TWI225481B - Chemically amplified polymer having pendant group with cyclododecyl and resist composition comprising the same - Google Patents

Abstract

The present invention relates to a chemically amplified polymer having a pendent group with cyclododecyl bonded thereto, a process for the preparation thereof and a resist composition comprising it, and more particularly, to a novel (meth)acrylic or norbomene carboxylate compound with cyclododecyl 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

1225481 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a novel (fluorenyl) acrylic acid or n-pinenecarboxylic acid vinegar compound, which has a pendant group connected to 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 high resolution and excellent Resistance to afterglow. [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, there is an urgent need for 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. According to the structural differences, the 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, anti-etching resistance, etc.) 'In these three types or compounds, the cycloolefin-maleic anhydride copolymer (CyCl. 〇lefin-1225481 maleic anhydride copolymer (COMA) -type photoresist is the most useful. However, because of the hydrolysis of maleic anhydride (MA) ff * (maleic anhydride, MA), the COMA-based photoresist will cause bad results in resolution, especially in linear density and spatial pattern. In addition, photoresists that include conventional COMA do not exhibit sufficient resistance, so dry etching processes still cannot be used.

[Content] Therefore, one of the objectives of the present invention is to provide a (fluorenyl) acrylic or n-pinene carboxylic acid ester compound that can solve one of the above-mentioned prior art problems, and it has a large fat that can increase high resolution and resistance to etching. Ring substituents; and methods of making the compounds. Another object of the present invention is to provide a photosensitive copolymer and terpolymer suitable as a chemically amplified photoresist, which comprises a side group with a cyclic structure and an aliphatic cyclic compound to obtain a highly integrated semiconductor The required sufficient resolution can also show very strong and sufficient anti-etching resistance to the dry etching process.

Another object of the present invention is to provide a chemically amplified positive photoresist composition for ArF, which comprises the photosensitive copolymer, terpolymer, and a mixture thereof. 5 1225481 In order to achieve the foregoing object, the present invention provides a (methyl) propanoic acid 1-alkyl-1-cyclododecyl vinegar represented by the following formula 1:

Wherein R is a methyl group or an ethyl group, and R * is a hydrogen or a methyl group. In addition, the present invention also provides a method for preparing the 1-alkyl-1-cyclododecyl (meth) acrylate of formula 1, which comprises the following steps: a) let cyclododecanone and a courtyard group Reaction of alkyl grinard reagent or alkyl lithium reagent to prepare 1-alkyl-1-cyclododecyl-1-ol; and b) let 1-alkyl prepared above 1-cyclododecyl-1-ol is reacted with (meth) propylene tritium gas.

Furthermore, the present invention also provides a 2-alkyl-1-cyclododecyl-4-n-pinene-1 · carboxylic acid ester compound represented by the following formula 2:

6 1225481 where R is monomethyl or ethyl, and R * is hydrogen or a methyl group. In addition, the present invention also provides a method for preparing the 2-alkyl-1-cyclododecyl-4-n-pinene-1-carboxylic acid ester of formula 2 by ) Prepared by 1-alkyl-1-cyclododecyl acrylate and cyclopentadiene by Diels-Aldeo reaction. The present invention also provides a photosensitizer represented by the following formula 3 Copolymer:

Wherein R is a methyl or ethyl group, R * is hydrogen or a methyl group, and η is an integer between 22 and 26. 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 1225481 In addition, the present invention also provides a photosensitive trimer represented by the following formula 4 ...

4-«where R is a methyl 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 methyl group; And m and η satisfy 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 4, It comprises the steps of polymerizing a compound of formula 1 with maleic anhydride and an n-pinene compound of formula 6:

6 wherein R 'is hydrogen, an alkyl group, or a hydroxyalkyl group; and R "is hydrogen or a methyl group. 8 1225481 In addition, the present invention also provides a photosensitive trimer represented by the following formula 5:

5

Where R is a methyl 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 methyl group; and m and η Meet the conditions of m + η = 1, 0 · l < 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 Steps for polymerizing a compound of formula 2 with maleic anhydride and a acrylate compound of formula 7:

Wherein R ′ is hydrogen, a monoalkyl group, or a hydroxyalkyl group; and R ″ is hydrogen or a 9 1225481 monomethyl group. 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, a photosensitive terpolymer of Formula 4, and a photosensitive terpolymer of Formula 5.

In particular, R 'in the above chemical formula is preferably one having C ^ C ,. Alkyl group of fatty hydrocarbon or one with CrC. Hydroxyalkyl groups of fatty hydrocarbons. 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 invention provides a photosensitive copolymer and terpolymer prepared from a (meth) acrylic acid carboxylic acid ester or n-pinene carboxylic acid ester compound having a large aliphatic cyclic substituent; and the high-resolution and resistant Etching copolymers and terpolymers to prepare chemically amplified positive photoresist compositions. 1-alkyl-1-cyclododecyl-1-ol is reacted with (fluorenyl) propene tritium gas to prepare 1-alkyl (1-cyclo · dodecane) (meth) acrylic acid of formula 1 of the present invention Based ester. 10 1225481 The preparation of the 1-alkyl-1-cyclododecyl (meth) acrylate is according to the following scheme 1 [Scheme 1]

Where R is monomethyl or ethyl, and X is chlorine or bromine. As shown in Scheme 1 above, 1-alkyl-1 -cyclododecyl-1-ol can be reacted on cyclododecane by reacting cyclododecanone with an alkyl alkyl reagent or an alkyl lithium reagent. Alkone is prepared by introducing an alkyl group at the first position. The above-mentioned alkyl gena reagent includes monoalkylmagnesium bromide, alkylmagnesium vaporizer, and the like; methylmagnesium bromide or fluorenylmagnesium vaporizer is preferred. Then, according to the present invention, the 1-alkyl-1-cyclododecyl (meth) acrylate can be obtained by letting 1-alkyl-1-cyclododecane-1-ol and (meth) propylene醯 Chlorine reaction to prepare, as shown in the following scheme 2: [Scheme 2]

Wherein R is monomethyl or ethyl, and R * is hydrogen or methyl. 11 1225481 Furthermore, according to the present invention, a compound of the n-pinene compound of formula 2 is prepared. According to the present invention, the 1-alkyl-1-cyclododecene-1-carboxylic acid ester compound of Formula 2 is prepared by allowing a compound of Formula 1 to undergo a Diels-Alder reaction. This is shown in column 3: [Scheme 3] [Formula 1 can be based on -4-normal cyclopentadiene, as follows

(2) ⑴ where R is monomethyl or ethyl, and R * is hydrogen or t In addition, according to the present invention, the photosensitive terpolymer of the photosensitive copolymer 〆 of formula 3 can also be a compound of formula 1 or 2 Preparation First, the photosensitive copolymer of Formula 3 is prepared according to the following formula: r group. L type 4, 5 equipment. 12 1225481 [Process 4]

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 4 1225481 [Process 6]

Wherein it is prepared as a compound of formula 1. In addition, it is composed of a polymerized diacid Sf • a photosensitizer such as a stack 4 and 5 100,000 f and a photoresist combination 3. R, R ,, R * and R "are as defined above.

As shown in Ji Scheme 5, the photosensitive copolymer of Formula 4 can be obtained by using the polymer and the n-pinene compound of Formula 6 and maleic anhydride. As shown in Scheme 6 above, the photosensitive copolymer of Formula 5 can borrow 2 Compounds and acrylate compounds of Formula 7 were prepared with monobutene. The polymerization reaction of the photosensitive terpolymers of the above formulae 4 and 5 may include a nitrogen bis (isobutyronitrile) (AIBN) starting material. Preferably, the weight-average molecular weight of the obtained phototrimer is between 3,000 and 3, and the dispersion coefficient is between 1.0 and 5.0. The present invention also provides a chemically amplified positive electrode that can be used in ArF, which comprises one or more polymers selected from the group consisting of: a final polymer, a photosensitive trimer of formula 4, and a photosensitive trimer of formula 5.

14 1225481 In the positive photoresist composition of the present invention, the content of the one or more polymers selected from the photosensitive copolymer of formula 3, the photosensitive terpolymer of formula 4 and the photosensitive terpolymer of formula 5 is based on the total weight of the polymer To calculate, it is preferably between 1% and 30% by weight, and more preferably between 5% and 8% by weight.

Furthermore, the photoresist composition of the present invention includes a photoacid generator and a solvent; if necessary, it can also be prepared by using various additives in combination; more preferably, based on 100 parts by weight of the total photoresist composition Its solid concentration is between 20% and 50% of the weight. After that, it was filtered through a 0.2 micron sieve and used again. Based on the total polymer weight being 100%, the content of the photoacid generator is preferably between 0.5% and 10%. Photoacid generators that can be used are phosphonium salts, organic continuous acids, or mixtures thereof.

Solvents that can be used in the present invention include ethylene glycol monomethyl ethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA), and toluene Benzene, acetophenone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, 2-hydroxy3-methyl Methyl ethyl butyrate, ethyl 3-methoxy-2-methylpropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxy-2-methylpropionate, ethyl 3-ethoxypropionate , Ethyl 3-methoxy-2-methylpropionate, ethyl acetate, butyl acetate, and the like. Furthermore, the photoresist composition of the present invention may further include an organic test, which accounts for about 0.01% to 2.00% by weight. Organic bases that can be used include triethylamine, triisobutylamine, triisooctylamine, diethanolamine, triethanolamine 15 1225481 or a mixture thereof.

In addition, the present invention can provide a semiconductor device having an excellent pattern. The photoresist composition is coated on a silicon wafer or an aluminum substrate by spin coating to form a photoresist film. Prepared by development and baking processes. 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 1-fluorenyl-1-cyclododecane (meth) acrylate (R = methyl) (Compound 1) a) Preparation of 1-fluorenyl-1-cyclododecane 1-ol

A solution of 210 ml (0.64 moles) of methyl magnesium bromide in diethyl ether (3.0 M) was diluted with 200 ml of anhydrous THF. Pour the solution into a 1 liter flask and maintain it at 0 ° C. Slowly drop cyclododecanone (5 8.3 g, 0.3 2 mol) into the above solution using a funnel, and then react 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 resulting product was purified by a chromatography column to obtain the title compound of 1-fluorenyl-1-cyclododecyl-1-ol (yield: 90%). 16 1225481 b) Synthesis of 1-methyl-1-cyclododecyl acrylate The 1-fluorenyl-1-cyclododecyl alcohol (5 36 g, 0.27 mol) of a) above and three Ethylamine (44.48 liters, 032 moles) was dissolved in 250 ml of THF, and propylene chloride (26 ml, 032 moles) was slowly added from a funnel. It was then reacted at room temperature for 2 hours. After the reaction was terminated, 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 diethyl ether, and dried with anhydrous sodium sulfate. The product was purified by a chromatography column (n-hexane: ethyl acetate = 4: 1) to obtain the title compound of 1-methyl_1-cyclododecyl acrylate (yield: 70%). ). c) Synthesis of (meth) acrylic acid 1-methyl-1β cyclododecanyl, except that methacrylic thoron gas is used instead of propylene thoron gas, and the same procedure as in b) above can be used to prepare (fluorenyl) acrylic acid 1-methyl-1-cyclododecane ester. Example ~ Formamidine dicyclododecyl-4-n-pinene-1-carboxene (R == formate 2) 1-methyl acrylic acid prepared in Example 1 -1 b) -1 -cyclododecyl ester (40 4 *. See '〇.16 moles) dissolved in 250 ml of THF, and cyclopentadiene (3168 g, 0.48 moles) was slowly dripped at' C, Increase the temperature afterwards; ^, to the temperature. While stirring at room temperature, react 24 Koriji Temple. Should be% ~ after the 'removal of excess THF with a rotary volatilizer, and the title compound of methyl-1-cyclododecyl-4- is obtained in a vacuum vaporizer ^ φ milk ( Yield: 70%). 17 1225481

· Synthetic group diethyl-bunn + dioxane. Compound U except that 1.0 OM ethyl magnesium hydride in diethyl ether solution was used instead of 3.0 mM methyl magnesium hydride in diethyl ether solution, The preparation is performed in the same manner as in the above Example 1-1 a), and ethyl ethyl β-cyclododecane acrylate and 1-ethyl cyclododecane (meth) acrylate can be prepared respectively. fExample 1-.4 ·· Synthesis of 1-ethylenedodecane-cardio-pinene-i · carboxylic acid ester (R = ethyl) (Compound 2) Except for the ethyl acrylate of Example 1-3 -^ Cyclododecanate was used in place of the methyl methacrylate β1_cyclododecyl acrylate prepared in Example 1-1 b), and was prepared according to the steps of Example 1-2 above. Complex- ^ 1 ^ 2-1: Example of preparing a copolymer (compound 3, 32.5 g (0.102 mole)) of Limethyl_1: cyclododecane-4-n-pinene-1-^^ Bu 2 of 1-fluorenyl- !, cyclododecyl-4-n-pinene-1-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 reactant was degassed by freezing. Then, the polymerization reaction was performed at 68 ° C for 24 hours. After the reaction was terminated, the reactant was slowly dropped into an excess of diethyl ether The precipitate was generated in the medium, and then dissolved in THF and diethyl ether to obtain a copolymer (yield: 40%). The weight average molecular weight and dispersion coefficient of the obtained copolymer were 8,000 and 1.80, respectively. 18 1225481 Compound _ 2: 1-Ethyl-1 -Heptaerythyl is gaining the Buddha-1 -Bei-1 copolymer (compound 3) _ Except for the use of ethyl-bucyclododecyl-cardioxin-1 in Example 4 -Except for the osmic ester, it was prepared according to the procedure of Example 2-1. The weight average molecular weight and dispersion coefficient of the obtained copolymer were 7,000 and 1.85, respectively.

Ai Example 3.1: He Rong terpolymer Bj) (Chemical_fe ·. 4) In addition to using 1-methyl-1-cyclododecane acrylate and 1 _methyl-1 -cyclodecamethacrylate In addition to the dialkyl esters, a copolymer composed of 1-fluorenyl-1-cyclododecyl acrylate or 1-methyl-1-cyclododecyl methacrylate can be prepared according to the following method. a) Synthesis of trimer (r = methyl, r3 = hydrogen)

51.5 g (0.2 04 mole) of p-methyl-1-cyclododecane acrylate of Example 1-1, 14.1 g of 5-n-pinene-2-carboxylic acid ester, 10.0 g (0.102 mole) The maleic anhydride and 0.7 g of azidobis (isobutyronitrileΗΑΙΒΝ) were dissolved in 50 g of anhydrous THF, and the reaction was degassed by freezing. The polymerization reaction was then carried out at 68 ° C for 24 hours. After the reaction is terminated, the reactant is slowly dropped into an excess of diethyl ether to form a sink, and 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 copolymer were 7,000 and 1.85, respectively. b) Synthetic trimer (R = methyl, r3 = hydroxyethyl) except for using 2-hydroxyethyl-5-n-pinene-2-carboxylic acid ester instead of% 19 1225481 n-pinene-2-carboxylic acid In addition, the terpolymer was prepared according to the procedure of Example 3-1 a). The weight average molecular weight and dispersion coefficient of the obtained trimer are 7.500 and 1.80 ° c) Synthetic trimer (R = ethyl, R3 = methyl) except that methyl-5-n-pinene-2-carboxylic acid ester is used Instead of 5-n-pinene-2-carboxylic acid, a terpolymer was prepared according to the procedure of Example 3-1 a).

The weight average molecular weight and dispersion coefficient of the obtained trimer were 8,000 and 1.80, respectively. Example 3-2: Synthesis of a trimer (R = ethyl) (Compound 4) In addition to using acrylic acid 1-ethyl-1-cyclododeca Alkyl esters and 1-ethyl-1 -cyclododecane fluorenyl acrylate, 1-ethyl-1 -cyclododecane acrylate or 1-ethyl-1-cyclododecane fluorenyl acrylate A copolymer having an ester composition can be prepared by the following method. a) Synthesis of trimer (R = ethyl, R3 = hydrogen)

Except using 1-ethyl-1 -cyclododecyl methacrylate in Example 1-3 instead of 1-fluorenyl-1 -cyclododecyl methacrylate, according to Example 3 -1 a) Steps to prepare. The weight average molecular weight and dispersion coefficient of the copolymer obtained were 6.500 and 1.8 ° b) Synthetic terpolymers (R = ethyl, R3 = triethyl) except for the use of 2-hydroxyethyl-5-n-pinene-2 A carboxylic acid ester was used instead of 5-n-pinene-2-carboxylic acid, and a terpolymer was prepared according to the procedure of Example 3-2 a). The weight average molecular weight and dispersion coefficient of the obtained terpolymer were 20 1225481 8,000 A 1.50. c) Synthesis of trimer (R = ethyl, R3 = methyl) Except using methyl-5-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 were 8,500 and 1.80, respectively.

Example 4-1: Synthesis of trimer (Compound 5) a) Synthesis of trimer (R = methyl, R3 = hydrogen)

35.5 g (0.102 mole) of 1-fluorenyl-1-cyclododecyl-4-n-pinene-1-carboxylic acid ester of Example 1-2 and 0.44 g (0.005 mole) of methyl group Acrylic 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. 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 cause precipitation, and then dissolved in THF and diethyl ether to obtain a trimer (yield: 40%). The weight average molecular weight and dispersion coefficient of the obtained terpolymer were 8.500 A and 1.80 〇b) Synthetic terpolymer (R = methyl, R3 = ylethyl) except for using methyldienoic acid 2-hydroxyethyl instead In addition to fluorenyl acrylic acid, a terpolymer was prepared according to the procedure of Example 4-1 a). The weight average molecular weight and dispersion coefficient of the obtained trimer are 8.500 and 1.80 ° 21 1225481 c) Synthetic trimer (R = methyl, R3 = methyl) In addition to using methyl methacrylate instead of methacrylic acid, A 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 8,500 and 1.80, respectively. Example 4-2: Synthesis of trimer (compound 5)

a) Synthesis of trimer (R = ethyl, R3 = hydrogen) except that 1-ethyl-1-cyclododecyl-4-n-pinene-1-carboxylic acid ester of Example 1-4 was used instead Except for 1-methyl-1-cyclododecyl-4-n-pinene-1-carboxylic acid ester, the weight average molecular weight and dispersion of the trimer obtained according to the procedure of Example 4-1 a) were used to prepare the trimer. The coefficients are 8.500 and 1.80, respectively. b) Synthesis of trimer (R == ethyl 'R3 = merylethyl). Except using 2-hydroxyethyl fluorenyl acrylate instead of fluorenyl acrylic acid, the trimer was prepared according to the procedure of Example 4-2 a). Thing.

The weight average molecular weight and dispersion coefficient of the obtained terpolymer were 8.500 A and 1.80, respectively. c) Synthesis of a trimer (R = ethyl, R3 = methyl) In addition to using methyl methyl acrylate instead of methacrylic acid, a trimer was prepared according to the procedure of Example 4-2 a). The weight average molecular weight and dispersion coefficient of the obtained terpolymer were 8.500 and 1.80, respectively. 22 ^ 5481 Example 5: Preparation of a photoresist composition 20 grams of the copolymer of Example 2-1 and 0.02 grams of triphenyl sulfonium triflate (TPS-105) were completely dissolved in 17 grams of propylene glycol Monomethyl ether acetate (PGMEA). Filter the solution through a 0.2-micron dish filter to obtain a photoresist solution. Then, the photoresist solution was coated on a silicon wafer treated with hexamethyldisilanes (HMDS) to a thickness of about 0.30 micrometers.

The silicon wafer coated with the photoresist solution was pre-baked at 110 ° C for 90 seconds, and exposed with an ArF laser with an aperture value of 0.60. Thereafter, post-exposure baking was performed at 130 ° C for 90 seconds. After that, the product was developed with a 2.38% (wt%) tetramethylammonium hydroxide (TMAH) solution for 30 seconds. As a result, when the exposure is performed with an energy of 20 mJ / cm 2, a rectangular photoresist pattern with a line width of about 0.1 3 μm 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 (PGMEA). 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 photoresist composition 23 1225481 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 mono Methyl 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, Fig. 3 and Fig. 4 respectively show the etching resistance of oxides and polymers by Examples 5 to 7 and the prior art COMA type photoresist. Table 1 Photosensitivity Resolution Pattern shape (mJ / cm2) (microns) Example 5 20 0.13 Rectangle Example 6 22 0.12 Rectangle Example 7 19 0.12 Rectangle COMA 25 0.14 Narrow

As can be seen from Table 1 and Figures 1-4, compared with the COMA photoresist of the prior art, the photoresist of the present invention has an excellent rectangular pattern shape, and at the same time has excellent resistance to oxides and polymers. As described above, the present invention can provide a copolymer or terpolymer prepared by using a novel (fluorenyl) acrylic compound or n-pinene carboxylic acid ester compound, the novel (fluorenyl) acrylic compound or n-pinene The carboxylic acid esterification 24 1225481 composition has a pendant group connected to the cyclododecyl group; and the copolymer or terpolymer can provide a chemically amplified positive photoresist composition that can use ArF, by using the polymerization The object can make it have excellent high resolution and etching resistance, and thus can obtain an excellent photoresist pattern. [Brief description of the drawings] FIG. 1 shows a photoresist pattern according to Embodiment 7 of the present invention.

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. 25

Claims (1)

1225481 Patent application scope 1 · A (alkyl) acrylic acid 1-alkyl-1 -cyclododecane compound of formula 1, Wherein R is a methyl group or an ethyl group, and R * is a hydrogen or a methyl group. 2. · A method for preparing a compound of formula 1 with 1-alkyl-1-cyclododecanyl (meth) acrylate in item 1 of the scope of patent application, which comprises at least the following steps: a) let cyclododecanone Reacted with an alkyl grinard reagent or an alkyl lithium reagent to prepare 1-alkyl-1-cyclododecanol; and b) The 1-alkyl-1-cyclododecanol prepared above is reacted with (meth) propylene sulfonium chloride. 3. 1-alkyl-1-cyclododecyl-4-n-pinene-1-carboxylic acid ester compound of formula 2, 26 1225481 Where R is a fluorenyl or ethyl group, and R * is hydrogen or a fluorenyl group. 4. A method for preparing a compound of formula 2 of 1-alkyl-1-cyclododecyl-4-n-pinene-1-carboxylic acid ester in item 3 of the scope of patent application, by allowing the scope of patent application The 1st (fluorenyl) 1-alkyl-1-cyclododecane acrylate compound prepared by performing a Diels-Alder reaction with cyclopentadiene. 27 1225481 and η wherein R is a fluorenyl or ethyl group, and R * is hydrogen or a fluorenyl group, and is an integer between 22 and 26. Formula and 6. A method for preparing a photosensitive copolymer of formula 3 according to the scope of the patent application, which comprises the step of polymerizing the maleic anhydride of the formula 2 of the scope of the patent application. 7. —photosensitive terpolymer of type 4, Where R is a methyl group or an ethyl group; R * is hydrogen or a fluorenyl group; hydrogen, an alkyl group of an aliphatic hydrocarbon having C! -C] 〇 or a Ci-Ci. A hydroxyalkyl group of a fatty hydrocarbon; R "is hydrogen or a radical; and m and η satisfy the conditions of m + n = 1, 0.1 < m < 0 (Kl < n < 0.9, respectively. 8 A method for preparing a photosensitive terpolymer of formula 4 as claimed in item 7 of the scope of patent application, which comprises polymerizing j R of a compound maleic anhydride of formula 1 as defined in item 1 of the scope of patent application and an n-pinene compound of formula 6 below. , Is a cube with a 曱 • 9 and a divination: 28 1225481 Where R 'is hydrogen, an alkyl group of a fatty hydrocarbon having Ci-Cw, or a hydrocarbyl group of a fatty hydrocarbon having c 1 -C 1 G; and R "is hydrogen Or a methyl group. 9. A photosensitive terpolymer of formula 5, 5 where R is a fluorenyl or ethyl group; R * is hydrogen or a fluorenyl group; R 'is hydrogen, an alkyl group of an aliphatic hydrocarbon with Ci-Cw, or an alkyl group with Ci-Cw A hydroxyalkyl group of a fatty hydride; R "is hydrogen or a methyl group; and m and η satisfy m + n = 1, 0.1 < m < 0.9 and 0 · 1 < η < 0 · Conditions of 9 〇 29 1225481 1 〇.-A method for preparing a photosensitive terpolymer of formula 5 in the scope of the patent application, which comprises the compound of formula 2 in the scope of the patent application and maleic anhydride and the following Step of polymerizing acrylate compound of formula 7: R " Wherein R 'is hydrogen, an alkyl group of a fatty hydrocarbon having C i -C i 〇 or a hydroxyalkyl group of a fatty hydrocarbon having CrCw; and R "is hydrogen or a 1 1. A chemically amplified positive photoresist composition for ArF, comprising at least one or more 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 the composition of the polymer: 30 1225481 R * 5 where R is a methyl group or an ethyl group; R * is hydrogen or a methyl group; hydrogen, an alkyl group of a fatty hydrocarbon having CpCw, or a fatty hydrocarbon of CrCa A hydroxyalkyl group; R "is hydrogen or a radical; and m and η satisfy m + n = 1, 0.1 < m < 0 R, respectively, having a 曱 • 9 and 31 1225481 0 · 1 < η < Condition 0.9: 1. The chemically amplified positive photoresist composition according to item 11 of the patent application range, characterized in that the content of the polymer is between 1% and 30% by weight of the total composition (weight percentage). 1 3 The chemically amplified positive photoresist composition according to item 11 of the patent application, characterized in that the photoresist composition further comprises a photoacid generator, and the content of the photoacid generator is about 0.5% to 10% by weight of the total polymer. % (Weight percentage). 1 4 · The chemically amplified positive photoresist composition according to item 13 of the patent application range, 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 photoresist composition according to item 11 of the patent application scope, characterized in that The composition further comprises an organic base selected from the group consisting of triethylamine, triisobutylamine, triisooctylamine, diethanolamine, triethanolamine or a mixture thereof; and the amount of the organic base used is based on the weight of the total polymer. 0.01% to 2.00 ° /% (weight percentage). 1 6. A semiconductor device prepared from a positive photoresist composition that can be used in ArF as described in item 11 of the patent application scope. 32