TWI238291B - Polymer mixture for photoresist and photoresist composition containing the same - Google Patents

Abstract

A polymer mixture for a photoresist composition, and a photoresist composition containing the polymer mixture. The polymer mixture includes a polymer that has two or more different monomers and an acid-labile di-alkylmalonate group bound to the backbone of the polymer; a polymer that has a monomer of (meth)acrylate derivative and one or more other monomers; or a polymer that has a monomer of alkoxystyrene and one or more other monomers. The polymer mixtures are suitable for forming photoresist compositions that generate a pattern having an excellent profile, due to the high contrast and high thermal decomposition temperature of the photoresist composition. The photoresist composition of the present invention further include a photosensitive acid generator.

Description

1238291 A7 _____B7_ V. Description of the Invention (() Field of Invention The present invention relates to a material for forming a semiconductor element, and particularly to a polymer mixture of a chemically amplified photoresist used in lithography, and related to A photoresist composition containing the polymer mixture. Description of related technologies. Current semiconductor wafers are highly integrated and require complex manufacturing processes. For example, it is sufficient to form fine patterns in the range of 0.25 microns or less The lithography process is necessary. This fine pattern must be formed using deep ultraviolet (UV) rays of 248 micrometers, which have a g-line (436 micrometers) and I-line (365 micrometers) than the conventional Rays have shorter wavelengths. However, when deep-UV rays are used, fewer protons are transferred when a dose equal to the energy of a conventional light source is used for radiation. Therefore, when deep-UV rays are used, in order to transfer To overcome this problem, the same number of protons and the same results achieved with conventional lithography are required. Using a novel material called "chemically amplified photoresist", because of its improved photosensitivity, even deep-UV radiation is highly sensitive to protons when it is irradiated with the same dose used by conventional light sources. Generally speaking, This chemically amplified photoresist includes an acid-labile group that is easily hydrolyzed by an acidic catalyst, so it functions as a dissolution inhibitor. The amplified photoresist also includes a photosensitive acid generator for exposure to light Proton Η + (ie acid) is generated. When a chemically amplified photoresist is exposed to light, the 'acid is generated by a photosensitive acid generator. It is bonded to the polymer main __ 4 i Paper size applies to China) A4 Specifications (210X 297 mm) (Please read the precautions on the back before filling out this page), printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1238291 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, A7 B7 V. Description of the invention (≫) The chain dissolution inhibitor is then hydrolyzed by a catalytic reaction that generates an acid, thereby changing the polarity (e.g., solubility) of the polymer. Acid dissolution of polymers by acid diffusion can produce patterns with higher transparency. Therefore, contrast (that is, an index indicating the difference in solubility of a chemically amplified photoresist before and after exposure to light) is determined by bonding an acid-labile group to the polymer backbone. U.S. Patent No. 4,491,628 discloses a polymer containing a chemically amplified photoresist and the use of tertiary-butoxycarbonyl (t-BOC) as an acid labile group. However, the thermal decomposition temperature [Td] of this chemically amplified photoresist is lower than its glass transition temperature [Tg]. Therefore, if the photoresist is baked at a temperature higher than the glass transition temperature to evaporate unnecessary organic solvents and harden the photoresist film before exposure to light, the photoresist will decompose. On the other hand, if the pre-baking temperature is low enough to avoid thermal decomposition, pollutants in the air will be absorbed into the surface of the exposed photoresist film, thus avoiding the catalytic reaction using acid. This will cause the pattern to have a secondary distribution pattern, such as a T-top distribution pattern. The distribution pattern of the T-top is caused by the pollutants in the air being absorbed into the surface of the photoresist film, which will neutralize the acid generated by the photoresist when exposed to light. As a result, a part of the exposed photoresist cannot be acid-decomposed and thus remains insoluble. The photoresist-insoluble portion is not developed by the developer and causes a T-tip distribution type. SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, an object of the present invention is to provide a polymer mixture for chemically amplified photoresist, which has greater contrast and excellent thermal properties. __ 5 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) (Please read the notes on the back before filling out this page) 1238291 Α7 Β7 5. Description of the invention (h) Another object of the present invention is to provide A photoresist composition having excellent thermal properties and high contrast and thus forming a high-resolution pattern. In order to achieve the first object, the present invention provides a polymer mixture for a chemically amplified photoresist, which includes a polymer (A) which is polymerized from two or more different monomers and is acid-labile. Di-alkylmalonate group is bonded to the polymer main chain; and polymer (B) is formed by polymerizing a (meth) acrylate derivative monomer with one or more other monomers Or polymer (B) is formed by polymerizing an alkoxystyrene monomer with one or more other monomers. Preferably, the polymers (A) and (B) are mixed in a weight ratio ranging from about 0.1: 0.9 to 0.5: 0.5. In a preferred embodiment, the di-alkylmalonate group is a di-tertiary butylmalonate group or a di-tetrahydropyranylmalonate group. The photoresist composition includes the polymer mixture and a photosensitive acid generator in a weight range of about 1 to 15 weight percent based on the weight of the polymer mixture. The preferred 'photoresist composition further comprises an organic base, such as an amine derivative, by weight from about 0.01 to 2.0 weight percent based on the weight of the polymer mixture. The polymer mixture of the present invention has a di-alkylmalonate group as a dissolution inhibitor and is bonded to the polymer backbone. The dissolution inhibitor was very bulky before exposure to light. However, 'exposure can cause the photosensitive acid generator to form an acid, which will hydrolyze the dissolution inhibitor and thereby produce malonic acid and reduce the volume of the dissolution inhibitor. Acid hydrolysis significantly increases the solubility of the photoresist, and results in far better contrast than those obtained using conventional photoresist compositions. Importantly, 6 (Please read the notes on the back before filling out this page) -5-¾ This paper is printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs, and the paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) 1238291 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (groan) The thermal decomposition temperature Td of the photoresist composition of the present invention is higher than the glass transition temperature Tg, so pre-baking above the glass transition temperature can be used. The temperature is pre-baked before exposure to harden the photoresist film. Such high temperature pre-baking can avoid the defect pattern distribution type caused by the damage of the contamination, such as T-tip. Brief description of the drawings The drawings are used to illustrate specific embodiments of the present invention, in which: FIG. 1 is a graph showing the results of thermogravimetric analysis of a copolymer composed of a polymer mixture used in the photoresist of the present invention; And FIG. 2 is a graph showing a comparative curve of the photoresist film. DESCRIPTION OF THE PREFERRED EMBODIMENTS The polymer mixture used for the chemically amplified photoresist and the photoresist composition containing the polymer mixture will be described in detail below with reference to FIGS. 1 and 2. A method for preparing the photoresist composition and a lithography process using the photoresist composition will also be described. Polymer mixture used in chemical ionizing agent of the present invention The polymer mixture used in the chemical amplification photoresist of the present invention is a mixture including polymer A which contains an acid-labile di-alkylmalonate The group is bonded to the polymer backbone and is formed by polymerizing two or more monomers. In addition to polymer A, the polymer mixture includes a polymer B, which is a polymer of a (meth) acrylate derivative monomer and one or more other monomers; or a polymer C, which It is made by polymerizing an alkoxystyrene monomer with one or more other monomers. In a preferred embodiment, the di-alkylmalonate group is a di-tertiary butylmalonate group or a di-tetrahydropyranylmalonate group. Polymer A vs. Polymer B 7 This paper is sized to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page) Order 1238291 A7 B7 V. Description of Invention (f) or The mixing ratio of the polymer C is preferably in a range from about 0.1: 0.9 to 0.5: 0.5 by weight. In the first embodiment of the present invention, the polymer mixture used in the chemical amplification photoresist is a mixture of a copolymer represented by the following chemical formula (CF1) and a copolymer represented by the chemical formula (CF2). (Please read the notes on the back before filling this page) R2

R 丨 CizC COzR 丨 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (CD (CF2) In the chemical formulas (CF1) and (CF2), R 1 and R 5 are tertiary butyl or tetrahydropyranyl; R 2 R 3 and R 4 are hydrogen or methyl, respectively; and m, η, X, and y are integers. The ratio m / (m + n) is 0.01 to about 0.5, and the ratio y / (x + y) is From about 0.01 to 0.5. Preferably, the mixing ratio of the polymers represented by the chemical formulae (CF1) and (CF2) is in a range from about 0.1: 9 to about 0.5: 0.5 weight, and the weight average molecular weight of each polymer The range is from about 5,000 to about 100,000. In a preferred embodiment, R 1 in the chemical formula (CF1) is tertiary butyl, R 2 and R 3 are hydrogen, and R 4 in the chemical formula (CF2) Is hydrogen, and R 5 is tertiary butyl or tetrahydropyranyl. In a preferred embodiment, R 1 8 in the chemical formula (CF1) applies to Chinese paper standard (CNS) A4 specifications (2丨 0'〆297 mm) 1238291 A7 B7 V. Description of the invention (t) is tertiary butyl, R 2 and R 3 are hydrogen, and R 4 in the chemical formula (CF2) is methyl, and R 5 is three Butyl or tetrahydropyranyl. The polymer mixture of the second embodiment of the invention is a mixture of a copolymer represented by the chemical formula (CF1) and a copolymer represented by the chemical formula (CF3). CH2 I CH / \

CH: —— CH

COzRt CH; CH \ -rCH2—CH ^ 7

OH 〇R? (CF1) (CF3) Printed in the chemical formulas (CF1) and (CF3) by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy, R1 is tertiary butyl or tetrahydropyranyl, R2 and R3 Is hydrogen or methyl, R 7 is alkoxy-1-ethyl, tetrahydropyranyl, tertiary butyl or tertiary butoxycarbonyl, and m, η, X and y are integers. The ratio of m / (m + η) is from 0.01 to about 0.5, and the ratio of y / (x + y) is from about 0.01 to about 0.5. Preferably, the mixing ratio of the polymers represented by the chemical formulae (CF1) and (CF3) is in a range from about 0.1: 9 to about 0.5: 0.5 by weight. The weight average molecular weight of each polymer ranges from about 5,000 to about 100,000. Preferably, R1 in chemical formula (1) is tertiary butyl, R2 and R3 are hydrogen, and R7 in chemical formula (3) is alkoxy-1-ethyl, tetrahydropyran Radical, tert-butyl or tert-butoxycarbonyl. Photoresist composition The size of this paper applies Chinese National Standard (CNS) A4 specifications (210 > < 297 mm) 1238291 A7 B7 V. Description of the invention (1) The photoresist composition of the present invention includes one of the above polymer mixtures , And the weight range is from about 1 to 15 weight percent of the photosensitive acid generator based on the weight of the polymer mixture. Preferably, a material having high thermal stability is used as the photosensitive acid generator. Accordingly, triarylsulfonium salts, diaryliodon salts, or sulfonates can be used. In another preferred embodiment, the photoresist composition of the present invention further contains an organic base in an amount of from about 0.01 to 2.0% by weight based on the weight of the polymer mixture. The organic base may be triethylamine, triisobutylamine, diethanolamine or triethanolamine. The organic base can avoid the critical size reduction of the pattern caused by the diffusion of the acid from the exposed part to the unexposed part after light exposure. The photoresist composition of the present invention has a dissolution inhibitor, which includes a polymer (A) having an acid-labile di-alkylmalonate group bonded to the polymer A main chain, and the polymer A is used as a dissolution inhibitor. The di-alkyl malonate is hydrolyzed to a malonic acid by a photoacid generator using an acid generated upon exposure to light. This acid hydrolysis causes the photoresist composition to be exposed to light, and the solubility (ie, contrast) is significantly increased by reducing the size of the dissolution inhibitor. That is, because the di-arylmalonate group and the photosensitive acid generator are both thermally stable, the photoresist composition of the present invention can be thermally stable even at a temperature higher than about 130 ° Ct glass transition temperature. Has important excellence. Preparation of polymerized ^^ ······························································································································································································ _________10_, This paper size applies to China National Standards (CNS) M specifications (Z10 > < 297 male thin) (Please read the precautions on the back before filling this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 1238291 A7 B7 5. Description of the invention (Sr) As shown in the following reaction formula (RF1), when the di-alkylmalonate (I) is dissolved to an organic solvent in which sodium hydride has been dissolved, such as tetrahydrofuran [THF], Chloromethylstyrene was added to the solution. Di-alkylpropanefluorenylstyrene (Π) is obtained by a substitution reaction.

CH2 = CH

〇II C

〇II C

CH2 two CH R10

CH2CI CH; ORi

NoH ΎηΓ ⑴ CH2 I CH 00 (RF1) In the general formula (RF1), R 1 is a tertiary butyl group or a tetrahydropyranyl group. 1-2. Di-alkylpropionylmethyl styrene (II) is polymerized with acetylene styrene or ethoxylated styrene derivative (III) monomer to prepare copolymer (IV) copolymer (IV) is obtained through a reaction represented by the following reaction formula (RF2). (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

CH2 = CH

R2 I CH2 = C

AI9N

-i CH2 —CH-^-(CH2 —C7T CH2

TOLUENE CHz R ». /, CChR, 0.0 CHJ (III) (RF2) CH / \ R.0: C COjR. (Tv) This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 1238291 A7 B7

Q 5. Description of the invention (In the reaction formula (RF2), R 1 is tertiary butyl or tetrahydropyranyl, R 2 and R 3 are hydrogen or methyl, and m and η are integers. M / ( The ratio of m + n) is from about 0.01 to about 0.5. After dissolving di-alkylpropionylmethylstyrene (Π) and ethoxylated styrene or ethoxylated styrene derivative (ΙΠ) in After an organic solvent, such as toluene, a polymerization initiator, such as azobisisobutyronitrile (AIBN), is added and the copolymer (IV) is obtained through polymerization. 1-3. Deacetylation of the copolymer (IV) As shown in the following reaction formula (RF3), the copolymer (IV) is dissolved in a solvent, and deacetylation is performed using an organic base (which is ammonium hydroxide or hydrazine) to form a weight average molecular weight range Copolymer (V) from about 5,000 to about 100,000 and expressed by chemical formula (CF1). (Please read the precautions on the back before filling this page) Order R2 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

(IV)

EASE

METHANOL (RF3) 12 This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1238291 A7 B7 V. Description of the invention (丨 D)

R > 〇2C CO2R »(V) 2. Preparation method of copolymer represented by chemical formula (2) 2.1 Copolymerized by styrene (VI) and (meth) acrylic acid ester monomer derived from acetonitrile (ΥΙΠ) preparation (Please read the precautions on the back before

Under the M-style heartbreaker

4 F R should be counter-indicated Η c 〇 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

CIC (V

3 H ^ (\ R — Η cr

F4 (R

N AIRI E N E u L To

〇 z 5 c——cI 0 — R

V 3 1 1 This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1238291 A7 B7 V. Description of the invention (//) In the reaction formula (RF4), R 5 is tertiary butyl or tetrahydro Pyranyl, R 4 is hydrogen or methyl, and X and y are integers. The ratio y / (x + y) is from about 0.001 to about 0.5. After dissolving ethoxylated styrene (VI) and (meth) acrylate derivative (VH) in an organic solvent, such as toluene, a polymerization initiator such as AIBN is added and a copolymer is obtained through polymerization (得到 ΠΟ 2-2. Deacetylation of the copolymer (M) As shown in the following reaction formula (RF5), the copolymer (Xinjiang) is dissolved in methanol, and deacetylation is performed using a base to form Copolymer (K) having an average molecular weight ranging from about 5,000 to about 100,000 and represented by chemical formula (CF2). * CH2 —CHCH2 —C- 〇I c = 〇I CH3 c =: oI 〇I Rs BASE;

METHANOL (RF5) (VIII) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

OH (IX) C = 〇I 〇I Ps5 14 This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 1238291 A7 B7

V. Description of the invention (/ tJ Photo MlLfflA preparation of square die, and the use of the composition according to the first specific embodiment of the present invention, has acid-labile di-hospray malonate group bonding Polymer (A) (such as a copolymer of chemical formula (CF1)) polymerized with two or more monomers to the polymer main chain and polymerized with a monomer containing a (meth) acrylate derivative (B) (such as a copolymer of chemical formula (CF2)), wherein the weight ratio of A to B ranges from about 0.1: 0.9 to about 0.5: 0.5 weight, and then dissolved in a suitable solvent. Then The weight range of the photosensitive acid generator from about 1 to 15 weight percent based on the weight of the polymer mixture is added to the solvent containing the polymer mixture to obtain a chemically amplified photoresist composition. In a preferred embodiment The photo-sensitive acid generator is a triarylsulfonium salt, a diaryl iodonium salt or a sulfonate which is thermally stable at 15 ° C. It is printed in a preferred embodiment by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy For example, weight range is based on polymer The organic weight of the mixture from about 0.01 to 2.0 weight percent is further added to the solvent / polymer / photosensitive acid generator mixture to form a photoresist composition. In a preferred embodiment, the organic base is three Ethylamine, triisobutylamine, diethanolamine or triethanolamine. According to a second embodiment of the present invention, an acid-labile di-alkylmalonate group is suspended from the polymer backbone and is attached to A polymer (A) ′ formed by polymerizing two or more monomers and represented by the chemical formula (CF1) is mixed with a polymer (B) containing an alkoxystyrene monomer and represented by the chemical formula (CF2), wherein The weight ratio of A to B ranges from about 0.1: 0.9 to 0.5: 0.5 weight, and then dissolved in a suitable solvent. Then, the light _________15____ This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1238291 A7 ____ B7 V. Description of the invention (I7 /) The sensitive acid generator and organic base are mixed with the solution according to the same method as in the first embodiment to obtain a photoresist composition. According to the above Method of preparation The chemically amplified photoresist composition is applied to a general lithography process. In particular, this chemically amplified photoresist composition is suitable for forming fine patterns with a design rule of 0.25 microns or less, in which deep Ultraviolet rays are used as a light source to expose the photoresist. First, the above photoresist composition is coated on a substrate having a layer to be patterned to form a photoresist film having a predetermined thickness. Then, the photoresist film Pre-bake before exposure. The acid-labile di-alkylmalonate-containing dissolution inhibitor and photoacid generator used in the photoresist composition of the present invention are both thermally stable. The photoresist composition has a relatively high thermal decomposition temperature Td of about 170 ° C or higher, which is higher than a glass transition temperature Tg of about 130 ° C. Because Td is higher than Tg, it is possible to use a high temperature pre-baked photoresist to harden it before exposure to light without causing the photoresist to decompose. Therefore, when the photoresist composition of the present invention is used, damage to the photoresist due to pollutants in the air can be effectively avoided. After pre-baking, the photoresist film is exposed under a deep ultraviolet light source using a mask having a preset pattern. The acid is generated in the photoresist film by a photosensitive acid generator on exposure, and the di-alkylmalonate group bonded to the polymer is acid-converted to propyl due to the generated acid-catalyzed reaction. Diacid. Such acid hydrolysis causes a significant difference between the polarity of the exposed portion of the photoresist film and the polarity of the unexposed portion, and thus produces high contrast. After the exposure, the photoresist film is subjected to a short post-exposure heat treatment before development. This kind of post-baking can stimulate acid hydrolysis, so it can be left in the exposed part ___16 _ This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before you ^ (^ This page)

Printed on line 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1238291 A7 V. Description of the invention 10) The di-alkylmalonate is completely converted to malonic acid and the contrast is increased. Then, the photoresist is developed using an appropriate developer, and the choice of the developer is based on whether the photoresist film is a positive or negative photoresist. Therefore, this standard process is performed to complete the formation of the photoresist pattern. A high-resolution photoresist pattern having a good distribution type can be formed by using the photoresist composition of the present invention. In the following, the polymer mixture, the photoresist composition containing the polymer mixture, and the lithography using the photoresist composition of the present invention will be described using the following non-limiting examples. Example 1 Preparation of Di-tertiary-butyl-propanedimethanone 7V benzene (DBMST) monomer 4.8 g (0.12 mole) of sodium hydride was dissolved in 250 ml of tetrahydrofuran [THF]. M grams (0.11 mole) of the di-tert-butylmalonate was slowly added dropwise to the solution and reacted at room temperature for about 1 hour. Then, 0.1 mol (16 g) of chloromethylstyrene was slowly added dropwise to the mixture at 0 ° C. The mixture was then warmed to room temperature and reacted for 12 hours to complete the substitution reaction. The reaction product was dissolved in water, neutralized with hydrochloric acid, and extracted with diethyl ether. Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs After using magnesium sulfate to dry the reactants, the reaction product DBMST monomer was separated by column chromatography (yield 65%). Nuclear magnetic resonance (NMR) and Fourier transform infrared radiation (FT-IR) spectral analysis was performed on the obtained DBMST monomer, and the results are shown below. lH-NMR (CDC13) (ppm):

1.4 (s, 18H), 3.1 (d, 2H), 3.5 (t, 1H), 5.2 (dd'lH), 5.7 (dd, lH), 6.6 (dd, lH), 7.2 ( m, 4H _ 17 This paper size applies Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 1238291 Λ7 B7 V. Description of the invention (/ Γ) FT-IR (NaCl) (cm'1): 2978 (CH , Tertiary butyl), 1777 (C = 0), 1369, 1140, 847 Example 2 Copolymer (DBMST-Ethyloxyphenylphenazine (AST) L. Turtle 3 g (9 mmol) DBMST monomer and 4.5 grams (27 millimoles) of AST were dissolved in 35 ml of toluene. Then, 0.35 grams of aibn was added as a polymerization initiator, and nitrogen was used for 1 hour. Polymerization Acted at 70 ° C for about 24 hours. After polymerization, the reaction product was precipitated in excess methanol (about 10 times methanol to a portion of the reaction solution), and the precipitate was maintained in a vacuum oven at 5 (rc). Dry for about 24 hours to isolate the reaction product (yield 70%). The obtained reaction product is a copolymer containing DBMST and AST monomers, which has a weight average molecular weight of 1U57, and a polydispersity of 1.6. The copolymer The results of FT-IR analysis are as follows: Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs ¾ FT-IR (KBr) (cm-1) ·· 2979 (CH, tertiary butyl), 1767 (C = 0, ethenyl) , 1727 (C = 0, propylene difluorenyl), 1369, 1216 Example 1 · Deacetylated copolymer (DBMST-hydroxy certain styrene (HST)) 10 g of the copolymer obtained from Example 2 Reflux the mixture in a mixed solution containing 10 ml of ammonium hydroxide (28%) and 50 ml of methanol for about 4 hours. Appropriate for this country (CNS) A4 (210X ^ 7 mm) Printed by Consumer Cooperative A7 B7 V. Description of the invention ([(^) Copolymer deacetylation. The reaction product slowly precipitates in excess water. After dissolving the precipitate in tetrahydrofuran THF, use excess n-hexane to precipitate The precipitate was dried in a vacuum oven maintained at 50 ° C. for about 24 hours to isolate the reaction product (yield 90%). The obtained reaction product was a copolymer containing DBMST and HST monomers and the molar ratio was about 25 ·· 75. The weight-average molecular weight of the copolymer is 9,438 'Polydispersity is 1.6, and the light transmission resistance to ultraviolet rays It was 74% / micron. The results of FT-IR analysis of the copolymer are as follows. FT-IR (KBr) (cm'1): 3440 (〇-Η), 2980 (CH, tertiary butyl), 1728 (C = 0), 1513, 1369, 1145 Copolymers having different polymerization ratios for each monomer were obtained under the same conditions as above. Then, the weight-average molecular weight (Mw), polydispersity, and UV-resistance (% / micron) of each copolymer were measured. To form a photoresist composition, 3.0 weight percent of triphenylmethanetrifluoromethanesulfonate (TPSOTf) based on the weight of the copolymer was added to the copolymer as a photosensitive acid generator. The optimum exposure energy required to form the photoresist composition when forming a pattern with a 0.3 micron line and pitch array was measured. The results are tabulated in Table 1. 19 (Please read the precautions on the back before filling in this page) The size of the paper used for the booklet is subject to the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) ------ 1238291 A7 B7 grams, invention description ((y ) Table 1 Optimized exposure energy for photoresist-resistant polymers DBMST- HST Weight average molecular weight polydispersity transmittance (% / micron) Optimized exposure energy (m) / cm2) 1 1 35: 65 10487 1.67 72 76 to 2 30:70 9954 1.75 73 55 to 3 28:72 8675 1.64 71 34 to 4 27:73 9627 1.61 73 35 to 5 26:74 10539 1.65 74 30 to 6 25:75 9438 1.60 74 30 1 7 20:80 9536 1.65 73 18% ΜΆΛΜ (AST-tertiary butyl acrylate (BA)) Preparation 7.8 g (60 mmol) of BA (tertiary butyl acrylate) and 20 g (12 () mmol) of ethoxylated styrene AST was dissolved in 140 ml of toluene. Then, the reaction product was separated by the same procedure as in Example 2, except that 1.48 g of AIBN was added as Polymerization initiator 〇- The reaction product printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs contains ΒA and AST The copolymer 'has a weight average molecular weight of 12,017, and a polydispersity of I · 83. The FT-IR analysis results of the copolymer are as follows. FT-IR (KBr) (cm · 1): 2978 (CH, 3 Grade butyl), 1767 (C = 0, ethylfluorenyl) '1727 (C = 0), 1506, 1369 (CH, tertiary butyl), 1217 (C-〇) 眚 Example 5 _____20_ ____ Paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) A7 1238291 V. Description of invention (M) Deacetylation (HST_BA). Disk 1 () $ 彳 # Borrowed from the copolymer of Example 4 From the same method as in Example 3. The obtained reaction product was a copolymer containing BA and hydroxystyrene HST_ ||. The weight average molecular weight of the copolymer was 11,438, the polydispersity was 1.82 ', and it was resistant to ultraviolet rays The light transmittance is 74% / micron. The results of FT-IR analysis of the cough polymer are as follows. FT-IR (KBr) (cm · 1): 3397 (〇-11), 2978 ((> 11, level 3) Butyl), 1699 (0 = 0), 1513, 1369 (OH, tertiary butyl), 1231 (C-0) Xuan Example i Preparation of ethoxystyrene-HST) In the dissolution of 2 grams of poly-hydroxy Styrene (poly (HST)) after 60 ml of THF, 3.6 Of ethyl vinyl ether was added to the solution. A sufficient amount of p-toluenesulfonic acid (P-TSA) was added to the mixture as a catalyst, and reacted at room temperature for 12 hours. After 12 hours, the reaction product was slowly added dropwise to the water at a ratio of 5 parts of water to 1 part of the reaction product, and neutralized with potassium carbonate. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs After dissolving the precipitate in THF, it slowly precipitates out of excess n-hexane. The precipitate was then dried in a vacuum oven maintained at 50 ° C to isolate the reaction product (85% yield). The obtained reaction product was a poly (ethoxy-1-ethoxystyrene-HST) copolymer. The copolymer had a weight-average molecular weight of 12,285, a polydispersity of 1.67, and a transmittance against ultraviolet rays of 73% / micron. Example 7 --- ^ _____ 21__ This paper size is applicable (CNS) A4 specification (210X2 ^ domain) " ~ 1238291 A7 _______B7_ V. Description of the invention (丨 ° |) — Make the spin-off (HST) and 3,4- Copolymer prepared from dipyridine-2-P phyran. Copolymer containing tetrahydropyran styrene and hydroxystyrene monomer was prepared by the same method as in Example 6, except that 4.2 g of 3,4-dihydro-2 was used. -Orthopyran-substituted ethyl vinyl ether (80% yield). The obtained copolymer had a weight-average molecular weight of 13,587, a polydispersity of 1.74, and a transmittance against ultraviolet rays of 72% / micron. Example 8 A mixture of li_poly_ (DBMST_HST) and poly (HST-BA) was used to prepare a sunblock LMM, and its lithographic effect was used according to 0.3 g of poly (DMST-HST) prepared according to Example 3, and 0.7 g of poly (HST-BA) prepared according to Example 5 was dissolved in 6.0 g of propylene glycol monomethyl ether acetate (PGMEA). Then, 0.03 g of TPSOTf was added as a photosensitive acid generator. The mixture was stirred and then filtered through a filter having a pore size of 0.2 m to obtain a photoresist composition. The photoresist composition printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs was spin-coated to a crystal pattern having a layer of a material to be patterned to a thickness of about 0.5 microns, and the wafer was then at about 140 ° C. Bake for about 90 seconds. After soft baking, the photoresist was exposed using a photomask with a 0.3 micron line and pitch array and a KrF excimer laser stepper with a chirp gap of 0.45. The wafer is then baked for about 90 seconds after about 140 ° C. Finally, the photoresist was developed using 2.38 weight percent of tetramethylammonium hydroxide for 60 seconds to form a photoresist pattern. Then, the material layer under the patterned photoresist is etched using the obtained photoresist pattern. Photoresist with excellent distribution pattern of 0.3 micron line and pitch array -_____ 22_ This paper size applies to Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) 1238291 Α7 Β7 V. Description of the invention (γ〇) Use 21 mJ / The exposure energy of cm2 is formed, and a material layer pattern with an excellent distribution type is obtained using the photoresist pattern. Several kinds of photoresist compositions were prepared by the same method as described above ', and only the mixing ratio of poly (DBMST-HST) and poly (HST-BA) was changed. Lithography is then performed on these compositions to measure the optimal exposure energy required to form a pattern of 0.3 micron 1 line and pitch arrays. The results are shown in Table 2. Table 2 Photoresist-resistance-resisting materials, the largest exposure energy composition poly (DST-HST): poly (HST-BA), optimized exposure energy (mJ / cm2) 1 50: 50 58 2 40:60 45 3 35:65 36 4 30:70 31 5 25:75 26 6 20:80 22 Printed by Consumer Consumption Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 9 Using Poly (DBMST-HST) and Poly ( HST-BA) mixture to prepare a photoresist composition and use its lithography effect. A photoresist composition was prepared by the same method as in Example 8 and lithography was performed thereon, except that 2 mg of diethanolamine was It was further added as an organic base, and soft baking was performed at 130 ° C. The photoresist with excellent distribution pattern of 0.3 micron line and pitch array is applicable to China National Standard (CNS) A4 specification (210X 297 mm) ~ 1238291 A7 B7 V. Description of the invention (vj) Use 34 mJ / The exposure energy of cm2 is formed. A material layer pattern having an excellent distribution type is obtained using the photoresist pattern. Example 10 A photoresist composition was prepared by using a mixture of poly (DBMST-HST) and poly (ethyl to yl-1-ethyl basic acetone-copolymer-hydroxystyrene styrene poly (EEST-HST) 1 and using the same The photolithographic effect was strictly prepared by the same method as in Example 8, and photolithography was performed thereon, except that 0.7 g of poly (EEST-HST) was used instead of 0.7 g of poly (HST- BA), and the soft baking is performed at 130 ° C. The photoresist pattern with an excellent distribution pattern of 0.3 micron line and pitch arrays uses an exposure energy of 30mJ / cm2 to form several photoresist compositions. It is prepared by the method described in 8, but the mixing ratio of poly (DBMST-HST) and poly (HST-EEST) is changed. Then lithography is performed on these compositions to measure the pattern of 0.3 micron line and pitch array The required optimal exposure energy. The results are shown in Table 3. Table 3 The best of the photoresist resist printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 Exposure energy composition poly (DBMST-HST): poly ( HST-EEST) Optimized exposure energy (mJ / cm2) 1 50:50 55 2 40:60 40 3 35:65 34 4 30:70 30 5 25:75 26 6 20:80 22 This paper size applies to China National Standards (CNS) Λ4 specifications (210 '乂 297 mm) A7 B7 5 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1238291

Xuanshi Example U Storage poly (dbmst-hst) and poly (eest-hst) p daily agent silk products, and using its lithographic effect to prepare a photoresist composition by the same method as in Example 10, And lithography was performed thereon, in addition to 2 mg of diethanolamine was further added as an organic base. A photoresist pattern with an excellent distribution pattern of 0.3 micron line and pitch arrays was formed using an exposure energy of 36 mJ / cm2. A material layer pattern having an excellent distribution type is obtained using the photoresist pattern.眚 Example 12 Properties of the photoadhesive composition (1) Thermal stability In order to measure the thermal stability of the photoresist of the present invention, thermogravimetric analysis was performed on a copolymer (DBMST-HST) formed by Example 3 Thing. When heated under nitrogen at 10 ° C / min, the weight change of the copolymer caused by the temperature change was measured and calculated based on the weight (%) at 100 ° C at 100 ° C weight(%). As seen in FIG. 1, when the copolymer having a di-alkylmalonate group is the main component of the photoresist composition of the present invention, it has a high thermal decomposition temperature (Td) of about 170 ° C. 0 (2 ) Contrast In order to obtain the contrast curve of the photoresist composition of the present invention, the thickness of the photoresist layer remaining after exposure is measured by changing the dose of exposure energy. Light

1 " 1 < ____ y N This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 螬

A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1238291 V. Description of the Invention (v ^) The resist composition is 1.0 grams of poly (DBMST-HST) and 0.3 grams of TPSOTf. The thickness of the photoresist layer originally applied was converted to 1 micron to calculate the normalized thickness (micron) of the photoresist layer remaining in the exposed portion. The results are shown in Fig. 2. As shown in FIG. 2, the normalized thickness is maintained close to 1 micron when the exposure energy is lower than about 10 mJ / cm2. However, when the exposure is higher than about 10 mJ / cm2, the normalized thickness drops sharply to 0 within a very narrow range of exposure energy. That is, the contrast curve shows a steep slope at a specific dose of about 10 mJ / cm2, which indicates that the contrast of the photoresist composition of the present invention is extremely high. The polymer and photoresist composition of the present invention have several advantages over conventional polymers and photoresist. Temperatures that allow pre- and post-exposure baking can harden the photoresist without causing decomposition, and they have increased solubility and contrast to allow for finer line and space arrays than conventional photoresists . The acid-labile di-alkylmalonate group bonded to the polymer main chain of the present invention is used as an effective dissolution inhibitor in a photoresist composition. Acidification of a bulk di-alkylmalonate to malonic acid during exposure to light can increase the solubility of the photoresist composition. The contrast caused by the difference in solubility before and after exposure can be significantly increased compared to conventional photoresist compositions using a tertiary butoxycarbonyl (t-BOC) group as an acid labile group. Contrast. Another advantage of the photoresist composition of the present invention is that the acid-labile dissolution inhibitor containing the photo-sensitive di-alkylmalonate and the photo-acid generator are both 1 "standard, suitable for household care standards (where) 44 specifications. (21 () > < 297 mm) ~ ~

1238291 A7 V. Description of the Invention (y +) is thermally stable. These polymers thus cause the photoresist composition of the present invention to have a higher thermal decomposition temperature than a glass transition temperature of about 130 ° C. Therefore, the photoresist can be hardened during pre-baking without decomposing the photoresist. This hardening step prevents absorption of contaminants into the photoresist layer, where the contaminants can hinder the photosensitive acid generator and cause pattern defects. The photoresist composition of the present invention can be pre-baked at a sufficiently high temperature, which can avoid the adsorption of contaminants that can cause pattern defects such as T-tops. The present invention is not limited to the specific embodiments described above, and it can be clearly understood that changes that can be made by anyone familiar with this art are still within the scope of the present invention and printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

I degree 1%

Claims (1)

1238291 A8 B8 C8 D8 VI. Patent application range Weight ratio mixing; and the weight average molecular weight range of each polymer (A) and (B) is from 5,000 to 100,000 002-a positive photoresist composition, which Containing: A polymer mixture for use as a positive photoresist, which comprises a polymer (A) which is an acid-labile di-alkylmalonate group formed by polymerizing two or more different monomers The group is bonded to the polymer main chain, and the polymer (B) is formed by polymerizing a (meth) acrylate derivative monomer with one or more other monomers, in which the polymers (A) and (B ) Mixed in a weight ratio ranging from 0.1: 0.9 to 0.5: 0.5; and a photosensitive acid generator, wherein the polymer (A) is the chemical formula (CF1) and the polymer (B) is the chemical formula (CF2); CH: — CH 7; ό I CH: • CH; OH CHi One CH CH;! _C Ten -------------------- Order --------- (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, CH / \ R 丨 0? C CO2R1 (CF1) (CF2) where: R 1 and R 5 are tertiary butyl or tetrahydropyranyl R 2 respectively, R 3 and R 4 are hydrogen or methyl, respectively. The size of this paper applies to China National Standard (CNS) A4 (210 X 297 public love). Rr Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. 1238291 Rhyme C8 D8 6. Apply for a patent Range η, X and y are integers, the ratio of m / (m + n) is from 0.01 to 0.5, and the ratio of y / (x + y) is from 0.01 to 0.5; each polymer (A) and (B ) Has a weight average molecular weight ranging from 5,000 to 100,000; and the amount of the photosensitive acid generator is from 1 to 15 weight percent based on the weight of the polymer mixture. 3. The positive photoresist composition according to item 2 of the scope of the patent application, wherein the positive photoresist composition further comprises an organic base in an amount of 0.01 to 2.0% by weight based on the weight of the polymer mixture. 4. The positive photoresist composition according to item 3 of the application, wherein the organic base is triethylamine, triisobutylamine, diethanolamine or triethanolamine. 5. The positive photoresist composition according to item 2 of the scope of the patent application, wherein the photosensitive acid generator is a triaryl salt, a diaryl iodonium salt, or a sulfonate. 6. The positive photoresist composition according to item 2 of the application, wherein R 1 is a tertiary butyl group; R 2, R 3 and R 4 are hydrogen; and R 5 is a tertiary butyl group. 7. A positive photoresist composition according to item 2 of the patent application, wherein R 1 is a tertiary butyl group; R 2, R 3 and R 4 are hydrogen; and R 5 is a tetrahydropyranyl group. 8. The positive photoresist composition according to item 2 of the scope of patent application, where R 1 is tertiary butyl; R 2 and R 3 are hydrogen; R 4 is methyl; and 3 (Please read the notes on the back before filling (This page) -nnnni one-on-one 'I nni ϋ n line · This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1238291 A8 B8 C8 D8 t, the scope of patent application R 5 is third-level Ding base. 9. A positive photoresist composition according to item 2 of the scope of the patent application, wherein R1 is a tertiary butyl group; R2 and R3 are hydrogen; R4 is a methyl group; and R5 is a tetrahydropyranyl group. 10 · —A polymer mixture for a chemically amplified positive photoresist, comprising: the polymer (A) is polymerized from two or more different monomers and has an acid-labile di- An alkylmalonate is bonded to the polymer backbone; and the polymer (B) is formed by polymerizing an alkoxystyrene monomer with one or more other monomers, where the polymer (A) is Chemical formula (CF1) and polymer (B) are chemical formula (CF3); (Please read the precautions on the back before filling this page) CH (CF1) (CF3) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs where: R1 is tertiary butyl or tetrahydropyranyl; R 2 and R 3 are hydrogen or methyl respectively; R 7 is alkoxy -1-Ethyl, Tetrahydropyranyl, Tertiary Butyl or Tertiary Butoxy This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) 1238291 A8 B8 C8 D8 6. Scope of Patent Application Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Mm Gan, 1! 1, 11, 1 and 7 are integers; the ratio of m / (m + n) is from 0.01 to 0.5; and y / (x + y) The ratio is from 0.01 to 0.5; the polymers (A) and (B) are mixed at a weight ratio ranging from 0.1: 0.9 to 0.5: 0.5; and the weight average molecular weight range of each polymer (A) and (B) is From 5,000 to 100,000 〇1 1 · A positive photoresist composition comprising: a polymer mixture used as a positive photoresist, comprising a polymer (A) composed of two or more different monomers An acid-labile di-alkylmalonate group formed by polymerization is bonded to the polymer main chain, and the polymer (B) is composed of alkoxystyrene alone Polymerized with one or more other monomers, wherein the polymers (A) and (B) are mixed at a weight ratio ranging from 0.1: 0 to 0.5: 0.5; and a photosensitive acid generator, wherein the polymer (A) is the chemical formula (CF1) and the polymer (B) is the chemical formula (CF3); R2 CH2 I CH / \ I 〇2〇CO? Ri (CF1) T CH 2-CH -JZ- OH 〇kR7 (Please read the precautions on the back before filling this page) ------- Order --------- line »(CF3) This paper size applies China National Standard (CNS) A4 specification (210 X 297 mm> 1238291 A8 B8 C8 D8 t, patent application scope where: R1 is tertiary butyl or tetrahydropyranyl; R 2 and R 3 are hydrogen or methyl R 7 is alkoxy-1-ethyl, tetrahydropyranyl, tertiary butyl or tertiary butoxy m, η, X and y are integers; the ratio of m / (m + n) is given by 0.01 to 0.5; and the ratio of y / (x + y) is from 0.01 to 0.5; each polymer (A) and (B) has a weight average molecular weight ranging from 5,000 to 100,000. And the amount of the photosensitive acid generator is from 1 to 15 weight percent based on the weight of the polymer mixture. 12. The positive photoresist composition according to item 11 of the patent application scope, wherein the positive photoresist composition It further comprises an organic base having a weight percentage of from 0.01 to 2.0% by weight based on the weight of the polymer mixture. 13. The positive photoresist composition according to item 12 of the patent application scope, wherein the organic base is triethyl , Triisobutylamine, diethanolamine or triethanolamine. 14. The positive photoresist composition according to item 11 of the application, wherein the photosensitive acid generator is selected from the group consisting of triaryl salts, diaryl Basic gun salts and sulfonates. 15 · According to the positive photoresist composition No. 11 in the scope of patent application 6 (Please read the precautions on the back before filling this page) Order ------- --Line_ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 1238291-C8 D8. 6. The scope of patent application v, where r 1 is a third level Butyl, R2 and R3 are hydrogen, and R7 is alkoxyethyl ° 1 6 _ A positive photoresist composition according to item 11 of the application, wherein R 1 is a tertiary butyl, R 2 and R3 is hydrogen, and R7 is tetrahydropyranyl. 17. The positive photoresist composition according to item 11 of the application, wherein R1 is tertiary butyl, R2 and R3 are hydrogen, and R7 is tri 18. A positive photoresist composition according to item 11 of the application, wherein R 1 is tertiary butyl, R 2 and R 3 Hydrogen and R7 are tertiary butoxycarbonyl. (Please read the notes on the back before filling out this page) —----- Order --------- · Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs The paper size for printing is applicable to China National Standard (CNS) A4 (210 X 297 mm)