TW593409B - Chemically amplified polymer having pendant group with camphoryl and resist composition comprising the same - Google Patents

Abstract

The present invention relates to a chemically amplified polymer having a pendent group with camphoryl bonded thereto, a process for the preparation thereof and a resist composition comprising it, and more particularly, to a novel (meth)acrylic or norbornene carboxylate compound with camphoryl bonded thereto, a process for the preparation thereof, a chemically amplified polymer synthesized therewith, and a positive photoresist composition for ArF comprising said polymer with high resolution and excellent etching resistance.

Description

State 409 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a novel (exo-bibutyl &) acrylic or n-pinene carboxylic acid ester compound, which has a connection with a hawthorn ^ camphor group A pendent group; a method for preparing the compound; and a chemically amplified polymer synthesized from the compound; and a photoresist composition containing the polymer for ArF; the photoresist composition has a high Resolution and excellent etch resistance. [Previous technology] As the integration degree of semiconductor devices increases, the demand for ultra-fine patterns below 0.25 micron also increases. For this reason, the wavelength of the light source used for patterning according to Rayleigh's rule has also become shorter, such as shortening from 436 nm (G-line) and 3 65 nm (I-line) to 193 nm (ArF ), 157 nm (VUV), and 248 nm (KrF). However, in the prior art, in order to obtain a pattern of a semiconductor device having a capacity of more than 1 G bit, a general photoresist material must be used at 248. nm. Therefore, a new photoresist that can be used at a short wavelength of 1 93 nm and can be continuously developed to meet the requirements of fine resolution is urgently needed. According to structural differences, polymers that are conventionally known as anti-ArF materials can be divided into three categories: polyacrylates, cycloolefin-maleic anhydride copolymers, and poly-n-pinene. In terms of lithographic performance (pattern collapse, line edge roughness, SEM beam contrast, etch resistance, etc.) 'In these three types of compounds, cycloolefin-maleic anhydride copolymer (cycloolefin · 593409 maleic anhydride copolymer (COMA) -type photoresist Yes. However, because of the maleic anhydride fff (maleic anhydride), the COMA-based photoresist will cause bad results in terms of resolution, density, and spatial pattern. In addition, the traditional COMA light Resistance can not show sufficient resistance, because the dry etching process cannot be used. [Content] Therefore, one of the objects of the present invention is to provide a solution of one of the foregoing (fluorenyl) acrylic or n-pinene carboxylic acid ester compounds, Large aliphatic ring substitution capable of increasing high resolution and etching resistance and a method for preparing the same. Another object of the present invention is to provide a photosensitive copolymer and terpolymer suitable as a chemical photoresist. It has cyclic side groups and aliphatic cyclic compounds to obtain sufficient resolution of highly integrated semiconductors, and at the same time, it can show very strong resistance to etching in dry etching processes. Another object of the present invention is to provide a method that can be used in ArF's Taisho photoresist composition, which is a mixture of the photosensitive copolymer and trimer. The most useful MA) water is a thread, which contains a group containing this technical problem; Required and adequate chemical radiation and

5 593409 In order to achieve the foregoing object, the present invention provides a 2-alkyl-2-camphoryl (meth) acrylate represented by the following Formula 1: R *

I) = 0

Where R is a methyl or ethyl group and R * is hydrogen or a fluorenyl group. In addition, the present invention also provides a method for preparing 2-alkyl-2-camphoryl (fluorenyl) acrylate of formula 1, which comprises the following steps: a) let camphor and alkyl grinard reagent Or reacting with an alkyl lithium reagent to prepare 2-alkyl-2-camphorol; and b) reacting the 2-alkyl-2-camphorol prepared above with (meth) acrylic acid chloride.

Furthermore, the present invention also provides a 2-alkyl-2-camphoryl-5-n-pinene-2-carboxylic acid ester compound represented by the following formula 2:

6 593409 where R is monomethyl or ethyl, and R * is hydrogen or a fluorenyl group. In addition, the present invention also provides a method for preparing the 2-alkyl-2-camphoryl-5-n-pinene-2-carboxylic acid ester compound of the formula 2, by allowing the (meth) acrylic acid of the formula 1 2-alkyl-2-camphoryl ester and cyclopentadiene are prepared by a Diels-Alder reaction. The present invention also provides a photosensitive copolymer represented by the following formula 3:

Where R is a fluorenyl or ethyl group, and R * is hydrogen or a fluorenyl group, and η is an integer between 25 and 30. The present invention also provides a method for preparing the photosensitive copolymer of Formula 3, comprising the step of polymerizing the compound of Formula 2 with maleic anhydride. 7 593409 In addition, the present invention also provides a photosensitive trimer represented by the following formula 4:

Where R is a methyl or ethyl group; R * is hydrogen or a fluorenyl group; R 'is hydrogen, an alkyl group, or a hydroxyalkyl group; R "is hydrogen or a methyl group; and m and η Meet the conditions of m + η = 1, 0.1 < m < 0.9 and 0 · 1 < η < 0.9, respectively. In addition, the present invention also provides a method for preparing the photosensitive trimer of Formula 4, which comprises letting Formula 1 Steps for polymerizing the compound with maleic anhydride and n-pinene compound of Formula 6:

RO 〇 6 wherein R ′ is hydrogen, an alkyl group, or a hydroxyalkyl group; and R ″ is a hydrogen group or a fluorenyl group 8 593409 In addition, the present invention also provides a photosensitive trimer represented by the following formula 5:

Where R is a fluorenyl or ethyl group; R * is hydrogen or a methyl group; R 'is hydrogen, an alkyl group, or a hydroxyalkyl group; R "is hydrogen or a fluorenyl group; and m and η Meet the conditions of m + η = 1, 0.1 < m < 0.9 and 0 · 1 < η < 0 · 9, respectively. In addition, the present invention also provides a method for preparing the photosensitive terpolymer of formula 5, which comprises letting Step of polymerizing a compound of formula 2 with maleic acid and an acrylate compound of formula 7: R " 593409 where R 'is hydrogen, an alkyl group, or a hydroxyalkyl group; and R "is a hydrogen-methyl group . In addition, the present invention also provides a chemically amplified photoresist composition that can be used in ArF, which comprises one or more polymers selected from the group consisting of a photosensitive copolymer of formula 3, a photosensitive terpolymer of formula 4, and a polymer of formula 5 Phototrimer. In particular, R 'in the above chemical formula is preferably an alkyl group having an aliphatic carbonitride of < C1Q or an alkyl group having C ^ -C ^. An alkyl group of a fatty hydrocarbon. In addition, the present invention also provides a semiconductor device prepared from the photoresist composition. [Embodiment] The present invention will be described in detail below. The present invention provides a photopolymer and terpolymer prepared from a (meth) acrylic acid carboxylate or n-pinene carboxylic acid ester compound having a large aliphatic cyclic substituent; and the high-resolution and anti-etching method is provided. Polymer and terpolymer to prepare chemically amplified positive photoresist compositions. 2-Alkyl-2- camphorol is reacted with (fluorenyl) propylene fluorene chloride to produce 2-alkyl-2-camphoryl (meth) acrylate of formula 1 of the present invention. Or, it is coated with sensitive lipids and fluorene sensitively. 10 593409 The (fluorenyl) acrylic acid 2-alkyl-2-camphoryl ester is prepared according to the following scheme 1: [Scheme 1]

Where R is monomethyl or ethyl, and X is gas or bromine. As shown in Scheme 1 above, 2-alkyl-2-camphorol can be prepared by reacting camphor with an alkyl gena reagent or alkyl lithium reagent and introducing an alkyl group at the second position of camphor. The above-mentioned alkyligna reagent includes monoalkylmagnesium bromide, alkylmagnesium chloride, and the like; fluorenylmagnesium bromide or fluorenylmagnesium chloride is preferred. Then, according to the present invention, the 2-alkyl-2-camphor (meth) acrylate can be prepared by reacting 2-alkyl-2-camphorol with (meth) acrylic acid chloride, as shown in the following scheme 2 As shown:

[Process 2]

11 593409 where R is monomethyl or ethyl and R * is hydrogen or methyl. In addition, according to the present invention, the n-pinene compound of Formula 2 can be prepared from the compound of Formula 1. According to the present invention, the 2-alkyl-2-camphoryl-5-n-pinene-2-carboxylic acid ester compound of Formula 2 is obtained by subjecting a compound of Formula 1 to cyclopentadiene to undergo a Diricht-Yard reaction ( Diels-Alder), as shown in the following process 3: [Process 3]

R * (1) (2) where R is a fluorenyl or monoethyl group, and R * is hydrogen or fluorenyl. In addition, according to the present invention, the photosensitive copolymer of Formula 3 and the photosensitive terpolymer of Formulas 4 and 5 can also be prepared from the compounds of Formula 1 and Formula 2. First, a photosensitive copolymer of Formula 3 was prepared according to the following formula: 〇! ≫ 7 12 593409

Where R and R * are as defined above. As shown in Scheme 4 above, the photosensitive copolymer of Formula 3 can be prepared by polymerizing an n-pinene compound of Formula 2 and a maleic anhydride. The polymerization reaction may include a starting material such as azidobis (isobutyronitrile) (AIBN). More preferably, the weight-average molecular weight of the obtained photosensitive copolymer of Formula 3 is between 3,000 and 100,000, and the dispersion coefficient is between 1.0 and 5.0.

In addition, the photosensitive terpolymers of formulas 4 and 5 can be prepared according to the following procedures 5 and 6, respectively:

13 593409 [Process 6]

The definitions of “R, R ,, R * and R” are as above. As shown in Scheme 5 above, the photosensitive copolymer of Formula 4 can be polymerized by n-pinene compound of formula 1 and 6 and maleic anhydride. In addition, as shown in Scheme 6 above, the photosensitive copolymer of Formula 5 can be prepared by polymerizing a compound of Formula 2 and an acrylate compound of Formula 7 and maleic anhydride. All of the above-mentioned photosensitive of Formula 4 and 5 The polymerization of the trimer may include a starting material such as azide bis (isobutyronitrile) (AIBN). The weight-average molecular weight of the obtained photosensitive trimer of the formulae 4 and 5 is 3,000 to 100,000. And the dispersion coefficient is between 1.0 and 5.0. In addition, the present invention also provides a chemically amplified positive photoresist composition for ArF, which comprises one or more polymers selected from the group consisting of: a photosensitive copolymer of formula 3, Photosensitive terpolymer of formula 4 and 1% of phototrimer of formula 5 0 14 593409 One hundred percent more advanced agent Sheng B. Alcohol. Hexyl B-A •• A. System: Lamine is included in the present invention In the positive photoresist composition, the one or more kinds are selected from a photosensitive copolymer of formula 3 and a photosensitive trimer of formula 4 The content of the photosensitive terpolymer polymer of Formula 5 is calculated based on the total weight of the polymer, preferably between 30% by weight, and more preferably between 5% and 8% by weight. Furthermore, the photoresist composition of the present invention comprises a photoacid generator and an agent; if necessary, it can also be prepared by using various additives in combination; preferably, it is based on 100 parts by weight of the total photoresist composition. In other words, the solid concentration is between 20% and 50% of the weight. After that, it is filtered through a 0.2 micron filter and then used. Based on the total polymer weight of 100%, the content of the photoacid is less than It is preferably between 0.5% and 10%. Photoacid generators that can be used are sulfonium salts, organic sulfonic acids, or mixtures thereof. Solvents useful in the present invention include ethylene glycol monomethyl ethyl ether. , Glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monoethyl ether acetate (PGMEA), toluene, xylene, methyl ethyl ketone, cyclic ketone, ethyl 2-hydroxypropionate, 2-hydroxy 2-methyl propionate, ethyl ethoxylate, ethyl hydroxyacetate, 2-hydroxy 3-methyl methyl butyrate, 3-oxy 2-methyl Acetate, Ethyl 3-ethoxypropionate, Ethyl 3-methoxy-2-propionate, Ethyl 3-ethoxypropionate, Ethyl 3-methoxy-2-acetoxypropionate, Ethyl acetate Butyl ester, etc. In addition, the photoresist composition of the present invention may further include an organic base, accounting for about 0.01% to 2.00% by weight. Organic triethylamine, triisobutylamine, and triisooctylamine may be used. , Diethanolamine, triethyl 15 593409, or a mixture thereof. In addition, the present invention can provide a semiconductor device having an excellent pattern, which is obtained by coating the photoresist composition on a silicon wafer or an aluminum substrate by spin coating. A photoresist film is formed on the material, and is prepared through the processes of exposure, development and baking. As the developing solution, a 0.1% to 10% alkaline aqueous solution of a basic compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, and tetramethylammonium hydroxide (TMAH) can be used. In addition, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol, and a surfactant may be used in the developing solution. After development, the photoresist film was washed with ultrapure water. Hereinafter, the present invention will be described by way of examples, but the scope of the present invention is not limited to the following examples. EXAMPLES Example 1-1: Synthesis of (methyl) propanoic acid 2-methyl-2-camphoryl ester (R = fluorenyl) (compound 1) a) Preparation of 2-methyl-2- camphorol at 200 Dilute 210 ml (0.64 mol) of methylmagnesium bromide in diethanol (3.0 M) with anhydrous THF. The solution was poured into a 1 liter flask and maintained at 0 ° C. Camphor (48.7 g, 0.32 mol) was slowly dropped into the above solution through a funnel, and then reacted at room temperature for 2 hours. After the reaction was terminated, excess THF was removed with a rotary volatile, and the reaction product was neutralized with dilute sulfuric acid, extracted with diethyl ether, and dried over anhydrous magnesium sulfate. The obtained product was purified by a chromatography column to obtain the title compound of 2-fluorenyl-2- camphorol (yield: 90%). 16 593409 b) Synthesis of 2-methyl-2- camphoryl valerate The 2 'fluorenyl-2- camphorol (45.4 g, 0.27 mol) of a) above and triethylamine (44.48 mL, 32 mol) was dissolved in 250 ml of tHf, and propylene chloride (26 ml, 032 mol) was slowly added from a funnel. Thereafter, the reaction was carried out at room temperature for 2 hours. After the reaction was terminated, the excess THF was removed with a rotary evaporator and the product was poured into pure water. After that, the reaction product was neutralized with dilute hydrochloric acid, extracted with diethylpyrene, and dried over anhydrous magnesium sulfate. Chromatography & column (n-hexane: ethyl acetate · i) was used to purify the obtained

The product can be obtained as the title compound of 2-propionate 2-methyl-2-camphoryl ester (yield: 70%). 〇c) Synthesis of (methyl) acrylic acid 2-methyl · 2 camphoryl ester except methyl propyl Chlorine is used instead of propane gas, and the same process as above is used to prepare 2-methyl · 2-camphoryl (meth) acrylate 0] n-pinene-2-carboxyfluorene (R = methyl) (Compound 2) The above-prepared example 1-1 b) above was dissolved in 25 liters of dibutyl cyanide (35.6 g, 0.16 mol) in Slowly drip cyclopentadiene (31.68 # n, translator a charge — 0.48 mol) at V, then increase the temperature k to room temperature. At room temperature, the reaction takes place for 24 hours. After completion of the reaction, the THF was removed by rotary volatile sand, and the title compound of 2-fluorenyl-2-camphoryl stilbene, knee 1, phytosanitary, and vinegar was obtained in a vacuum base (yield: 70 %). 17 593409 AAtLl-3: Synthesis of (methyl) propanoic acid 2-ethylcamphoryl) 1) Except the use of 1.0 M ethyl magnesium chloride in diethyl ether instead of 3.0 M methyl magnesium chloride in diethyl ether The solution was prepared in the same manner as in the above Example 1 -1 a), and 2-ethyl-2-camphor acrylate and 2-ethyl-2-camphor acrylate (fluorenyl) acrylate could be prepared separately. : Synthesis of 2-ethyl-2-carnosyl-n-pinenebismuth (Compound 2), except that the 2-ethyl-2-camphoryl acrylate of Example 1-3 was used in place of Example 1_1 b) In addition to 2-methyl-2-camphoryl acrylate, it was prepared according to the procedure of Example 1-2 above. Child AA 2-1 ·· 2-fluorenyl · 2_ camphor some 5-n-acrylene 2 · carboxyl octyl polymer (compound 3) Example 1 of 3 9.4 g (0.102 mole) -2 of 2-methyl-2-camphoryl-5-n-pinene-2-carboxylic acid ester, 10.0 g (0.102 mole) of maleic anhydride and 0.7 g of azidobis (isobutyl) Nitrile) (AIBN) was dissolved in 25 g of THF and the reaction was degassed by freezing. Thereafter, the reaction was carried out at 68 ° C for 24 hours. After the reaction was terminated, the reactant was slowly dropped into an excessive amount of diethyl ether to form a precipitate, which was then dissolved in THF and diethyl ether was precipitated to obtain a copolymer (yield 40%). The weight average molecular weight and dispersion coefficient of the obtained copolymer were 8,000 and 1.80 ft. 5 von 593409. Example 2-2: 2-ethyl-2-camphoryl-5-n-pinene-2- Carboxylic acid ester copolymer (Compound 3) In addition to 2-methyl-2-camphor acrylate and 2-fluorenyl-2-camphor methacrylate, 2-methyl-2-camphor acrylate A copolymer composed of an ester or 2-fluorenyl-2-camphoryl methacrylate can be prepared according to the following method. a) Synthesis of a trimer (R = methyl, R3 = hydrogen) 4 5.4 g (0.204 mole) of the 2-acryl-2-camphoryl acrylate of Example 1-1, 14.1 g (0.1 02 mole) ) Of 5-n-pinene-2-carboxylic acid, 10.0 g of maleic anhydride and 0.7 g of azidobis (isobutyronitrile) (AIBN) were dissolved in 50 g of anhydrous THF, and the reaction was removed by freezing. gas. Thereafter, polymerization was carried out at 68 ° C for 24 hours. After the reaction was terminated, the reaction product was slowly dropped into an excess of diethyl ether to form a precipitate, which was then dissolved in THF and precipitated with diethyl ether to obtain a trimer (yield: 40%). The weight average molecular weight and dispersion coefficient of the obtained terpolymers are 7.000 and 1.80 °, respectively. B) Synthetic terpolymers (R = fluorenyl, R3 = transylethyl) except for using 2-hydroxyethyl-5-n-pinene- A trimer was prepared according to the procedure of Example 3-1 except that 2-carboxylic acid ester was used instead of 5-n-pinene-2-carboxylic acid. The weight average molecular weight and dispersion coefficient of the obtained terpolymer are 8.000 and 1.80 ° c) Synthetic terpolymer (R = fluorenyl group, R3 = fluorenyl group) Except using fluorenyl-5-n-pinene-2-carboxylic acid ester Instead of 5-n-pinene • 2-carboxylic acid, a terpolymer was prepared according to the procedure of Example 3-1. 19 593409 The weight average molecular weight and dispersion coefficient of the terpolymer obtained are 8.000 A 1.80. Example 3-2: Synthetic trimer (R = ethyl) (Compound 4) In addition to using 2-ethyl-2-camphor acrylic acid Ester and 2-ethyl-2-camphoryl methacrylate, a copolymer composed of 2-ethyl-2-camphoryl acrylate or 2-ethyl-2-camphoryl methacrylate can be carried out according to the following method preparation. a) Synthesis of a trimer (R = fluorenyl, R3 = hydrogen) except that 2-ethyl-2-camphoryl methacrylate was used in place of 2-methyl-2-camphoryl methacrylate in Example 1-3 In addition, the weight average molecular weight and dispersion coefficient of the terpolymer obtained by preparing the terpolymer according to the procedure of Example 3-1 were 6,500 and 1.80, respectively. b) Synthesis of trimer (R = ethyl, R3 = hydroxyethyl) except that 2-hydroxyethyl-5-n-pinene-2-carboxylic acid ester is used instead of 5-n-pinene-2-carboxylic acid According to the procedure of Example 3-2 a), a trimer is prepared. The weight average molecular weight and dispersion coefficient of the obtained terpolymer were 8.000 and 1.80, respectively. c) Synthesis of trimer (R = ethyl, R3 = methyl) Except using 5-methyl-n-pinene-2-carboxylic acid ester instead of 5-n-pinene-2-carboxylic acid, according to the examples Step 3-2 a) to prepare a trimer. The weight average molecular weight and dispersion coefficient of the obtained terpolymer are 8.000 and 1.80 »20 593409, respectively. Example 4-1: Synthesis of a trimer (Compound 5) a) Synthesis of a trimer (R = methyl, R3 = hydrogen) 29.4 grams (0.102 moles) of Example 1-2 2-fluorenyl-2-camphoryl-5-n-pinene-2-carboxylic acid vinegar, 0.44 grams (0.05 moles) of methacrylic acid, 10.0 g (0.102 mole) of maleic anhydride and 0.7 g of azidobis (isobutyronitrile) (AIBN) were dissolved in 25 g of anhydrous THF, and the reaction was degassed by freezing. The polymerization was then carried out at 68 ° C for 24 hours. After the reaction was terminated, the reactant was slowly dropped into an excess of diethyl ether to form a precipitate, which was then dissolved in THF and precipitated with diethyl ether to obtain a trimer (yield 40%). The weight average molecular weight and dispersion coefficient of the obtained terpolymer were 8,500 and 1.80, respectively. b) Synthesis of a trimer (R = methyl, R3 = hydroxyethyl) In addition to using 2-hydroxyethyl methacrylate instead of methacrylic acid, the trimer was prepared according to the procedure of Example 4-1 a). The weight average molecular weight and dispersion coefficient of the obtained terpolymer were 8.000 A and 1.80, respectively. c) Synthesis of trimer (R = fluorenyl, R3 = methyl) Except using fluorenyl methyl acrylate instead of fluorenyl acrylic acid, the terpolymer was prepared according to the procedure of Example 4-1 a). The weight average molecular weight and dispersion coefficient of the obtained terpolymer were 8.000 A 1.80 ° Example 4-2 »Synthetic trimer (Compound 5) 544 21 593409 a) Synthetic trimer (R = ethyl, R3 = hydrogen) Except replacing 2-methyl-2-camphoryl-5-n-pinene-2-carboxylate with 2-ethyl-2-camphoryl-5-n-pinene-2-carboxylic acid ester of Example 1-4 Except for the acid ester, the weight average molecular weight and dispersion coefficient of the terpolymer obtained by preparing the terpolymer according to the procedure of Example 4-1 a) were 8.500 A and 1.80, respectively. b) Synthesis of trimer (R = ethyl, R3 = hydroxyethyl) Except using 2-hydroxyethyl fluorenyl acrylate instead of methacrylic acid, the trimer was prepared according to the procedure of Example 4-2 a). The weight average molecular weight and dispersion coefficient of the obtained terpolymers are 8.500 and 1.80, respectively. C) Synthetic terpolymers (R = ethyl, R3 = methyl). Except using methacrylic acid ester instead of methacrylic acid, according to the implementation The procedure of Example 4-2 a) produces a trimer. The weight average molecular weight and dispersion coefficient of the obtained terpolymer were 8.500 A and 1.80, respectively. Example 5: Preparation of a photoresist composition 20 g of the copolymer of Example 2-1 and 0.02 g of triphenyl sulfonium triflate (TPS-1 05) were completely dissolved in 17 g of propylene glycol monomethyl Ether acetate (PGME A). Filter the solution through a 0.2 micron dish filter to obtain a photoresist solution. After that, the photoresist solution was coated on a silicon wafer treated with hexamethylene disilane (HMDS) to a thickness of about 0.30 micrometers. Γ> 4'7 22 593409 The silicon wafer on which the photoresist solution has been applied is pre-baked at 110 ° C for 90 seconds, and the laser beam is exposed with an aperture of 0.60 ". Then, it is exposed at 130 ° Post-exposure bake at 90 ° C.

Thereafter, the product was developed with a 2.38% (wt%) solution of tetramethylammonium hydroxide (TMAH) for 30 seconds. As a result, when the exposure is performed with an energy of 20 mJ / cm², a rectangular photoresist pattern with a line width of about 0.1 3 microns can be obtained. The copolymer of the present invention can reduce the etching rate to polysilicon by about 20%. Therefore, compared with the conventional COMA, it exhibits better etching resistance. Example 6: Preparation of a photoresist composition 20 grams of the terpolymer of Example 3-1 and 0.02 grams of triphenyl sulfonium triflate (TPS-105) were completely dissolved in 17 grams of propylene glycol monomethyl ether Acetate (PGME A). The same procedure as in Example 5 was used to prepare a photoresist solution. The line width of the rectangular photoresist pattern is about 0.1 2 microns.

Example 7: Preparation of a photoresist composition 20 grams of the terpolymer of Example 4-1 and 0.02 grams of triphenyl sulfonium triflate (TPS-105) were completely dissolved in 17 grams of propylene glycol monofluorenyl ether Acetate (PGME A). The same procedure as in Example 5 was used to prepare a photoresist solution. The line width of the rectangular photoresist pattern is about 0.1 2 microns. The photosensitivity, resolution, and pattern shape of the above-mentioned Examples 5-7 and the aforementioned COMA type photoresist are shown in Table 1 below. In addition, the COMA photoresist patterns of Example 7 and the prior art are shown in Fig. 1 and Fig. 2, respectively. In addition, Figures 3 and 4 of 23 593409 show the etching resistance of oxides and polymers with Examples 5 to 7 and the prior art COM A type photoresist. Table 1 Photosensitivity resolution pattern shape (亳 Joules / cm²) (microns) Example 5 20 0.13 Rectangular_Example 6 21 0.12 Rectangular Example 7 18 0.12 Rectangular front technology COMA 25 0.14 Narrowing from Tables 1 and 1 As can be seen from the figure -4, compared with the prior art COMA type photoresist, the photoresist of the present invention has an excellent rectangular pattern shape, and at the same time has excellent resistance to etching of oxides and polymers. As described above, the present invention can provide a copolymer or terpolymer which is prepared by using a novel (meth) acrylic compound or n-pinene carboxylate compound. The carboxylate compound has a pendant group connected to the camphor group; and the copolymer or terpolymer can provide a chemically amplified positive photoresist composition that can use ArF. By using the polymer, it can have an excellent photoresist composition. High resolution and etch resistance 'and thus can obtain excellent photoresist patterns. [Brief description of the drawings] FIG. 1 shows a photoresist pattern according to Embodiment 7 of the present invention. β44 '24 593409 Figure 2 shows the pattern results of a prior art COMA photoresist. Figure 3 shows the results of the etching resistance of the oxides of Examples 5 to 7 of the present invention. Figure 4 shows the results of the etching resistance of the previous poly COMA photoresist. fyM% 25

Claims (1)

593409 Brother Qiao's "Hong" patent case amended in March ‘pick up and apply for patent scope 1. A 2-alkyl-2-camphoryl (meth) acrylate compound of formula 1, Where R is a methyl or ethyl group and R * is hydrogen or a fluorenyl group. 2. · A method for preparing a compound of formula 1 with 2-alkyl-2-camphoryl (meth) acrylate in the first patent application scope, which comprises at least the following steps: a) let camphor and monokidna reagent (Alkyl grinard reagent) or alkyl lithium reagent to produce 2-alkyl-2-camphorol; and b) the aforementioned 2-alkyl-2-camphorol and (methyl) Propylene and chlorine react. 3. A 2-alkyl-2-camphoryl-5-n-pinene-2-carboxylic acid ester compound of formula 2, 26 593409 where R is monomethyl or ethyl, and R * is hydrogen or a methyl group. 4. A method for preparing a compound of formula 2 with 2-alkyl-2-camphoryl-5-n-pinene-2-carboxylic acid ester in item 3 of the scope of patent application, which is obtained by allowing item 1 in the scope of patent application (Methyl) 2-alkyl-2-camphoryl acrylate is prepared by a Diels-Alder reaction with cyclopentadiene. 5. —photosensitive copolymer of type 3, Wherein R is a monomethyl group or an ethyl group, R * is a hydrogen or a monomethyl group, and 27 593409 η is an integer between 25 and 30. 6. A method for preparing a photosensitive copolymer of formula 3 in the scope of the patent application, which comprises the step of polymerizing a compound of formula 2 in the scope of the patent application, and maleic anhydride. Where R is a methyl group or an ethyl group; R * is hydrogen or a methyl group; R 'is hydrogen, an alkyl group, or a hydroxyalkyl group; R "is hydrogen or a methyl group; and m and η The conditions of m + n = 1, 0.1 < m < 0.9 and 0 · 1 < η < 9 · 9 are satisfied, respectively. 8. A method for preparing a photosensitive terpolymer of the formula 4 in the scope of the patent application, which comprises allowing the compound of the formula 1 in the scope of the patent application and the maleic anhydride and the n-pinene compound of the following formula 6 Aggregation steps: 28 593409 wherein R 'is hydrogen, an alkyl group, or a hydroxyalkyl group; and R "is hydrogen or a fluorenyl group. 9. A photosensitive trimer of Formula 5, Where R is a methyl group or an ethyl group; R * is hydrogen or a methyl group; R 'is hydrogen, an alkyl group, or a hydroxyalkyl group; R "is hydrogen or a methyl group; and m and η Meet the conditions of m + n = 1, 0.1 < m < 0.9 and 0.1 < n < 0.9 respectively. 1 〇-a method for preparing a photosensitive terpolymer of formula 5 in the ninth item of the scope of patent application, which comprises Step of polymerizing a compound of formula 2 with maleic anhydride and an acrylate compound of formula 7 below in the scope of patent application: 29 593409 R " Wherein R 'is hydrogen, a monoalkyl group or a hydroxyalkyl group; and R "is a hydrogen or a fluorenyl group. 1 1 · A chemically amplified positive photoresist composition for ArF, comprising at least one or more polymers selected from the group consisting of a photosensitive copolymer of Formula 3, a photosensitive trimer of Formula 4, and a photosensitive trimer of Formula 5 in: 30 593409 wherein R is a fluorenyl or ethyl group; R * is hydrogen or a methyl group; R 'is hydrogen, an alkyl group, or a hydroxyalkyl group; R "is hydrogen or a fluorenyl group; and m · And η satisfy the conditions of m + n = 1, 0.1 < m < 0.9 and 0 · 1 < η < 0 · 9, respectively. 1 2 · The chemically amplified positive light group composition according to item 11 of the patent application scope, which is characterized in that The content of the polymer is from 1% to 30% by weight (% by weight) of the total composition. 1 3. If the chemically amplified positive light composition of the scope of the patent application No. 11 is applied, the feature is the photoresist combination The product further contains a photoacid generator, the content of the photoacid generator is about 0.5% to 10% of the total polymer weight (% by weight). 14 · Chemically amplified positive light as described in item 13 of the scope of patent application Composition,-characterized in that the photoacid generator is selected from the group consisting of a phosphonium salt, an organic sulfonic acid, or a mixture thereof. 1 5. The chemically amplified positive light group according to item 11 of the scope of patent application Composition, 31 593409, characterized in that the photoresist composition further comprises an organic base, the organic base is selected from triethylamine Triisobutylamine, tri-iso-octylamine, diethanolamine, triethanolamine, or the mixtures thereof; and the amount of the organic base is between 0.01 to 2.00 percent by weight of the total polymer (wt%). 32