Water-soluble composition

Abstract

The present disclosure provides a water-soluble composition comprising: a photofading compound A; a resin B; a surfactant C containing an alkenyl group containing a perfluoroalkyl substituent; and a solvent D. The invention also relates to a water-soluble layer formed by the water-soluble composition.

Description

Technical Field

[0001] The present disclosure relates to a water-soluble composition and a water-soluble layer formed therefrom, and more particularly to a water-soluble composition having excellent flatness and release properties and a water-soluble layer formed therefrom. Background Art

[0002] With the development of high integration and high density of semiconductor integrated circuits, the precision requirements for various fine pattern sizes in the patterning process are also increasing.

[0003] Generally speaking, various fine patterns are formed using "photolithography", which forms a photoresist layer on a substrate through methods such as spin coating, and then transfers the mask pattern to the photoresist layer through subsequent exposure and development steps, and then forms a pattern on the substrate through an etching step. In order to reduce the pattern size and improve the accuracy of the pattern size, a reduced projection exposure machine (stepper) is usually used in photolithography.

[0004] However, in this method of using only a photoresist layer, as the pattern size decreases and the precision increases, it becomes increasingly difficult to maintain its dimensional stability. One of the reasons is that the focal depth decreases due to the reduction in pattern size. To solve this problem, a method of directly or indirectly setting a water-soluble layer on the photoresist layer has been developed to improve the contrast when the pattern is formed by photolithography. This method is called contrast enhancement photolithography or contrast enhancement layer.

[0005] For the above method, it is most desirable that the water-soluble layer can be stripped directly using the developer unit without any adjustment to the existing device. In the developer unit currently used for the positive photoresist layer, the solutions used are alkaline aqueous solution as the developer and pure water as the washing solution. Therefore, the water-soluble composition used to make the water-soluble layer is preferably one that can be easily removed directly using these solutions.

[0006] However, in order to improve the production efficiency of semiconductor processes, as the area of ​​the silicon substrate increases, the area that the water-soluble composition must cover also increases, resulting in a serious shortage of effective coating area, affecting the flatness of the water-soluble layer formed by the overall water-soluble composition on the photoresist layer, thereby making it difficult to form a photoresist pattern.

[0007] However, it is difficult to achieve both flatness and release properties of the water-soluble layer in the prior art. To solve the flatness problem, a surfactant can be used. However, as the amount of surfactant used increases, the release property will decrease due to the variation of hydrophilic and hydrophobic properties, making it difficult to form a photoresist pattern. Summary of the invention

[0008] In order to solve the above problems, the main purpose of the present invention is to provide a water-soluble composition, which can not only improve the flatness of the water-soluble layer formed on the substrate or the photoresist layer, but also take into account the release property.

[0009] According to the above, the present invention provides a water-soluble composition comprising:

[0010] Photofading compound (A);

[0011] Resin (B);

[0012] A surfactant (C) containing an alkenyl group containing a perfluoroalkyl substituent; and

[0013] Solvent (D).

[0014] In one embodiment, in the surfactant (C), the alkenyl group containing a perfluoroalkyl substituent is selected from the group consisting of the following formula (1) and formula (2):

[0015]

[0016] In formula (1) and formula (2), * indicates a bonding site.

[0017] In one embodiment, the surfactant (C) is selected from the group consisting of the following formulas (3) to (5):

[0018]

[0019] In formula (3) to formula (5), q, r, and p are each independently an integer greater than 1, R is a monovalent organic group, and Rf each independently represents an alkenyl group containing a perfluoroalkyl substituent. In one embodiment, based on the total amount of the solvent (D) used being 100 parts by weight, the amount of the surfactant (C) used is 0.01 parts by weight to 1 part by weight.

[0020] In one embodiment, the solvent (D) includes water (D1).

[0021] In one embodiment, the solvent (D) further comprises an organic solvent (D2), and the organic solvent (D2) is selected from the group consisting of aliphatic monohydric alcohols having carbon numbers of 1 to 7 and aliphatic dihydric alcohols having carbon numbers of 1 to 7. In one embodiment, based on the total usage of the solvent (D) being 100 parts by weight, the usage of the organic solvent (D2) is 1 part by weight to 60 parts by weight.

[0022] In one embodiment, the photofading compound (A) comprises a nitrone compound.

[0023] The present invention further provides a water-soluble layer formed by the water-soluble composition.

[0024] The present invention further provides a use of a water-soluble layer for improving the contrast when forming a pattern using yellow light lithography technology.

[0025] The present invention further provides a method for manufacturing a semiconductor device, comprising:

[0026] Providing a substrate and a photoresist layer, wherein the photoresist layer is disposed on the substrate;

[0027] Forming a water-soluble layer on the photoresist layer using the water-soluble composition according to any one of claims 1 to 8;

[0028] exposing the water-soluble layer and the photoresist layer; and

[0029] The water-soluble layer and the exposed portion of the photoresist layer are removed to form a photoresist pattern. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 A schematic diagram of a process of directly forming a water-soluble layer on a photoresist layer to form a photoresist pattern is shown.

[0031] Figure 2 A schematic diagram of a process of disposing an intermediate layer made of a neutral substance between a photoresist layer and a water-soluble layer to form a photoresist pattern is shown.

[0032] Symbols and Markings

[0033] 1:Substrate

[0034] 2: Photoresist layer

[0035] 3: Water-soluble layer

[0036] 4: Ultraviolet rays

[0037] 5: Photoresist pattern

[0038] 6: Middle layer DETAILED DESCRIPTION

[0039] Water soluble ingredients

[0040] In one embodiment, the present invention provides a water-soluble composition comprising:

[0041] Photofading compound (A);

[0042] Resin (B);

[0043] A surfactant (C) containing an alkenyl group containing a perfluoroalkyl substituent; and

[0044] Solvent (D).

[0045] Light fading composition (A)

[0046] In one embodiment, the light-fading composition (A) includes but is not limited to diazonium salts (diazo compounds), nitrone compounds, polysilanes, styryl pyridinium salts, etc. Preferably, the light-fading composition (A) may include a nitrone compound represented by formula (7):

[0047]

[0048] In formula (7):

[0049] R 1 , R 2 and R 3 are each independently alkyl, aryl or hydrogen;

[0050] R 4 , R 5 , R 6 , R 7 and R 8 are the same or different alkyl, hydrogen or carboxyl, and R 4 , R 5 ,

[0051] R 6 , R 7 and R 8 At least one of them is a carboxyl group;

[0052] X is R 9 O-denoted alkoxy, R 10 R 11 N-dialkylamino or hydrogen, R 9 is an alkyl group, R 10 and R 11 are the same or different alkyl groups;

[0053] n is 0, 1 or 2, preferably 0 or 1.

[0054] The aforementioned alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclohexyl, etc.; among which methyl, ethyl, propyl, and butyl are more preferably used. The aforementioned aryl group is preferably an aryl group having 6 to 15 carbon atoms, such as phenyl, substituted phenyl, naphthyl, substituted naphthyl, etc.; among which phenyl, benzyl, and phenethyl are more preferably used.

[0055] Wherein, the nitrone compound represented by formula (7) can be represented by the following formula (7a) to formula (7d):

[0056]

[0057] In formula (7c) and formula (7d), m is 1 or 2.

[0058] Specific examples of the nitrone compound represented by formula (7) include α-[p-(dimethylamino)phenyl]-N-(4-carboxyphenyl)nitrone, α-[p-(diethylamino)phenyl]-N-(4-carboxyphenyl)nitrone, α-[p-(dibutylamino)phenyl]-N-(4-carboxyphenyl)nitrone, α-[p-(diethylamino)phenyl]-N-(3-carboxyphenyl)nitrone, α-[p-(diethylamino)phenyl]-N-(2-carboxyphenyl)nitrone, α-[p-(diethylamino)phenyl]-N-(2-methyl-4-carboxyphenyl)nitrone, nitrone, α-[p-(diethylamino)phenyl]-N-(2-methyl-3-carboxyphenyl)nitrone, α-(p-methoxyphenyl)-N-(4-carboxyphenyl)nitrone, α-(p-ethoxyphenyl)-N-(4-)carboxyphenyl)nitrone, α-(o-methoxyphenyl)-N-(4-carboxyphenyl)nitrone, α-(p-methoxyphenyl)-N-(3-carboxyphenyl)nitrone, α-(p-methoxyphenyl)-N-(2-carboxyphenyl)nitrone, α-(p-methoxyphenyl)-N-(2-methyl-4-carboxyphenyl)nitrone, α- (p-Ethoxyphenyl)-N-(3-methyl-2-carboxyphenyl)nitrone, α-[p-(dimethylamino)phenylvinyl]-N-(4-carboxyphenyl)nitrone, α-[p-(diethylamino)phenylvinyl]-N-(4-carboxyphenyl)nitrone, α-[p-(dimethylamino)phenylvinyl]-N-(3-carboxyphenyl)nitrone, α-[p-(dimethylamino)phenylvinyl]-N-(2-carboxyphenyl)nitrone, α-[p-(dimethylamino)phenylvinyl]-N-(2-methyl-4-carboxyphenyl)nitrone, α-[p-(diethylamino)phenylvinyl]-N-(4-carboxyphenyl)nitrone

[0047] α-(4-methyl-2-carboxyphenyl)nitrone, α-(o-methoxyphenyl)-N-(4-carboxyphenyl)nitrone, α-(o-methoxyphenyl)-N-(3-carboxyphenyl)nitrone, α-(p-methoxyphenyl)-N-(4-carboxyphenyl)nitrone, α-(p-methoxyphenyl)-N-(3-carboxyphenyl)nitrone, α-(o-methoxyphenyl)-N-(2-methyl-4-carboxyphenyl)nitrone and α-(p-methoxyphenyl)-N-(2-methyl-3-carboxyphenyl)nitrone.

[0059] The nitrone compound represented by formula (7) can be synthesized by the following steps: using an alkyl nitrobenzoic acid represented by formula (7-1) which is easily available industrially as a raw material, and performing a hydrogenation reaction as shown in the following reaction formula to obtain a compound represented by formula (7-2), which is then reacted with a compound represented by formula (7-3) to obtain the nitrone compound represented by formula (7).

[0060]

[0061] The above reaction is preferably carried out in an organic solvent such as methanol. The hydrogenation reaction of the alkyl nitrobenzoic acid of formula (7-1) can be carried out at room temperature and in the presence of an appropriate amount of catalyst (such as carbon-supported platinum) at 1 kg / cm 2 Up to 10kg / cm 2 The reaction mixture is charged with 1.7 to 2.3 equivalents of hydrogen gas relative to the alkylnitrobenzoic acid at a pressure of 100 Å.

[0062] In addition, the hydrogenated alkyl nitrobenzoic acid is preferably reacted with the compound of formula (7-3) in the presence of an acid such as acetic acid, and 0.8 mol to 1.2 mol of the compound of formula (7-3) can be added per 1 mol of the hydrogenated alkyl nitrobenzoic acid. The reaction conditions are preferably 20° C. to 50° C., 3 hours to 8 hours. After the reaction is completed, the precipitated crystals can be separated by filtration and washed with a suitable solvent to obtain the nitrone compound represented by formula (7).

[0063] Based on 100 parts by weight of the total amount of the solvent (D), the amount of the light-fading composition A may be 0.5 parts by weight to 30 parts by weight, preferably 1 part by weight to 20 parts by weight, and more preferably 2 parts by weight to 10 parts by weight.

[0064] Resin (B)

[0065] The resin (B) may be, for example, an inert organic polymer. In one embodiment, the resin (B) may be, for example, a copolymer of styrene and allyl alcohol, polystyrene, poly(methyl methacrylate), poly(α-methylstyrene), poly(vinyl pyrrolidone), polyphenylene ether, a copolymer of vinyl pyridine and styrene, a copolymer of acrylonitrile and butadiene, a copolymer of butyl methacrylate and isobutyl methacrylate, cellulose propionate and other hydrocarbon-soluble cellulose esters, ethyl cellulose and other hydrocarbon-soluble cellulose ethers, a copolymer of ethylene and vinyl acetate, polyacenaphthene, polybenzyl methacrylate, polyethylene oxide, poly-2-hydroxyethyl methacrylate, poly-4-isopropylstyrene, polyallyl alcohol, polyhydroxypropyl methylcellulose, polymethylcellulose and polyhydroxypropyl cellulose, polychloroprene, polyethylene oxide and polyvinyl pyrrolidone, acetal resin, a copolymer of acrylonitrile and butadiene, and / or polysaccharides.

[0066] Preferably, the resin (B) comprises a copolymer of 1-vinyl-2-pyrrolidone and vinyl acetate, such as commercially available Luviskol™ VA64 (manufactured by BASF); or a polysaccharide, such as pullulan PI20 (manufactured by Hayashibara Company Limited).

[0067] Based on 100 parts by weight of the total amount of the solvent (D), the amount of the resin B may be 1 part by weight to 30 parts by weight, preferably 2 parts by weight to 20 parts by weight, and more preferably 4 parts by weight to 15 parts by weight.

[0068] By using the resin (B), when coating (eg, spin coating) the water-soluble pattern composition, the coating thickness can be adjusted according to the use requirements, thereby forming a water-soluble layer of a desired thickness.

[0069] Surfactant (C)

[0070] In one embodiment, the surfactant (C) contains an alkenyl group containing a perfluoroalkyl substituent. The alkenyl group containing a perfluoroalkyl substituent is not particularly limited, and can be a linear or branched type, preferably a branched type; in addition, the number of carbon atoms is not particular, for example, it can be 2 to 20, preferably 5 to 20, and more preferably 5 to 15.

[0071] Preferably, the alkenyl group containing a perfluoroalkyl substituent can be selected from the group consisting of the following formula (1) and formula (2):

[0072]

[0073] In formula (1) and formula (2), * indicates a bonding site.

[0074] The surfactant (C) may be, for example, an acrylic polymer containing an alkenyl group containing a perfluoroalkyl substituent on the side chain, or an alkenyl compound containing a perfluoroalkyl substituent selected from the group consisting of the following formulas (3) to (5):

[0075]

[0076] In formula (3) to formula (5), q, r, and p are each independently an integer greater than 1, and R is a monovalent organic group, such as hydrogen, an alkyl group having 1 to 30 carbon atoms, or a hydroxyalkyl group having 1 to 30 carbon atoms;

[0077] and Rf each independently represents an alkenyl group containing a perfluoroalkyl substituent.

[0078] The surfactant (C) may be, for example, an acrylic polymer containing an alkenyl group containing a perfluoroalkyl substituent, and commercially available examples thereof include Ftergent series KB-L82, KB-L85, KB-L97, KB-L109, KB-L110, KB-F2L, KB-F2M, KB-F2S, KB-F3M, KB-FaM, etc. manufactured by NEOS Co., Ltd. of Japan; or may be a surfactant (C) containing an alkenyl group containing a perfluoroalkyl substituent and simultaneously containing at least one of the structural formulas (3) to (5), and commercially available examples thereof include Ftergent series 100, 100C, 110, 140, etc. manufactured by NEOS Co., Ltd. of Japan. A. 150, 150CH, AK, 501, 250, 251, 222F, FTX-218, 300, 310, 400SW, 212M, 245M, 290M, FTX-207S, FTX-211S, FTX-220S, FTX-230S, FTX-209F, FTX-213F, FT X-222F, FTX-233F, FTX-245F, FTX-208G, FTX-218G, FTX-230G, FTX-240G, FTX-204D, FTX-280D, FTX-212D, FTX-216D, FTX-218D, FTX-220D, FTX-222D, etc.

[0079] By adding the alkenyl surfactant (C) containing a perfluoroalkyl substituent, a better balance between hydrophilic and hydrophobic properties can be achieved, thereby taking into account both flatness and release properties.

[0080] Based on 100 parts by weight of the total usage of the solvent (D), the usage of the surfactant (C) may be 0.01 to 1 parts by weight, preferably 0.05 to 0.75 parts by weight, and more preferably 0.1 to 0.5 parts by weight.

[0081] If the water-soluble composition does not use the surfactant (C), the flatness of the formed water-soluble layer is poor. If the amount of the surfactant (C) in the water-soluble composition falls within the above range, the formed water-soluble layer can have better flatness. In addition, if the surfactant (C) includes a group selected from the group consisting of formula (3) to formula (5), the water-soluble layer formed by the water-soluble composition can also have better flatness.

[0082] Other surfactants (C')

[0083] In one embodiment, the water-soluble composition may further selectively include other surfactants (C'), which may include common non-ionic surfactants, such as polyoxyethylene alcohol, tristyrylphenol, nonyl or octylphenol, esters, diesters, sorbitol esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene / propylene block copolymers, fatty acid sorbitan esters, polyoxyethylene fatty acid sorbitan esters, ethoxylated siloxanes, acetylene glycols and / or polyglucosides, etc., or may be fluorine-based surfactants other than the aforementioned surfactants (C).

[0084] For example, the polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether; the polyoxyethylene alkyl aryl ethers include polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; the fatty acid sorbitan esters include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate and sorbitan tristearate; the polyoxyethylene fatty acid sorbitan esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate.

[0085] Solvent (D)

[0086] In one embodiment, the solvent (D) includes water (D1), examples of which include but are not limited to pure water or deionized water, preferably deionized water.

[0087] Based on 100 parts by weight of the total amount of the solvent (D), the amount of the water (D1) used is 40 parts by weight to 100 parts by weight.

[0088] In one embodiment, the solvent (D) may further selectively include an organic solvent (D2), wherein the organic solvent (D2) is selected from the group consisting of aliphatic monohydric alcohols having 1 to 7 carbon atoms and aliphatic dihydric alcohols having 1 to 7 carbon atoms.

[0089] The aliphatic monohydric alcohol having 1 to 7 carbon atoms may be, for example, ethanol, propanol, butanol, heptanol, allyl alcohol, crotyl alcohol (2-butene-1-ol) and / or cyclohexanol. The aliphatic dihydric alcohol having 1 to 7 carbon atoms may be, for example, 1,2-ethylene glycol (ethylene glycol), 1,2-propylene glycol (propylene glycol), 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol and / or 1,6-hexanediol.

[0090] Based on 100 parts by weight of the total usage of the solvent (D), the usage of the organic solvent (D2) may be 1 to 60 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight.

[0091] If the water-soluble composition contains the organic solvent (D2), the formed water-soluble layer may have better release properties; if the usage amount of the organic solvent (D2) falls within the above range, the formed water-soluble layer may have better release properties.

[0092] Bactericide (E) and dissolution aid (F)

[0093] In one embodiment, the water-soluble composition may further optionally include a bactericide (E) and / or a dissolution aid (F).

[0094] The bactericide (E) can be used to prevent the growth of bacteria or fungi in the water-soluble composition, and an example thereof may be Kathon (manufactured by Rohm and Haas).

[0095] Based on 100 parts by weight of the total usage of the solvent (D), the usage of the fungicide (E) may be 0.001 parts by weight to 30 parts by weight, preferably 0.005 parts by weight to 20 parts by weight, and more preferably 0.01 parts by weight to 3 parts by weight.

[0096] The dissolution aid (F) is used to increase the solubility of the aryl nitrone compound soluble in alkaline aqueous solution in water, and can be various organic bases, examples of which include tris(hydroxymethyl)aminomethane, pyridine, triethylamine, tetramethylammonium hydroxide solution, tetraethylammonium hydroxide solution, 2,2',2"-nitrotriethanol and / or triethylenediamine (DABCO), etc.

[0097] Based on 100 parts by weight of the total usage of the solvent (D), the usage of the dissolution aid (F) may be 0.1 parts by weight to 30 parts by weight, preferably 0.5 parts by weight to 20 parts by weight, and more preferably 1 parts by weight to 10 parts by weight.

[0098] Method for preparing water-soluble composition

[0099] The preparation method of the water-soluble composition disclosed herein is not particularly limited. It only requires that the above components are uniformly dissolved in the solvent (D). The water-soluble composition can be prepared by any common method.

[0100] Application of water-soluble compositions

[0101] The present invention further provides a water-soluble layer formed by the water-soluble composition.

[0102] The present invention further provides a use of a water-soluble layer, which is used to enhance the contrast when forming a pattern using yellow light lithography technology. That is, the water-soluble layer can be used as a contrast enhancement layer.

[0103] The present invention further provides a method for manufacturing a semiconductor device, comprising:

[0104] Providing a substrate and a photoresist layer, wherein the photoresist layer is disposed on the substrate;

[0105] forming a water-soluble layer on the photoresist layer with the water-soluble composition;

[0106] exposing the water-soluble layer and the photoresist layer; and

[0107] The water-soluble layer and the exposed portion of the photoresist layer are removed to form a photoresist pattern.

[0108] The photoresist layer may be directly or indirectly disposed on the substrate, and the water-soluble layer may be directly or indirectly disposed on the photoresist layer. The water-soluble layer may be formed in any manner, for example, the water-soluble composition may be coated (e.g., spin-coated) on the photoresist layer, and may be dried (e.g., air-dried and / or heated) to form the water-soluble layer. When performing exposure, a light source corresponding to the photoresist layer (e.g., ultraviolet light of a specific wavelength) may be used to irradiate the water-soluble layer and the photoresist layer through a photomask of a specific pattern, so that the exposed portion of the water-soluble layer fades, and the light can reach the photoresist layer through its faded portion, thereby achieving an effect of enhancing contrast.

[0109] After exposure, the water-soluble layer can be washed and removed with a washing liquid (e.g., water), and the exposed portion of the photoresist layer can be removed with a developer (e.g., a TMAH developer, a KOH developer). In one embodiment, if the water-soluble layer is soluble in the developer, the developer can also be used to remove the water-soluble layer and the exposed portion of the photoresist layer at the same time. In one embodiment, the above-mentioned manufacturing method is used for the formation of positive photoresist. In addition, since the water-soluble layer has the effect of improving contrast, it is particularly beneficial to the pattern formation of lithography (reduction projection method).

[0110] Specifically, in the method for manufacturing the semiconductor device, the steps of forming a water-soluble layer with the water-soluble composition of the present invention and forming a photoresist pattern can be as follows: Figure 1 Or as shown in 2.

[0111] Figure 1 The water-soluble layer is directly formed on the photoresist layer. First, a photoresist layer 2 is formed on a substrate 1 such as a silicon chip by spin coating or the like, and then the water-soluble composition of the present invention is coated on the photoresist layer 2 by spin coating or the like to form a water-soluble layer 3. Then, by a reduced projection method, ultraviolet rays 4 of a specific wavelength are used to form a predetermined pattern shape (e.g. Figure 1The water-soluble layer 3 (part A) is exposed to light to discolor the part A of the water-soluble layer 3. At the same time, the part A of the photoresist layer 2 is exposed to light, and the water-soluble layer 3 is removed with water. The photoresist layer 2 is developed with a developer to form a photoresist pattern 5.

[0112] Figure 2 In the example, an intermediate layer 6 made of a neutral substance (e.g., polyvinyl alcohol) is provided between the photoresist layer and the water-soluble layer to separate the photoresist layer and the water-soluble layer. At this time, since the water-soluble composition of the present invention is soluble in water, the water-soluble layer 3 and the intermediate layer 6 can be directly washed with water without generating scum.

[0113] Example

[0114] The components and formulations of the water-soluble compositions of Examples 1 to 14 and Comparative Examples 1 to 6 are shown in Tables 1-1, 1-2 and 2 below. The water-soluble compositions can be prepared by uniformly dissolving the components in a solvent (D).

[0115] Table 1-1:

[0116]

[0117] Table 1-2:

[0118] Table 2:

[0119] In Table 1-1, Table 1-2 and Table 2: A-1

[0120]

[0121] A-2

[0122]

[0123] A-3

[0124]

[0125] A-4

[0126]

[0127] B-1Luviskol TM VA64 (manufactured by BASF)

[0128] B-2 Pullan PI20 (manufactured by Hayashibara Company Limited) B-3 Polyvinyl alcohol with an average molecular weight of 1000 and a saponification degree of 88% C-1 Ftergent KB-F2M

[0129] C-2Ftergent KB-FaM C-3Ftergent KB-L85

[0130] C-4Ftergent FTX-213F

[0131] C-5Ftergent FTX-218G

[0132] C-6Ftergent FTX-220D

[0133] C-7Ftergent FTX-212M

[0134] C'-1 C'-2 C'-3Surfynol TM 465

[0135] C'-4Fluorad FC-430 (manufactured by Sumitomo 3M)

[0136] C'-5CF 3 -(CF 2 ) 8 -COO - (CH 3 ) 4 N + H

[0137] D1-1 Deionized water

[0138] D1-2 Pure water

[0139] D2-1 tert-Butanol

[0140] D2-2 Isopropyl alcohol

[0141] D2-3 Ethylene glycol

[0142] D2-4 Butanediol

[0143] F-1 Tris(hydroxymethyl)aminomethane

[0144] F-2 Triethylenediamine (DABCO)

[0145] Evaluation method

[0146] Flatness

[0147] First, a positive photoresist was coated on a 12-inch silicon wafer substrate using a spin coater to form a photoresist layer with a film thickness of 4um. Thereafter, the positive photoresist layer was pre-baked at 100°C for 5 minutes in air using a hot plate. Next, the water-soluble composition of the embodiment and the comparative example was coated on the pre-baked positive photoresist layer using a 1500rpm spin coater to form a water-soluble layer with a film thickness of 0.5um. Thereafter, the maximum step difference of the water-soluble layer was measured using a stylus-type film thickness meter as an indicator of flatness. The evaluation criteria are as follows:

[0148] ◎: Maximum step difference ≦20nm

[0149] ○: 20nm<maximum step difference≦30nm

[0150] △: 30nm<maximum step difference≦40nm

[0151] X: Maximum step difference>40nm

[0152] Release

[0153] The film thickness of the pre-baked positive photoresist layer obtained in the above flatness is measured by an optical film thickness meter (Hongming Technology, MFS-630-F), and the value of La can be obtained. Then, the water-soluble composition of the embodiment and the comparative example is coated on the above-mentioned pre-baked positive photoresist layer using a rotary coater to form a water-soluble layer including a positive photoresist layer and a film thickness of 0.5um. Then, it is heated at 105°C for 3 minutes. Then, an alkaline developer (2.38% TMAH developer) is added to the water-soluble layer and placed at 23°C for 15 seconds. The development process is repeated 5 times, and the film thickness of the developed coating (that is, only the positive photoresist layer and the residual water-soluble layer) is measured to obtain L. b According to L b / L a The percentage value of is used as the index of release property. The evaluation criteria are as follows.

[0154] ◎:98≦L b / L a ≦102%

[0155] ○:95≦L b / L a <98%, or 102<L b / L a ≦105%

[0156] X:L b / L a <95%, or 105<L b / L a

[0157] The above embodiments are only for explaining the principle and effect of the present invention, but not for limiting the present invention. The modification and changes made by the persons skilled in the art to the above embodiments still do not violate the spirit of the present invention. The scope of rights of the present invention shall be as listed in the scope of the patent application described later.

Claims

1. A water-soluble composition comprising: Photofading compound A; Resin B; A surfactant C containing an alkenyl group containing a perfluoroalkyl substituent; and Solvent D.

2. The water-soluble composition of claim 1, wherein in the surfactant C, the alkenyl group containing a perfluoroalkyl substituent is selected from the group consisting of the following formula (1) and formula (2): In formula (1) and formula (2), * indicates a bonding site.

3. The water-soluble composition of claim 1, wherein the surfactant C is selected from the group consisting of the following formulas (3) to (5): In formulae (3) to (5), q, r, and p are each independently an integer greater than 1, R is a monovalent organic group, and Rf each independently represents an alkenyl group containing a perfluoroalkyl substituent. 4 . The water-soluble composition of claim 1 , wherein the amount of the surfactant C is 0.01 to 1 parts by weight based on 100 parts by weight of the total amount of the solvent D. The water-soluble composition of claim 1 , wherein the solvent D comprises water D1.

6. The water-soluble composition of claim 5, wherein the solvent D further comprises an organic solvent D2, and the organic solvent D2 is selected from the group consisting of aliphatic monohydric alcohols having 1 to 7 carbon atoms and aliphatic dihydric alcohols having 1 to 7 carbon atoms. 7 . The water-soluble composition according to claim 6 , wherein the amount of the organic solvent D2 is 1 to 60 parts by weight based on 100 parts by weight of the total amount of the solvent D.

8. The water-soluble composition of claim 1, wherein the photofading compound A comprises a nitrone compound.

9. A water-soluble layer formed from the water-soluble composition according to any one of claims 1 to 8.

10. Use of the water-soluble layer as claimed in claim 9 for improving the contrast of patterns formed by yellow light lithography.

11. A method for manufacturing a semiconductor device, comprising: Providing a substrate and a photoresist layer, wherein the photoresist layer is disposed on the substrate; Forming a water-soluble layer on the photoresist layer using the water-soluble composition according to any one of claims 1 to 8; exposing the water-soluble layer and the photoresist layer; and The water-soluble layer and the exposed portion of the photoresist layer are removed to form a photoresist pattern.

Images