coating with a thickness of 38 nm.

[0277] The working composition 16 is spin-coated onto the substrate and soft-baked at 110°C for 60 seconds to form a resist layer with a thickness of 0.50 μm on the substrate.

[0278] Exposure and subsequent processing were performed in the same manner as described in the preparation example of the substrate used for evaluating working composition 1, except that the mask with only dense areas was changed. Then, a substrate for evaluating working composition 16 was obtained.

[0279] Preparation examples of substrates used to evaluate working compositions 17-20 and reference composition 1

[0280] Except for changing working composition 16 to working compositions 17-20 and changing reference composition 1, each substrate is prepared in the same manner as described in the preparation example of the substrate used to evaluate working composition 16.

[0281] Evaluation example of resist pattern shape

[0282] The shape of the resist patterns exposed in dense areas (line:space = 1:1) at 0.25 μm intervals on each substrate of working compositions 16–20 and reference composition 1 was evaluated using a SEM instrument SU8230. The evaluation criteria are specified below.

[0283] A: No resist pattern collapse was found.

[0284] B: The resist pattern was found to have collapsed.

[0285] The evaluation results are shown in Table 2-2 below.

[0286] Example of resolution evaluation

[0287] Exposure was performed using an exposure level that could reproduce a 300nm pattern through a 300nm slit (line). Cross-sectional SEM was observed to confirm the pattern shape from the 400nm pattern to the narrower patterns. Here, resolution is the spatial width before spatial collapse.

[0288] The evaluation criteria are specified as follows.

[0289] A: Resolution equal to or less than 260nm.

[0290] B: Resolution greater than 260nm.

[0291] Table 2-2

[0292]

[0293] The resist layer made from the working composition exhibits better resolution than the resist layer made from the reference composition.

[0294] Preparation Examples of Working Compositions 21-24

[0295] The preparation was carried out in the same manner as in Preparation Example 1, except that the components and / or amounts were changed according to Table 3-1 below, and the total solid component concentration reached 24.0% by mass.

[0296] Working compositions 21–24 were obtained.

[0297] Polymer A3: Random copolymer p-hydroxystyrene (90) styrene (10) (Mw approximately 10400; CST-90, Maruzen Petrochemical)

[0298] Polymer A4: Random copolymer p-hydroxystyrene (85) styrene (15) (Mw approximately 9,300; CST8515, Maruzen Petrochemical)

[0299] Dye (9-AM, Heraeus)

[0300] Table 3-1

[0301]

[0302] Examples 21-24 of substrate preparation for evaluating working compositions

[0303] Each substrate was prepared in the same manner as described in the preparation example of the substrate used to evaluate working composition 1, except that working composition 1 was changed to working compositions 21 to 24, a mask having only dense areas was used, and a resist layer with a thickness of 1.50 μm was formed on the substrate.

[0304] Evaluation example of resist pattern shape

[0305] The shape of the resist pattern exposed on each substrate of working compositions 21–24 through a 0.7 μm interval (line:space = 1:1) in a dense region was evaluated using a SEM instrument SU8230. The evaluation criteria are specified below.

[0306] A: No resist pattern collapse was found.

[0307] B: The resist pattern was found to have collapsed.

[0308] The evaluation results are shown in Table 3-2 below.

[0309] Example of removability evaluation

[0310] Prepare 20mm × 20mm portions cut from each substrate of working compositions 21–24. Bake these portions at 110°C for 90 seconds. Place each portion on a petri dish, sufficiently far from the center. Slowly add resist remover (AZ Remover 700, MPM Ltd.) to the petri dish. Mix with a stirrer and heat the solution to 70°C. After mixing the solution for 10 minutes, remove each portion. Then wash off the resist remover with sufficient pure water. Finally, dry each portion by spray drying with N2 gas.

[0311] The resist pattern before removal was observed using an optical microscope, from a pattern exposed in 1.0 μm line space to a gradually narrowing pattern. The evaluation criteria are specified below.

[0312] A: Resist patterns exposed in line spaces of 0.7 μm or less are cleanly removed.

[0313] B: Resist patterns exposed in line spaces exceeding 0.7 μm were cleanly removed.

[0314] The evaluation results are shown in Table 3-2 above.

[0315] Table 3-2

[0316] Pattern Shape Removability Composition 21 A A Composition 22 A A Composition 23 A A Composition 24 A A

[0317] The resist pattern made from the composition of the working example can be cleanly removed.

[0318] [Explanation of reference numerals in the attached figures]

[0319] 1.Substrate

[0320] 2. Resist layer

[0321] 3. Mask

[0322] 4. Irradiation

[0323] 5.Metal film

[0324] 6.Substrate

[0325] 7.Metal film

[0326] 8. Resist layer

[0327] 9. Face mask

[0328] 10. Irradiation

[0329] 11. A line 1.0 μm wide

[0330] 12. A space 1.0 μm wide

[0331] 13. A region with a line width of 1.0 μm and a line-to-space ratio of 1:1.

[0332] 14. A line 0.9μm wide

[0333] 15. A space 0.9μm wide

[0334] 16. A region with a line width of 0.9 μm and a line-to-space ratio of 1:1.

[0335] 17. A line 1.0 μm wide

[0336] 18. A space 5.0 μm wide

[0337] 19. A region with a line 1.0 μm wide and a line-to-space ratio of 1:5.

[0338] 20. A line 0.9μm wide

[0339] 21. A space 4.5 μm wide

[0340] 22. A region with a line width of 0.9 μm and a line-to-space ratio of 1:5.

Claims

1. A negative stripping resist composition comprising one or more (A) alkali-soluble resins and one or more (B) photoacid-generating agents; wherein (A) Alkali-soluble resins include (A1) resin and (A2) resin; (B) Photoacid generators contain (B1) onium salts and / or (B2) sulfonyl compounds; (A1) Resin is represented by the following formula (A1); (A1) R 11 R 12 R 14 R 15 R 17 and R 18 Each independently is hydrogen, C 1-6 Alkyl, carboxyl, halogen, or cyano groups R 13 and R 16 Each independently is C 1-6 Alkyl, C 1-6 Alkyl, halogen, or cyano groups, R 19 C 1-15 Alkyl or C 1-15 Alkoxy, where R 19 The alkyl portion may form saturated and / or unsaturated rings or not form rings at all. m 11 n is a number between 0 and 4. 11 It is a number from 1 to 3, m 11 +n 11 ≤5,m 12 It is 0. p A1 q A1 and r A1 It is a repetition number, [p A1 / (p A1 +q A1 +r A1 The percentage is 30-98%, [q] A1 / (p A1 +q A1 +r A1 The percentage is 10-40%, [r] A1 / (p A1 +q A1 +r A1 The percentage is 0-70%. (A2) The resin is represented by the following formula (A2); (A2) R 21 R 22 R 24 and R 25 Each independently is hydrogen, C 1-6 Alkyl, carboxyl, halogen, or cyano groups R 23 C 1-6 Alkyl, C 1-6 Alkyl, halogen, or cyano groups, R 26 C 1-15 Alkyl or C 1-15 Alkoxy, where R 26 The alkyl portion may form saturated and / or unsaturated rings or not form rings at all. m 21 n is a number between 0 and 4. 21 m is a number between 1 and 3. 21 +n 21 ≤5, p A2 and r A2 For the number of repetitions, [p A2 / (p A2 +r A2 The percentage is 30-100%, [r] A2 / (p A2 +r A2 The percentage is 0-70%. (B1) Onium salts are represented by the following formula (B1); [B m+ [Cation][B] m- [Anion] (B1) B m+ The cation is represented by the following formula (B1)-C1 and / or formula (B1)-C2, and its overall valence is m, where m = 1~3; R 31 R 32 R 33 R 34 and R 35 Each independently is C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, m 31 m 32 m 33 m 34 and m 35 Each number is independently between 0 and 3; B m- Anions are represented by the following formulas: (B1)-A1, (B1)-A2 and / or (B1)-A3; R 41 R 42 and R 43 Each independently represents either unreplaced or C 1-6 Alkyl-substituted C 6-12 aryl, unsubstituted or halogenated or carbonyl C 1-12 Alkyl, m 41 =1 or 2; (B2) Sulfonyl compounds are represented by the following formula (B2)-1 or (B2-2); R 51 R 52 and R 53 Each independently is hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy or C 6-12 Aryl, wherein R 51 R 52 and R 53 The alkyl groups may combine with each other to form cycloalkyl or aryl groups, or they may not combine with each other. m 52 =0 or 1, R 54 C is unsubstituted or halogenated 1-6 alkyl, R 55 Each independently is C 5-12 cycloalkyl or C 6-12 Aryl.

2. The negative stripping resist composition according to claim 1, further comprising (C) a solvent.

3. The negative stripping resist composition according to claim 1 or 2, wherein, The mass ratio of the alkali-soluble resin (A) to the total mass of the negative stripping resist composition is 5-50% by mass; and The mass ratio of (B) photoacid generator to (A) alkali-soluble resin is 1 to 20 by mass.

4. The negative stripping resist composition according to claim 1 or 2, further comprising (D) a crosslinking agent; wherein the (D) crosslinking agent comprises at least one selected from aryl compounds, melamine compounds, guanidine compounds, glycourea compounds, urea compound epoxy compounds, thioepoxide compounds, isocyanate compounds, azide compounds and alkenyl compounds; and each compound is unsubstituted or substituted by at least one group selected from hydroxyl, hydroxymethyl, alkoxymethyl and acyloxymethyl.

5. The negative stripping resist composition according to claim 1 or 2, further comprising (D) a crosslinking agent, wherein the (D) crosslinking agent comprises (D1) a crosslinking agent represented by formula (D1) and / or (D2) a crosslinking agent represented by formula (D2); (D1), R 61 C 2-8 Alkoxyalkyl, R 62 C 2-8 Alkoxyalkyl R 63 For not replaced or by C 1-6 Alkyl-substituted C 6-10 Aryl, unsubstituted or C 1-6 Alkyl-substituted C 1-8 Alkyl, or -NR 61 R 62 , R 64 For not replaced or by C 1-6 Alkyl-substituted C 6-10 Aryl, unsubstituted or C 1-6 Alkyl-substituted C 1-8 Alkyl, or -NR 61 R 62 , (D2), R 65 It is unreplaced or C 1-6 Alkyl-substituted C 1-20 alkyl, l D2 It is 1, 2, 3 or 4, m D2 It is 0, 1, or 2, n D2 It is 0, 1, or 2, and l D2 +m D2 +n D2 ≤6.

6. The negative stripping resist composition according to claim 1 or 2, wherein, The weight-average molecular weight (Mw) of the alkali-soluble resin (A) is from 2,000 to 100,000.

7. The negative stripping resist composition according to claim 1 or 2 further comprises at least one additive selected from quenchers, surfactants, dyes, contrast enhancers, acids, free radical generators, agents for enhancing adhesion to the substrate, alkalis, surface leveling agents, and defoamers.

8. A method for manufacturing a resist pattern, comprising: A coating of the negative stripping resist composition according to any one of claims 1 to 7 is formed on a substrate; Baking the resist composition to form a resist layer; Expose the resist layer; The resist layer is developed to form a resist pattern.

9. The method for manufacturing a resist pattern according to claim 8, wherein, Exposure is performed using light with wavelengths of 13.5–365 nm.

10. A method for fabricating a metal film pattern on a substrate, comprising: To manufacture the resist pattern according to claim 8 or 9, A metal film is formed on the resist pattern; and Remove any remaining resist patterns and metal film.

11. A method for manufacturing a device, comprising a method for manufacturing a resist pattern or a metal film pattern on a substrate according to any one of claims 8 to 10.

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