TWI230320B - Positive photoresist - Google Patents

Abstract

A polymer with structure (II) is disclosed. R1 is H or alkyl (from C1 to C4). R2 is hydroxyl, alkoxy (from C1 to C8), or alkylthio (from C1 to C8). G is (CH2)n, O or S where n=0, 1, 2, 3, or 4. Rc is lactone, m=1, 2, or 3. This polymer is suitable to be a positive photoresist. This polymer can be used at general semiconductor lithography, especially used at 193 nm light wavelength with higher resolution, sharper shape, and higher sensitive.

Description

1230320 A7 I_ B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (丨) [Technical Field of the Invention] The present invention relates to a photoresist composition, especially a chemically amplified light containing a high molecular polymer A method for applying a resist composition and the chemically amplified photoresist composition of the present invention to lithography imaging. [Background of the Invention] With the rapid increase of the integration level of semiconductor integrated circuits, the line width required by lithography technology is also getting smaller and smaller. Theoretically, in order to make the resolution of the pattern obtained by the lithography process better, a light source with a short wavelength or an optical system with a large aperture can be used. Recently, a polymer with a suitable light source wavelength of 193nm has been published. It is a polymer copolymer polymerized by four kinds of polymer monomers. It is called poly iBMA-MMA-tBMA-MMA (poly isobornyl methacrylate- methyl methacrylate -t-butyl methacrylate-methacrylic acid) ,. Its structure is as follows: ch3 CH,? h3 -C) ^ &w; ww (CH2—C) '/ ww (CH2—C), / VAW c = oc = oc = o ch3

0CH3 c (ch3) 3 (Please read the notes on the back before filling this page)

OH However, the above-mentioned high-molecular polymers have some unsatisfactory aspects. First, the high-molecular polymers copolymerized by the four kinds of high-molecular monomers have a weak resistance to etching, and their adhesive properties are not good. OK, so, ^ ί, order --------- ^ 丨 · ---------------------- 丨 This paper ruler! Printed by the Chinese National Standard (CNS) A4 (2) 0 x 297 per household 1230320 Printed by the Intellectual Property Corporation of the Ministry of Economic Affairs

The present invention is to provide a lithographic imaging manufacturing method for semiconductor devices, especially a 193nm lithographic imaging manufacturing method, which has excellent resolution, contour, and sensitivity. A7 ----, ___ 5. Description of the invention (y) To apply this South molecular polymer to photoresist resists, a new process needs to be developed. In addition, U.S. Patent Nos. 6,271,412, 6'280,898, 6,3 丨 6, 丨 59, and Japanese Patent Publication No. 2001-242627 disclose a variety of different photoresist compositions and are used in semiconductor products. Production of bulk circuit components. The novel photoresist composition disclosed in the present invention can simultaneously have excellent properties such as good hydrophilicity, adhesion and resistance to dryness. These superior properties will increase the adhesion of the photoresist composition to the substrate and increase the photoresist. The film-forming property and the photoresist pattern after development are less likely to fall. In addition, due to the increased hydrophilicity, the developing solution can be evenly distributed on the surface of the photoresist, thereby improving the uniformity of the surface of the photoresist pattern. The main object of the present invention is to provide a chemically amplified photoresist composition. The chemically amplified photoresist composition is used in a lithography imaging process and has excellent resolution, contour, and sensitivity. The chemically amplified photoresist composition of the present invention has the following formula. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 f love). ----------- Order --- ( Please read the precautions on the back before filling in this page) i · / · 1230320 A7 V. Description of the invention (^) (II) High molecular polymer R1 with structural repeating unit

〇〇R2 (CH2) m Rc (II) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R1 is a pyrene or CVC4 alkyl group; R2 is a methyl group, Ci-Cs alkyloxy group, or Ci-Cs alkylthio group G is (CH2) n, oxygen, or sulfur, where η is an integer of 0 to 4; Rc is a lactone group; m is an integer of 1 to 3. The chemically amplified photoresist composition of the present invention mainly includes a high molecular polymer having a structural repeating unit of formula (II), and may further include other components according to actual needs: a photo-acid generator (PAG), The components include an acid quencher, an additive, and a solvent. The chemically amplified photoresist composition of the present invention can be maturely applied to a general lithography imaging process, especially a 193nm lithography imaging system ^, and has excellent resolution, contour, and sensitivity. The lithography and 1k methods are well known to those skilled in the art and will not be repeated here. The present invention is also related to the aforementioned chemically amplified photoresist composition ~ is intended to be used for semiconducting 'paper size applicable to China National Standard (CNS) A4 specifications (210 X 297 heli) (Please read the precautions on the back before filling this page )-· H ϋ ϋ ϋ ϋ ϋ aδ, · H ϋ ϋ ϋ I ^ 1 1 I ϋ n ϋ ϋ I ϋ ϋ H IIIH ϋ I ϋ I ϋ ϋ ϋ n ϋ I ϋ. 1230320

V. Description of the invention (present) 70 pieces "lithographic imaging manufacturing method, especially the exposure step of the lithographic imaging manufacturing method, using a light source with a wavelength of 193 ㈣. The lithography imaging method of the present invention has excellent resolution, contour, and sensitivity. [Specific description of the invention] The polymer containing a repeating unit of the formula (Π) in the composition of the present invention is composed of the compound R1 of the following formula (I)

(Please read the notes on the back before filling out this page) The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs prints an alkyl group in which R1 is pyrene or CVC4; R2 is a hydroxyl group, (^-(: 8 alkoxy or CVC: 8 Alkylthio; G is (CH2) n, oxygen or sulfur, where η is an integer from 0 to 4; Rc is a lactone group; m is an integer from 1 to 3, and self-polymerization is performed in the presence of a catalyst, Or it can be copolymerized with other high molecular monomers containing acetamidine functional group to produce a high molecular polymer. With regard to the preparation of the compound of formula (I), the following formula can be used (step 1 to step 5) Synthesis, but not limited to the following methods: This paper size applies to China National Standard (CNS) A4 specifications (210 x 297 $ cent)

f 'I · nn ϋ ^ OJ · ϋ ϋ I ϋ n II ϋ ϋ ϋ ϋ I ϋ ϋ ^ 1 ϋ I 1_1 n ϋ ϋ ϋ 1 ϋ ϋ ϋ1 I n ϋ ϋ I 1230320 A7 ------ -B7 ___ V. Description of the invention (k) " ~ ~ ~-Step 4 (step 4) is the product obtained in step 3 under acidic conditions with appropriate nucleophiles (such as water, alcohols and thiol compounds) A ring-opening addition reaction is performed to obtain a derivative having a light group. Step 5 (steP 5) is the esterification reaction of the product obtained in step 4 with (alkyl) acryloylchloride or propylene chloride to obtain the compound of formula (I). The aforementioned photosensitive polymer of the formula (I I) of the present invention can be formed by a copolymerization reaction between the compound of the formula (I) and other different acetamidine-containing polymer monomers in the presence of a catalyst. There are no particular restrictions on the selection of the other different high-molecular monomers containing acetamidine functional groups; however, in order to make this high-molecular polymer capable of being penetrated by a 193nm light source, a non-aromatic structure is selected. A polymer monomer containing an ethylene functional group, so that the polymer can be penetrated by a light source of 193 nm. Among them, the polymer monomers containing ethylene functional groups can be listed as follows: (where R3 is fluorene or C1 ~ C4 alkyl)-· ---- (Please read the precautions on the back before filling this page) Order ---------line!

1230320 A7 Β7 V. Description of the invention (Ί) R3 " r3 '/ {ο 〇 〇 fe, δ R3, / R3 / = ° 〇-{〇 R3, R3, R3 > 〇) 〇 R3 / > 〇

〇

〇 〇

(Please read the notes on the back before filling this page) _ · ---- ch2oh c〇2h

HO

〇 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Compounds of formula (i) can be synthesized by self-polymerization or copolymerization reactions to polymer polymers containing repeating units of formula (II):

1 ° J · ϋ n I in ϋ in an I 1 ϋ l · ϋ n ϋ ϋ ϋ ϋ ^ 1 ^ 1 n · ϋ ϋ ^ 1 ϋ ni ^ i 1.1 I This paper size applies to China National Standard (CNS) A4 (210 X 297 & li) ί / · 3 · 1230320 A7 B7 Printed by the Consumer Consumption Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of Invention (X) R1

(II) wherein R1, R2, G, Rc, and m are as defined above. The compound of formula (I) can be polymerized by itself or in combination with one or more other high molecular monomers containing ethylene functional groups to produce a high molecular polymer. Among them, the preferred ones include the following formula (III), formula (IV) Or high molecular polymer of formula (V):

This paper size applies to Chinese National Standard (CNS) A4 (210 X 297) (Please read the precautions on the back before filling out this page)! · Nn ϋ ϋ H n H-5, 1 ϋ III ϋ ϋ ϋ II ϋ ϋ I ϋ ϋ ϋ n ϋ III ϋ ϋ H ϋ I ϋ ϋ i ϋ ϋ ϋ.

R

', The middle R ruler and ruler are hydrogen or methyl, and g + h + i = i 戋 g + h + 1 + j = 1; more preferably, where g / (g + h + i) = 0.01 To 0.5, 'h / (g + h + 1) = (M to 0.5, i / (g + h + i) = 〇i to 〇5, or (rule) = 0.01 to 0_5, h / ( g + h + i + i) —n! Ben n < w /, δ n 1 10 J 0 0 to 1 · 5, " (g + h + i + j) = 0 ″ to 0.5, and j / (g + h + i + j 〇 ″ to 〇 5 〇 The above-mentioned polymer can be used alone, two or more than two mixed. The fluorene molecular polymer used in the present invention is preferably, It is soluble in organic solvents, and has a glass transition temperature Tg between 50 and 22 (rc, a molecular weight between 1,000 and 500,000, and a decomposition temperature Td greater than 800c. The fluorene molecular polymer used in the present invention The synthesis method is not particularly limited, and it is preferred to mix the above polymer monomers and polymerize in the presence of a catalyst initiator. The catalyst initiator can be used by those skilled in the art. Catalyst, but the preferred catalyst initiator is 2,2'-azo-bis-isobutyronitrile (2,2'-azo-bis-isobutyronitrile; AIBN) or dimethyl 2,2 , -Azobisisobutyl ester radical initiator This paper has been oversized using Chinese National Standard (CNS) A4 specifications (21 × 297 & Love)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1230320 A7 B7 V. Description of the invention (1.) (dimethyl_2,2, _azo-bis-isobutyrate radical initiator; V-601) 〇 The chemically amplified photoresist composition of the present invention, A high-molecular polymer including structural repeating units of formula (II), and other components such as a photo acid generator (PAG), an acid quencher, an additive, and a solvent. The photoacid generator used in the present invention is not particularly limited, as long as the current can be generated by irradiation with ultraviolet rays or other radiation. Other basic requirements are that it can have a certain degree of stability before exposure to avoid affecting the process. reliability. The better photoacid generator can be: (Please read the precautions on the back before filling in this page) ------- 丨 Order --------- Line I ------- ----------------

CM s C8 03 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

: 9S〇a

π3 c

1230320 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

(Please read the notes on the back before filling this page) €.

1 · I > ^ 1 · 1 I 1 II III ϋ na ^ i · ϋ I ϋ ϋ ϋ ϋ ϋ n ϋ 1 ^ 1 ϋ (ϋ ϋ ^ 1 ϋ I This paper standard applies to China National Standard (CNS) A4 Specifications (210 x 297

V. Description of the invention (1230320 The photoacid generator mentioned above can be used alone, two or more of them can be mixed. Under 100 parts of resin weight, the amount of photoacid generator can be 0.1 to 20 parts, which is better. The addition amount is 0.5 to 7 parts (all ratios here are calculated by weight). The acid trapping agent of the present invention is used to adjust the diffusion characteristics of the sexual ions generated by PAg in the photoresist to make the photoresist. Better characteristics. The preferred acid trapping agents suitable for the present invention are: tetrabutylammonium hydroxide, tetrabutylammonium lactate, tributylamine, trioctylamine , Triethanolamine, tri [2- (2-methoxyethoxy) ethyl] amine, tris [2- (2-methoxyethoxy) ethyl] amine, N_ (2,3-dihydroxypropyl) group ) Six-mouth-to-mouth syndrome (N- (2-hydroxyethyl) piperidine), morpholin, N_ (2-hydroxyethyl) morpholin, N_ (2-hydroxyethyl) N- (2-hydroxyethyl) pyirolidine, or N- (2-hydroxyethyl) N- (2-hydroxyethy l) piperazine) and so on. The addition amount of the acid trapping agent may be 0.001 to 10 parts of the photoacid generator, and the preferable addition amount is 0.01 to 1 part per part of the photoacid generator (all proportions herein are calculated by weight) ° The additives of the present invention are not particularly limited, and can optionally be added with appropriate amounts of sensitizers, dissolution inhibitors, surfactants, stabilizers, and paper size. Applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page)

-'«III — — — — I-01 IIII — IIIIIIIIIIII ^ III ^ Shengtong ^ I 1230320 V. Description of the invention (dyes and other resins, making the photoresist to meet the required requirements. II tr line use There are no particular restrictions on the solvents used in the manufacture of the chemically-based photoresist composition of the present invention. Examples include higher alcohols (eg, n-octanol), vinegars such as glycolic acid (eg, lactic acid, vinegar, ethyl lactate, or Ethyl glycolate), Glycol ethers, "German derivatives (for example: ethylene glycol acetate acetic acid, ethylene glycol methyl ether acetate or propylene glycol monoacetate acetate), isopropyl vinegar (for example: propyl (E.g. methyl vinegar or ethyl pyruvate), oxybenzoic acid @purpose (for example: ethyl 2-ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate Vinegar or methyl ethoxypropionate), ketone derivatives (for example: methyl ethyl ketone, methyl amyl ketone, acetoacetone, cyclopentanone, cyclohexanone or 2-heptanone), keto ethers Derivatives (for example: diacetone methyl ether), keto alcohol derivatives (for example, methanol or diacetone), alcohol bond derivatives For example: Ethylene glycol butyl ether or propylene glycol), amine derivatives (for example: dimethylacetamide or dimethylformamide), ether derivatives (for example: anisole or diglyme Ether) or a mixture thereof, among which n-octanol, propylene glycol monomethyl ether acetate, ethyl 2-ethoxyacetate, methyl 3-methoxypropionate, methyl ethoxypropionate, methyl ethyl Ketones, methylpentyl ketones, cyclopentanone, methyl lactate, ethyl lactate, ethylene glycol butyl ether, propylene glycol acetic acid, or mixtures thereof are preferred as the solvent for the main component. A suitable solvent weight is 100 parts by weight. Resin weight, 200 to 2000 parts of solvent is added, and 400 to 1000 parts is more preferable (all proportions are calculated by weight). The chemically amplified photoresist composition of the present invention is obtained by mixing the above It can be obtained by dissolving the above-mentioned high-molecular polymer in a solvent, and then mixing other components. Or the other papers except the high-molecular polymer can be used in accordance with Chinese National Standard (CNS) A4. (210 X 297 g centimeters

V. Description of the invention (J 1230320 The components are mixed and dissolved in the solvent, and then mixed into the polymer. The amount of impurities (such as trace metals and halogens) contained in the chemically amplified photoresist composition should be reduced as much as possible. Before mixing the components to obtain a chemically amplified photoresist composition, purification can be applied to improve the purity. Alternatively, the components can be mixed to obtain a chemically amplified photoresist composition, and then purified before use. The present invention < chemically amplified photoresist composition can be maturely used in general lithography imaging processes, and more particularly, the chemically amplified photoresist composition of the present invention can be applied to general traditional wavelength light except In addition to the lithographic imaging process of lithography, it can also be applied to the lithographic imaging process of 193nm light. The chemically amplified photoresist composition of the present invention can be patterned using conventional methods. For example, the chemically amplified photoresist composition Coating on the substrate, followed by steps of exposure, development, etc. The substrate can be a hard wafer or have a variety of materials, and the coating can be applied by, for example, transfer coating , Spraying method or roll coating method. After the substrate is coated, it is usually placed on a hot plate to remove the solvent, and then exposed through a photomask to form the desired pattern on the substrate. The imaging solution can be selected from ammonia, triethylamine, dimethylamine, methanol, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or dimethyl emulsified dimethyl ethyl acetate. The chemically amplified photoresist composition of the present invention has excellent resolution, profile, and sensitivity, and has excellent performance in the depth of focus, exposure boundary, and removal boundary. In order to better understand the present invention The technical content, especially the better specific implementation (please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy-·· ------- —1T — ^ — 线- ---------------------- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 1230320 A7 B7 V. Description of invention (6 examples are explained below) [Preferred Embodiment of the Invention] Preparation Example 1: Synthesis of Polymer Monomer (I · 1) 0

Η + ChUOhT

Methacryloyl chloride CH2CI2 / Et3N 〇

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 16.6 g of 8,9-epoxy-3-one-4-oxo-sancycline [5.2.1.〇2'6] decane was dissolved in 200 ml of methanol. 0.25 ml of concentrated sulfuric acid was added. After the reaction was completed, the solution was neutralized. After concentrating, 200 ml of dichloromethane and 10.2 g of triethyl amine were added, and then 10.5 g of methyl propane was added. Chlorine (methacryloyl chloride), stir until the reaction is complete. After filtration and cycloconcentration, it was separated by chromatographic analysis to obtain 9-methoxy-5-one-4-oxo-reference ring [5 · 2 · 1 · 02,6] dec- 9-methoxy-5-oxo-4-oxa-tricyclo [5.2.1.02,6] dec-8-yl methacrylate) (1-1) 18.9 g (yield: 75%). Spectral identification: h-NMR (CDC13, 300MHz) d 5.89 (1H, brs), 5.37 (1H, brs), 4.81 (lH, m), 3.96 (lH, m), 3.67_3 · 57 (2H, m ), 3.54 (3H, s), 2.79 (1H, m), 2.57 (1H, m), 2.55 (1H, m), 2.37 (1H, m), 1.77-1.74 (4H, m ), 1.38 (1Η, m) 〇13C-NMR (CDC13, 75MHz) cM71.4, 165.6, 136.0, 124.8, 84.9, 79.5, 70.0, 51.0, (Please read the precautions on the back before filling this page) -·· -------- tr ---- ά / φ ---------------------- This paper size applies to Chinese National Standards (CNS ) A4 specification (210 x 2971 | centi) 1230320 A7 _____JB7_ V. Description of the invention (| b) 46.1, 45 · 7, 40.4, 39.1, 32.4, 17.8 Preparation Example 2: Polymer monomer (I · 2) Synthesis 〇Η +

_ acryloyl chloride CH3OH CH2CI2 / Et3N 〇

(1-2) The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 16.6 grams of 8,9 · epoxy-3-one-4-oxo-shen ring [5 · 2 · 1 · 〇2，0] Decanoate was dissolved in 200 ml of methanol, and 0.25 ml of concentrated sulfuric acid was added. After the reaction was completed, the solution was neutralized. After concentrating, 200 ml of dichloromethane and 10.2 g of triethyl amine were added Then, add 9.1 g of acrylyl chloride and stir until the reaction is complete. After filtration and cycloconcentration, separation by chromatographic analysis, a light yellow oily liquid product, 9_methoxy-5-one-4-oxanacycline [5 · 2_1 · 02,6] dec-8-yl, was obtained. 18.9 g (9-methoxy-5-oxo-4-oxa-tricyclo [5.2.1.02,6] dec-8-yl acrylate) (1-2) (yield: 75%). Spectral identification: j-NMR (CDC13, 300MHz, J in Hz) β 6 · 38 (1H, dd, J = 17.4, 0.6), 6 · 11 (1H, dd,] = 17 · 4, iq 5), 5.82 (1H, dd, J = 10.5, 0.56), 5.01 (1H, brs), 4 ″ 7 (ipj, d, J = 5.0), 3.86 (1H, d, J = 5.6), 3.79 (1H, dd, J = 56, 2.7), 3.72 (3H, s), 2.95 (1H, m), 2.81 (1H, m), 2.73 (ijj, m), 2.56 (1H, brs), 1.95 (1H , D, J = 10.9), 1.57 (iH, d, J = 10.9) 〇 (Please read the precautions on the back before filling this page) — Zhao -------- Order ----

Line — _----------------------- A7 1230320 V. Description of the invention (1 13C-NMR (CDCI3, 75MHz) d 171 · 9, 165.0, 130 · 7, 128.6, 85.4, 80.0, 70.5, 51.6 46.7, 46.2, 40.8, 39.6, 32.9 〇 Preparation Example 3: Synthesis of polymer monomer Η + Repeat the procedure of Example 2 and change to 3,4-epoxy 7-keto-8-oxy-bicyclo [4.3.0] i) fe (3,4-epoxy-7-oxo-8-oxa-bicyclo [4.3.0] nonane) replaces 8,9-epoxy-3- Keto-4-oxo-reference ring [5.2.1.02,6] decane (8,9-epoxy-3-oxo-4-oxa-tricyclo [5.2.1.〇2,6] decane) as the starting material, And using anhydrous ethanol instead of methanol as the solvent to carry out the reaction, a colorless oily liquid product 4-ethoxy-9-one-8-oxy-bicyclo [4.3.0] non-3-ylpropene ester (4-ethoxy -9-oxo-8-oxa-bicycl0 [4.3.0] non-3-yl acrylate) (1-3). Spectral identification: W-NMR (CDC13, 300MHz, J in Hz) β 6 · 28 (1H 'dd' J = 17.4 '1.8), 5.99 (1H, dd, J = 17.4, 10.6), 5.75 (1H' dd , J = 10.6, 1.8), 4.91 (1H, brs), 4.11 (1H, m), 3.85 (1H, m), 3 · 5 8 (1H, m), 3.44 (1H, m), 3 · 22 (1H, m), 2.61-2.47 (2H, m), 2.25 (1H, m), 1.91-1.72 (2H, m), 1.09_0 · 97 (5H, m) 〇13C-NMR (CDCI3 , 75MHz) I This paper size is applicable to China National Standard (CNS) A4 (210 x 297 @ 7 (Please read the precautions on the back before filling this page)

Ο acryloyl chloride C2H5〇ri CH2CI2 / Et3N

Ο

Order --- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 11 I ---------------------- 1230320 A7 B7 V. Description of the Invention (θ) 〇71 -6, 164.7, 130.9, 128.0, 71.2, 70.8, 69.2, 63.8, 35.7, 30 · 3, 25_1, 20.7, 14.9. Preparation Examples 4 to 7 The steps in Preparation Example 1 were repeated, and the reaction was performed with different starting materials and solvents. The results are shown in Table A. Table A _ Starting Material Solvent Product

、 This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 & centimeters (please read the precautions on the back before filling this page) -------- Order · --- 1-4

1-6 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1230320 A7 V. Description of Invention (彳) B7

Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Preparation Example 8 Synthesis of high molecular polymer type (II-1). 20 ml of tetrahydrobuffan and tert-butyl methacrylate were added to the reactor. ) 2.13 g, 2-methyl-2-adamantyl methacrylate (2_methyl_2-adamantyl methacrylate) 4.69 g, and 9-methoxy-5 (or 3) -one-4-oxo · ring ring [5 · 2 · 1 · 02,6] dec-8-ylmethylpropanyl ester (9-methoxy-5 (or 3) -oxo-4, oxa-tricyclo [5 · 2 · 1 · 02,6] dec_8-yl methacrylate) 3_99 g, and then add 1.1 g of 2,2'-azobisisobutyl (AIBN) as the starter, and raise the temperature to 65 to 70 ° C. After the reaction is complete, add 20 ml of tetrahydrofuran The reaction product was poured into a container filled with 1 liter of hexane to cause precipitation of a white solid. After filtration and drying, 8.43 g of a high molecular polymer white powder with the following formula (II-1) was obtained, with a yield of 78%. GPC measurement, weight average molecular weight 14,100, glass transition temperature Tg two 169. (:. (Please read the notes on the back before filling out this page) Zhang scale is applicable to China National Standard (CNS) A4 specifications (210 X 297-* · ------- — Order ------- -^ I AW ----------------------- 1230320 A7 B7 V. Description of the invention (,) CH〇CH3 CH,

(II _ 1) ϋ * ^ 1 · ϋ n ϋ ni ^ i ϋ I · ni an (Please read the notes on the back before filling in this page) [g = 0.30, h = 0.40, i = 0.30, Mw = 14100] Preparation Example 9 Synthesis of high molecular formula (II-2) In the reactor, 20 ml of tetrahydrofuran and tert-butyl methacrylate 2 · 1 3 g, 8_ Methyl reference ring [5.2.1.02,6] dec-8-yl methacrylate (8-methyltricyclo [5 · 2 · 1 · 02'6] deca-8-yl methacrylate) 4.69 g and 4-ethyl Oxy-7 (or 9) -one-8-oxy_bicyclo [4.3.0] non-3_ylmethylpropanyl ester (4-ethoxy-7 (or 9) -oxo-8-oxa-bicyclo [ 4.3.0] non-3-yl methacrylate) 4.02 g, then add the starter 2,2, -azobisisobutyl- 2 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1. · Base 1 · 1 g , And the temperature was raised to 70 ° C, and after reaction overnight, 20 ml of tetrahydrofuran was added, and then the reaction product obtained above was poured into a container filled with 1 liter of sintered, so that a white solid precipitated, which was dried by filtration, 6.83 g white polymer powder of the following formula (π -2) can be obtained with a yield of 63%, measured by Gpc. An average molecular weight of 19,200, a glass transition temperature Tg = l2rc.

1230320 A7 B7 V. Description of the invention (d) ch3 ch3

〇

〇 Formula (Π-2) [g = 0.30, h = 0.40, i = 0.305 Mw = 19200] Preparation Examples 10 to 34 Repeat step 1 of Example 1 and use different monomers to polymerize to obtain white powder. Polymer, the synthesis results are shown in the following formula (11-3) to formula (11-27),

〇 Formula (II _3) [g = 0.30, h = 0.40, i = 0.3 (Mw = l6200] (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

(II -4) [g = 0.30, h = 0.40, i = 0.3 丨 Mw = 18700]

· N H ϋ n ϋ ϋ. 一 S ^ J · m ϋ n ϋ —ϋ II---ϋ ϋ ϋ I ϋ 1-ϋ li- I n I-ϋ -1 ϋ-I— I Private paper scale Applicable to China National Standard (CNS) A4 specification (210 x 297 1230320 A7 B7 V. Description of the invention (> ^) ch3 ch3

ο Formula (II -5) [g = 0_30, h = 0.40, i = 0.30 Mw = 17300]

(II _6) [g = 0.30, h = 0.40, i = 0.30, Mw = 15400] (Please read the precautions on the back before filling this page) CH3

〇 Formula (II_7) [g = 0.30, h = 0.40, i = 0.30, Mw = 14600] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Γ ch3 ch3

Formula (II -8) [g == 0.50, h = 0.10, i = 0.40 Mw = l 0200] * tr ----- ----- line ι · ----------- ------------ This paper size applies to China National Standard (CNS) A4 (210 x centimeter) 1230320 A7 B7 V. Description of the invention (/)

OC2H5 formula (II _9) [g = 0.50, h = 0 ″ 0, i = 0.40, Mw = 9700]

〇 Formula (II-10) [g = 0.50, h = 0.10, i = 0.40 Mw = 11600] (Please read the precautions on the back before filling out this page). system

〇 Formula (π-ll) [g = 0.50, h = 0.10, i = 0.40, Mw = 11500] Formula (II-12) [g = 0.50, h = 0.10, i = 0_40, Mw = 9300]-line 丨-^^ ---------------------- This paper size applies to China National Standard (CNS) A4 (210 X ^ centimeter) 1230320 A7 V. Description of the invention ( 4) ch3 ch3 ch3

〇 B7 formula (11-13) [g = 0.50, h = 0.10, i = 0.40, Mw = 8700]

(11-14) [g = 0.05, h = 0.30, i = 0.40, j = 0_25, Mw = 10500] (Please read the precautions on the back before filling this page) Φ CH3 ch3

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

HO P〇2H5 Formula (II-15) [g = 0.05, h = 0_30, i = 0.40, j = 0.25, Mw = 13300] Formula (II_16) [g = 0.05, h = 0.30, i = 0.40, j = 0.25, Mw = 12600]

* One SOI »i ^ in ϋ II ϋ ^ 1 ί I ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ^ 1 ^ 1 II 本 II This paper size applies to China National Standard (CNS) A4 (210 x mm) 1230320 A7 B7 V. Description of the invention (〆) Cl-b CH3 CK3 Cl-b

Equation (π_17) [g = 0.05, h = 0_30, i = 0.40 j = 0.25, Mw = 9500]

PH formula (II_18) [g = 0.05, h = 0.30, i = 0.40, j = 0.25, Mw = 11100] (Please read the precautions on the back before filling this page) CH CH3 CH;

O, OCH3 formula (II_19) [§ = 0.05, h = 0.30, i = 0.40, j = 0.25, Mw = 11700]

........... 7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3

HO pCH3 formula (II -20) [g = 0.05, h = 0.40, i = 0.30, j = 0.25, Mw = 10800] This paper size applies to China National Standard (CNS) A4 (210 x mm) I · n I ϋ · ϋ ϋ ϋ I I · ϋ ^ 1 ϋ ϋ ^ 1 ϋ ϋ I ϋ ϋ ϋ 1 · ϋ ϋ ϋ I ϋ ^ 1 ϋ ϋ ϋ ϋ I ϋ ϋ > .1 H ^ 1 ϋ n. 1230320 A7 B7 V. Description of the invention (〆〇

〇 Formula (II-21) [g = 0.05, h = 0.40, i = 0.30, j = 0.25, Mw = 9600] Formula (11-22) [g = 0.05, h = 0.40, i = 0.30, j = 0.25 , Mw = 9900] (Please read the precautions on the back before filling this page)

Chb Chb

Formula (II -23) [g = 0.05, h = 0.40, i = 0.30 j = 0.25, Mw = 10500] I I .---I -I --------δ 3 Intellectual property of the Ministry of Economic Affairs Printed by Bureau employee consumer cooperative

〇 This paper size applies the Chinese National Standard (CNS) A4 specification (210 x @ 7mm)-δι · ϋ ϋ ϋ I I I ϋ ϋ —ϋ ϋ ϋ ί I ϋ a ^ i ϋ in n in I I ϋ n-1230320

Description of the invention (β)

Formula (II · 26) [g = 0.05, h = 0.40, i = 0.45, j = 0.10? Mw = 13400] Formula (11-27) [g = 0.05, h = 0.40, i = 0.45, j = 0.10, Mw = 1 1700] (Please read the precautions on the back before filling this page) Example 1 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and the photoresist composition formula (Η-1 ) 2 g of high molecular polymer, triphenyl sulfonium perfluoro-1-butanesul fonate (TPS-PFBS), 0.05 g and tert-butyl cholate; TBC) 0.06 g, propylene glycol monomethyl

This paper size applies to China National Standard (CNS) A4 (210 X ^ $ 7 mm) AA. · «1 ^ 1 ϋ 1- · 1 ϋ ^ aJβ ΜΗ MB ·! Ea Μ» Tengxian — .---- ------------------- 1230320 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (J) propylene glycol monomethyl ether acetate; PGMEA) 10.4 g and N- (hydroxymethyl) piperidine 0.5 mg, mix well, and then filter this solution with a filter of 0.45 μm, then apply this solution Cover a silicon dry sheet and spin-coat at 2800 rpm for 30 seconds to obtain a uniform film. This film was then dried at 130 ° C for 90 seconds to obtain a 306.7 nm thick film. After the film was irradiated with deep ultraviolet (DUV) at an energy of 10 to 30 mj / cm2 at 193 nm, the dry sheet was heated on a hot plate at 130 ° C for 90 seconds. Then, a 2.38% tetramethyl ammonium hydroxide (TMAH) aqueous solution was used to visualize the irradiated film, washed with deionized water, spin-dried, and scanned and analyzed the structure of the photoresist with an electron microscope. μιη resolution structure. Examples 2 to 16. 6. The photoresist composition formula was repeated as described in Example 1. The polymer obtained in Preparation Examples 9 to 15, 21 to 27, and 31 was used instead of the polymer in Example 1. The results are shown in the following table B: nf ---- (Please read the precautions on the back before filling in this page) Order——1 ----- line—0 Table B Thickness of polymer film (nm) Resolution (μηι) Example 2 (II-2) 317.8 0.18 Example 3 (II-3) 326.0 0.18 This paper size is applicable to Chinese national standards (CNS> A4 specification (2〗 0 X Μ? Today) 1230320 V. Description of the Invention (d) A7 B7 Example 4 (II-4) 298.5 0.15 Example 5 (II-5) 278.8 0.15 Example 6 (II-6) 321.0 0.15 Example 7 (II-7) 306.8 0.18 Example 8 (II-8) 304.5 0.15 Example 9 (11-14) 320.7 0.20 Example 10 (II-15) 334.9 0.20 Example 11 (II-16) 310.2 0.15 Example 12 (II-17) 296.6 0.15 Example 13 (II-18) 275.8 0.15 Example 14 (II-19) 330.5 0.18 Example 15 (11-20) 309.7 0.15 Example 16 (II-24) 318.5 0.20 丨 -------- ^- -7 (Please Read the back of the precautions to fill out this page) Ministry of Economic Affairs Intellectual Property Office employees consumer cooperatives printed

AP The chemically amplified photoresist composition of the present invention can be maturely applied to general lithography imaging processes, especially 193nm lithography imaging processes, and has excellent resolution, contour, and sensitivity. In summary, the present invention, regardless of its purpose, means, and effect, shows its characteristics that are quite different from the conventional technology. However, it should be noted that many of the above-mentioned embodiments are merely examples for the convenience of explanation. The scope of the claimed rights should be based on the scope of the patent application, rather than being limited to the above embodiments. Applicable to China National Standard (CNS) A4 specification (210 x 297) Fine I I I ----------------------

Claims (1)

1230320 A8 BS C8 D8 6. Scope of Patent Application 6. For the composition of the scope of patent application item 1, G is oxygen or sulfur. 7. For example, the composition of claim 1 in the scope of patent application, wherein the high molecular polymer is the following formula (Π-1), (Π-2), (Π · 3), (Π · 4), (Π- 5), (Π-6), or (Π-7): ch3 〇 Formula (π CH Seal of the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇 Formula (Π-2 〇 〇 Formula (Π- The size of this paper is applicable to 0S Standards (CNS) A4 (210 X 29 ^ Public issued) 1230320 A8 B3 C8 D8 VI. Application for patents (Please read the notes on the back before filling out this page)!% Then fill in the husband ------- order ----- 1 ---- line ------------- -r ------------ The size of this paper is 0 National Standard (CNS) A4 Regulation (210 X 2 to 5 issued) 1230320 Αδ BS C8 D8 12), or (Π- 13): ch3 ch3 ch. PCH3 6. Scope of patent application Where g + h + i = 1. 8. If the composition of the scope of application for item 7 of the patent, wherein g / (g + h + i) 0.01 to 0.5, h / (g + h + i) = 0.1 to 0.5, and i / (g + h + i) = 0.1 to 0.5. 9. The composition of item 1 in the scope of patent application, wherein the polymer is the following formula (Π-8), (Π-9), (Π 10), (Π-11), (Π- (Π-8) First, read the precautions on the back, this book · page I w IIII order CH3 ch3 Line Consumer Goods Cooperative Association of the Intellectual Property Bureau of the Ministry of Economic Affairs Formula (Π-9) 〇 The paper size is suitable for 0 national standard (CNS) A4 specifications (210 > < 2 # publicly available 1230320 A8B3C8D8 VI. Patent application scope CH, 〇 Formula (Π-10 〇 Formula (Π-11) Formula (Π-12 Read the note on the back side of the book 瓤 This page 1 I ^ I I I I LINE Sealed by the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇 Formula (Π-13 This paper is suitable for the standard of the Chinese Standard (CNS) A4 (210x2 in / issued 1230320 A8 B3 C8 D8) 6. Application scope of patents where g + h + i = 1. 10 · For example, the composition of the 9th patent application scope, where g / (g + h + i) = 0.01 to 0.5, h / (g + h + i) = 0.1 to 0.5, and i / (g + h + i) two 0.1 to 0_5. 1 1 As the composition of the first scope of the patent application, wherein the high molecular polymer is the following formula (Π-1.4), (Π-15), (Π-16) , (. Π-17), (Π-18), or (Π19) ·· Please read the notes on the back of this page m Page 1 of this page I Printed by the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^^ Formula (Π-14 Formula (Π 15 〇 I I I Alignment) The paper size is applicable to the standard of China Standard (CNS) A4 (210 X 29 ^ public) 1230320 A8 B8 CS D8 6. Apply for the patent * (Π- 16) CH3 ch3 ch (Π-17 Please read the notes on the back first, the discussion of this book, page order ch3 ch3 ch3 (Π _ 18) Line Printed by the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economy ^ i CH3 CH3 ch3 HO formula (Π-19) This paper size is applicable to 0 National Standards (CNS) A4 specifications (210 x 2 # public hair) 1230320 r \ 〇B8 C8 D8 Six, the scope of patent application where g + h + i + j: = i. 1 2 · As for the composition in the 11th scope of the patent application, where g / (g + h + i + j) = 〇 · 〇1 to 0.5, h / (g + h + i + j) = 0.1 to 0 · 5. i / (g + h + i + j) = 0.1 to 0.5, and j / (g + h + i + j) = 0.1 to 0.5. 13. The composition according to item 1 of the scope of patent application, wherein the high molecular polymer is the following formula (Π-20), (Π-21), (Π-22), or (Π-23): (Π- 20) 〇 pC2H5 (Π-21 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Grid A4 S) N (C quasi-standard country 0 suitable & rule paper ¾ male X ο 1230320 A8B3C8D8 VI. Patent application scope ch3 ch3 ch3 ch3 CH3 CH3 CH3 CH3 Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs print li where g + h + i + j = l. 14. For the composition of the scope of application for item 13, where g / (g + h + i + j) E01 to 0.5, h / (g + h + i + j) = 0.1 to 0.5, i / (g + h + i + j) = 0.1 to 0.5, and j / (g + h + i + j) = 0.1 to 0.5. 15. If the composition of the scope of application for item 1 of the patent, wherein the high molecular polymer is the following formula (Π-24), (Π-25), (Π-26), or (Π-27): this paper Standards are applicable to China National Standards (CNS) A4 regulations (210 X 2 # publicly available 1230320 A8B8C8D8) 6. Scope of patent application CH, 5 2H C Π ------------- ·%, --- (Please read the notes on the back before filling out this page) Order C Printed by the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Π type Π type -line-The paper size is suitable for the 0 national standard (CNS) A4 specification (210 X 2 private release) A8SC8D8 1230320, the scope of patent application ', medium g + h + i + j = l. 16. The composition of item 15 in the scope of the patent application, wherein g / (g + h + i + j) 0.001 to 0.5, h / (g + h + i + j) = 〇. 1 to 0.5, i / (g + h + i + j), 0.21 to 0.5, and j / (g + h + i + j) = 0.1 to 0.5. 17. The composition according to item 1 of the patent application range, wherein the high molecular polymer can be 'organic solvent' and the glass transition temperature Tg is between 50 and 220. (In between, the molecular weight is between 1,000 and 500,000, and the decomposition temperature Td is greater than 80 ° C. Sealed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 8. The composition in item 1 of Shenqiao's patent scope, where the photoacid generator 2 is: 1230320 A8 B8 C8 D8 6. Scope of patent application Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to 0 National Standard (CNS) A4 specifications (210 X 2 to public money 1) 6. Scope of patent application 0 No 0 ii ir μ F3C-SCS--CF3 〇〇19. If the composition of the scope of patent application No. 18, wherein the weight of the photoacid generator can be added per 100,000 parts of the resin weight, add 0 to 20 servings. 〇〇II 〇 一 S II 〇20. For example, the oldest composition in the scope of patent application, # includes an acid trapping agent (Add quencher), the acid trapping agent is tetrabutylammonium hydroxide (tetrabutylammonium hydroxide), lactate Tetrabutylammonium lactate, tributylamine, trioctylamine, triethanolamine, tri [2- (2-oxoethoxy) ethyl] amine Ministry of Economic Affairs Seals of employees of the Property Bureau Consumers Cooperatives (tris [2- (2-methoxyethoxy) ethyl] amine), N- (2,3-dihydroxypropyl) Hexahydrokoupidin (N- (2,3-dihydroxypropyl) ) piperidine), N- (2-Ethyl) piperidine (N- (2-hydroxyethyl) piperidine), morpholin, N- (2-Ethyl) morphine (N- (2-hydroxyethyl) morpholin), N- (2-Ethyl) via mouth (N- (2-hydroxyethyl) pyrrolidine), or N- (2-Ethyl) via mouthhead ( N- (2-hydroxyethyl) piperazine). This paper standard is applicable to China National Standard (CNS) A4 Regulations (210 X) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1230320 D8 VI. Application for Patent Scope 2 1. If the composition of item 20 of the patent scope is applied, of which The acid scavenger may be added in an amount of 0.001 to 10 parts per part of the photoacid generator. This paper is suitable for 3 Chinese National Standard (CNS) A4 regulations (210 X) 12 recommended ρ8 February 1993 revised page A7 B7 won J9 η 93. 2. 27 W ^ \ Supplement 1 [Diels-Alder] Step 1 H〇 、 ^ [Reduction]-^ Step 2 Peroxide -► Step 3 H + (Please read the notes on the back before filling in this page) 〇Step 4 〇〇Ji, CI Λ -► R2 /, b Step 5 Ministry of Economy The Intellectual Property Bureau employee consumer cooperatives have printed the definitions of R1, R2 and G as described above. Step l (step 1) is to select an appropriate diene compound, such as: butadiene (131 ^ & (1 丨 611 €), cyclopentadiene (〇) ^ 1〇06111 & (116116), ° Di (: [\ ^ 11), σ thiophene, etc., perform a Diels-Alder reaction with maleic anhydride. Step 2 (step 2) is a step of reducing the product obtained in step 1 with a reducing agent ( (For example, LiA1H4 or NaBH4, etc.) in a non-aqueous polar solvent to reduce the acid anhydride to lactone. • Step 3 (step 3) is to oxidize the double bond to peroxide with the peroxide obtained in step 2 Epoxide. --------- Order ---------. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1230320 No. 91005108 , February 1993 revised page A8SC8D8 | Zhengchong # 补 a 7 2 belongs to 2 years 9a (CH2) rT ^ C (Π) VI. Patent Application Range 1. A chemically amplified photoresist composition comprising: a high molecular polymer having the following structural unit of the formula (II); R1 where R1 is Η or CVC4 Alkyl; R2 is hydroxy, d-alkoxy or < ^ < 8 alkylthio; 0 is ((^ 2) 1 ^ oxy or sulfur, where 11 is an integer from 0 to 4; Rc is one Lactone group; m is an integer from 1 to 3; and the weight percentage of the polymer is 1 to 60% of the total composition; a photo-acid generator (PAG), the weight percentage of which is 0.1 to 50% of the high molecular weight polymer; and ~ solvent, the weight percentage of which is 40 to 98% of the total composition. 2. The composition of item 1 in the scope of patent application, wherein R1 is hydrogen or fluorenyl. For example, for the composition of the scope of patent application, where R2 is a hydroxyl group, C1 ~ C4 alkoxy or alkylthio group. 4. As for the composition of scope 1 of the patent application 5 • As for scope 1 of the patent scope The composition is an integer of 0, 1, or 2. -------- ^ --------- (Please read the notes on the back of tf before filling out this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Eliminate Thorium partnership split printing wherein m is an integer of 1, wherein G is a ...:. ^, Η 2933 ^ ¾)