TWI225571B - Polymer monomer for chemically amplified photoresist composition - Google Patents

Abstract

A kind of compound as shown in equation (I) is disclosed in the present invention. R1 is hydrogen or the alkyl of C1-C4. R2 is hydroxyl, C1-C8 alkoxy, or C1-C8 thioalkyl. G is (CH2)n, oxygen, or sulfur, in which n is an integer from 0 to 4. Rc is a lactone; and m is an integer from 1 to 3. The compound is suitable for use as polymer monomer, and can be synthesized to form polymer with good hydrophilic characteristics, adhesion characteristic, and anti-dry-etching characteristic; and, particularly, it can be incorporated with the other polymer monomer to form the co-polymerized polymer.

Description

1225571 A7 B7 V. Description of the invention (/) [Technical Field of the Invention] The present invention relates to a novel polycyclic unsaturated ester compound, especially a polycyclic unsaturated ester polymer monomer, which is suitable for synthesizing with good hydrophilicity. Polymer with good adhesion, adhesion and resistance to dry etching. [Background of the Invention] With the rapid increase of the integration level of semiconductor integrated circuits, the line width required by the lithography technology is also getting smaller and smaller. In theory, in order to make the pattern resolution 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 suitable light source with a wavelength of 193nni has been published. A polymer copolymer obtained by copolymerizing various polymer monomers is called poly iBMA-MMA-tBMA-MMA (poly isobornyl methacrylate-methyl methacrylate-t-butyl methacrylate-methacryliC acid), and its structure is as follows:

However, the above-mentioned high molecular polymers have some unsatisfactory points. The first is that the polymer formed by the copolymerization of four kinds of polymer monomers has a very low resistance to etching, and its adhesion properties are not good. Therefore, if you want to score this high 4 paper standards for China Standard (CNS) A4 specification (21〇X 297 mm) (Please read the notes on the back before filling this page) -------- ^ --------- Intellectual Property Bureau, Ministry of Economic Affairs Printed by Employee Consumer Cooperative 1225571 A7 B7 V. Description of Invention (>) The application of a sub-polymer to photoresist resists requires the development of a new process. U.S. Patent Nos. 6,271,412, 6,280,898, and Japanese Patent Publication No. 2001-242627 disclose a variety of different polymer monomers, all of which can be used to polymerize into photosensitive polymers and configured as photoresist composition applications For the production of semiconductor integrated circuit components. [Summary of the invention] The main purpose of the present invention is to provide a novel polycyclic unsaturated ester compound, which is suitable as a polymer monomer for polymerization reaction, which can be used to produce good hydrophilicity, adhesion and resistance to drying. Etched polymer; it can also be copolymerized with other different polymer monomers to form different polymers. The compound provided by the present invention is represented by formula (I): R1 (CH2) m Rc, where R1 is fluorene or (VC4's alkyl); R2 is hydroxyl, Ci_C8 ^ alkoxy, or Ci_C8 Sulfur-based 5 This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- ^ ------ · —

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225571 A7 _ B7 _ V. Description of the Invention (multi) An integer of 0 to 4; & is a lactone; m is an integer of 1 to 3. The compound of formula (I) can be polymerized in the presence of a catalyst to form a new type of high-yield polymer, or it can be produced by copolymerization with other polymer monomers containing different acetamidine functional groups in the presence of the catalyst. Polymer. The polymer can be combined with a photo-acid generator (PAG), an acid quencher, an additive, and a solvent to make a chemically amplified photoresist composition. The chemically amplified photoresist composition can be maturely applied to general lithography imaging processes, especially 193nm lithography imaging processes, and has excellent resolution, contour and sensitivity. [Specific description of the invention] The present invention provides a compound of the following formula (I),

Where R1 is Η or CCc4 alkyl; r2 is hydroxyl, Cl_C8 alkoxyxy ^ CCC8 sulfur sulfur basic paper size is suitable ^ Chinese National Standard (CNS) A4 m ) Each (210 χ 297 male n I ϋ ϋ I i I · III 1 «ϋ I n order --------- line if · Γ Please read the notice on the back before filling this page) 1225571 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (+) (thioalkyl); 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 of 1 to 3. The preparation of the compound of formula (I) of the present invention can be listed by the following method (step 1 to step 5), but is not limited to the following method:

[Diels-Alder] Step 1 [Reduction]-^ Step 2 Peroxide

Step 3 H + • I _ i -------- ^ ------- (Please read the precautions on the back before filling this page)

Step 4

The definitions of R1, .R2 and G are as described above. Step 1 (step 1) is to select appropriate diene compounds, such as: butadiene, cyclopentadiene, furan, and thiophene, etc. Acid anhydride (maleic anhydride) enters this paper standard applicable to China National Standard (CNS) A4 specification (210 X 297 mm) line _ · 1225571 A7 _I ---- B7__ 5. Description of the invention (5) Diels-Alder reaction. Step 2 (step 2) is a reduction reaction of the product obtained in step 1 with a reducing agent (such as LiAlH4 or NaBH4, etc.) in an anhydrous polar solvent to reduce the acid liver to internal @purpose. Step 3 is to oxidize the double bond to epoxide with peroxide in the product obtained in Step 2. Step 4 (step 4) is to perform the ring-opening addition reaction of the product obtained in step 3 with an appropriate nucleophile (such as water, alcohols, and thiol compounds) under acidic conditions to obtain a derivative having a hydroxyl group. Step 5 (steP 5) is the product obtained in step 4 and then acetic acid reaction with (alkyl) acryloyl chloride (acryloyl chlOHde) or acetyl chloride to obtain the "Formula (I ) Compounds. For a more detailed preparation method, refer to the examples in the description of this case. The polymer of formula (I) of the present invention can synthesize a high-molecular polymer containing repeating units of the following formula (II) through polymerization, I ;: -------- ^ --------- (Please read the notes on the back before filling this page)

It is hydroxyl 1225571 A7 V. & Description of the invention (hydr〇xyl), Cl_Cs alkoxy (Aik〇xy) or Ci_Cs alkylthio (thioalkyl); G is (CH2) n, oxygen or sulfur, where n is An integer of 0 to 4; & is a lactone; m is an integer of 1 to 3. The compound of formula (I) can be copolymerized with other high molecular monomers containing acetamidine functional groups in the presence of a catalyst to form different high molecular polymers. There are no particular restrictions on the selection of other high molecular monomers containing ethylene functional groups. However, if the polymer can be penetrated by a light source of 193nm, it should be selected without aromatic structure. The polymer monomer containing ethyl functional group is used to make the polymer of this molecule can be penetrated by the light source of 93nrn. Among them, the acetamidine-containing polymer monomers can be listed as follows: (where R3 is fluorene or an alkyl group of C1-C4) zR3 R3, R3, R3, R3, R3 line van '

Printed by R, R3, R3, R3, R3, R3 10 _

OH This paper size is in accordance with Chinese National Standard (CNS) A4 specifications (2) 0 χ 297 mm 1225571 A7 B7 V. Description of the invention (7) R3 Λ R3

CH2〇H

co2h

〇

| >: ----------------- (Please read the phonetic on the back? Matters before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (I ) A polymer copolymer compound can be synthesized by combining one or more of the above-mentioned polymer monomers containing ethylene functional groups. The above polymer or polymer copolymer compound can be used to manufacture chemically amplified photoresist. This chemically amplified photoresist can be maturely applied to general lithography imaging processes. More specifically, the chemically amplified photoresist produced by the polymer formed by using the polymer monomer of the present invention can be used in addition to the lithography imaging process of the conventional traditional wavelength light, and can also be applied. Lithography process at 193nm light. 10 This paper size applies to Chinese National Standard (CNS) A4 specifications (2) 0 X 297 mm 1225571 A7 B7 V. Description of the invention (3) In order to better understand the technical content of the present invention, better specific examples will be given. as follows. [Preferred embodiment of the invention] Example 1: 9-methoxy-5-one-4-oxo-paracyclo [5 · 2 · 1 · 02'6] dec-8-ylmethacrylic ester (9 Synthesis of -methoxy-5 -oxo-4-oxa-tricyclo [5.2.1.02,6] dec-8-yl methacrylate) (1-1) (Please read the precautions on the back before filling this page)

CH3〇H H + 〇

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs? π Dissolve 16.6 grams of 8,9-epoxy-3-one-4-oxo-sylcyclo [5 · 2 · 1 · 02,6] decane in 200 ml of methanol and add 0.25 ml of concentrated sulfuric acid to start Ring reaction. After the reaction is completed, the solution is neutralized. After concentrating, 200 ml of dichloromethane and 10.2 g of triethyl amine are added, and then 10.5 g of methylacryloyl gas (methacryloyl) is added. chloride) and stir until the reaction is complete. After filtration and cycloconcentration, it was separated by chromatographic analysis to obtain 9-methoxy-5-one-4-oxo-paracyclo [5.2.1.02'6] dec-8-ylmethyl, which was a pale yellow oily liquid product. 18.9 g (9-methoxy-5-oxo-4-oxa-tricyclo [5.2.1.02,6] dec-8-yl methacrylate) (1-1) (yield: 75%). Spectral identification: lH-NMR (CDC13 ^ 300MHz) 11 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 1225571 Printed clothing A7 B7 of the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs (?) D 5.89 (1H, brs), 5.37 (1H, brs), 4.81 (1H, m), 3.96 (1H, m), 3.67-3.57 (2H, m), 3.54 (3H, s), 2.79 (1H, m), 2.57 (lH, m), 2.55 (lH, m), 2.37 (lH, m), 1.77-1.74 (4H, m), 1.38 (1H, m). I3c-NMR (CDC13, 75MHz) β 171.4, 165.6, 136.0, 124.8, 84.9, 79.5, 70.0, 51.0, 46.1, 45.7, 40.4, 39.1, 32.4, 17.8 Example 2: 9-methoxy-5-one -4-oxo-paracyclo [5.2.1.02,6] dec-8-yl acrylate (9-methoxy-5-oxo-4-oxa-tricyclo [5.2.1.02,6] dec-8-yl acrylate) ( Synthesis of 1-2) Η + Dissolve 16.6 g of 8,9-epoxy-3-one-4-oxo-paracyclo [5 · 2 · 1.〇2,6] decane in 200 ml of methanol And add concentrated sulfuric acid 0.251 to carry out the ring-opening reaction. After the reaction is completed, the solution is neutralized. After concentrating, 200 ml of dichloromethane and 10.2 g of triethyl amine are added, and then 9.1 is added. Gram of acrylyl 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-paracyclo [5.2.1.〇2,6] dec-8, a light yellow oily liquid product. -Methyl methacrylate (9-12) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) J ----: -------------- 丨tr --------- Turn (Please read the precautions on the back before filling this page) 〇

Ο

1225571 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (θ)

Hiethoxy-5-ox〇-4-〇xa-tricyclo [5.2.1.02,6] dec-8-yl acrylate) (ϊ_2) 18.9 g (yield: 75%). Spectral identification: 1h_NMR (CDC13, 300MHz, J in Hz) J 6.38 (1H, dd, J = 17.4, 0.6), 6.11 (1H, dd, J = 17.4, 10.5), 5.82 (1H, dd , J = 10.5, 0.56), 5.01 (1H, brs), 4.17 (1H, d, J = 5.0), 3.86 (1H, d, J = 5.6), 3.79 (1H, dd, J = 5.6, 2.7), 3.72 (3H, s), 2.95 (1H, m), 2.81 (1H, m), 2.73 (1H, m), 2.56 (1H, brs), 1.95 (1H, d, J = 10.9), 1.57 (1H, d, J = 10.9).

1 Q JC-NMR (CDCI3, 75MHz) cM71.9, 165.0, 130.7, 128.6, 85.4, 80.0, 70 · 5, 51.6, 46.7, 46.2, 40.8, 39.6, 32.9 Example 3 4-ethoxy-9 _Keto-8-oxy-bicyclo [4.3.0] non-3-yl acrylate (1-4ethoxy-9-oxo-8-oxa-bicyclo [4.3,0] non-3-yl acrylate) (1-3 ) Synthesis of H + acryloyl chloride The procedure of Example 2 was repeated, and 3,4-epoxy-7-one-8-oxy-bicyclo [4 · 3 · 0] nonane (3,4-epoxy-7_oxo-8_oxa -bicyclo [4.3.0] nonane) instead of 8,9 -soil-3-one_4_oxo-shencycline [5 · 2 · 1 · 02'6] decane (8,9-epoxy-3- 13 The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 丨 ^: -------- Order --------- line (please read the precautions on the back first) (Fill in this page)

〇 C2H5〇H CH2CI2 / Et3N

〇 〇

1225571 A7 B7 V. Description of the invention (II) oxo-4-oxa-tricyclo [5.2.1.02,6] decane) as the starting material, and the reaction was carried out by replacing methanol as the solvent with anhydrous ethanol, and then a colorless oily liquid product was obtained. 4_ethoxy-9-one_8-oxy-bicyclo [4.3.0] non-3_yl allyl ester (4-ethoxy-9_oxo-8, oxa-bicyclo [4.3.0] non-3-yl acrylate ) (1-3). Spectral identification: i-NMR (CDC13, 300MHz, J in Hz) (ί 6.28 (1H, dd, J = 17.4, 1.8), 5.99 (1H, dd, J = 17.4, 10.6), 5.75 (1H, dd, Bu 10.6, 1.8), 4.91 (1H, brs), 4.11 (1H, m), 3.85 (1H, m), 3.58 (1H, m), 3.44 (1H, m), 3.22 ( lH'm), 2.61-2.47 (2H, m), 2.25 (lH, m), 1.91-1.72 (2H, m), 1.09-0.97 (5H, m). UC_NMR (CDC13, 75MHz) cM71.6, 164.7 , 130.9, 128.0, 71.2, 70.8, 69.2, 63.8, 35.7, 30.3, 25.1, 20.7, 14.9 〇Examples 4 ~ 7 The steps of Example 1 were repeated, and the reaction was performed with different starting materials and solvents. The results were As shown in Table A, m —ϋ βϋ (Please read the precautions on the back before filling out this page} --- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs π This paper size applies to Chinese National Standard (CNS) A4 ^ T ^ ;; 297 ~ ---- 1225571 A7 B7 V. Description of the invention (l >)

Form A Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

; J .-------------- ^ --------- (Please read the notes on the back before filling in this page) The paper size applies to China National Standard (CNS) A4 size (210 X 297 mm) 1225571

A7 B7 V. Description of the invention (6) Application example 1 〇 (in-1) where g + h + i = l 20 ml of tetrahydrofuran and tert-butyl methacrylate were added to the reactor 2.13 Grams, 2-methyl-2-adamantyl methacrylate (2-methyl-2-adamantyl methacrylate) 4.69 grams and 9-methoxy-5-keto-4-oxo-paracyclo [5 · 2 · 1 · 02,6] dec-8-ylmethylpropylacrylate (, methoxy-5-ox〇-4-oxa-tricyclo [5.2.1.02j6] dec-8-yl methacrylate) 3.99 g, then 1.1 g of 2,2, -azobisisobutene (AIBN) as an initiator was further added, and the temperature was raised to 65. (: After the reaction is completed, add milliliters of soil, and then pour the product of the reaction into a container containing 1 liter of hexane. A white solid precipitates, which is filtered and dried to obtain the formula (III). Molecular polymer white powder 8.43 g, yield 78%, ^ Measured by GPC, weight average molecular weight 14,100, glass transition temperature Tg, two paper sizes are applicable to Chinese National Standard (CNS) A ^ specifications (210 x 297 公 爱) —. ~ 1 ^ ----------------- (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225571 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of Invention (, +) Application Example 2

CH

〇〇2Η5 Where g + h + i = l Into the reactor was added 20 ml of tetrahydrofuran, tert-butyl methacrylate 2.13 g, 8-methylparacycline [5.2.1.02'6 ] Deca-8-ylmethylpropane (8-methyltricyclo [5.2.1.02,6] deca-8-yl methacrylate) 4.69 g and 4-ethoxy-9-one-8-oxy-bicyclo [4.3 .0] 4-ethoxy-9-oxo-8-oxa-bicyclo [4.3.0] non-3-yl methacrylate 4.02 g, and then add the starter 2, 1.1 g of 2'-azobisisobutyl, and the temperature was raised to 70 ° C. After reaction overnight, 20 ml of tetrahydrofuran was added, and then the reaction product obtained above was poured into a container containing 1 liter of hexane to produce A white solid precipitates. After filtering and drying, a white polymer powder of the formula (IV-1) with a repeating unit of 6.83 g can be obtained. The yield is 63%. It is measured by GPC with a weight average molecular weight of 19,200. The glass transition temperature Tg = 121 ° C. Application example 3 Formula of photoresist composition The polymer obtained from application example 1 containing structural repeating unit of formula (III-1) 17 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 丨^: -------- Order --------- Line (Please read the notes on the back before filling this page) 1225571 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Description (<) polymer 2 grams, difengyl sulfide ion full-gas-1-butanthic acid (triphenylsulfonium perfluoro-1-butanesul fonate; TPS-PFBS) 0. 05 grams and tertiary butyl cholate (Tert-butyl cholate; TBC) 0.06 g, propylene glycol monomethyl ether acetate (PGMEA) 10.4 g, and N- (hydroxy methyl) η bite (N- (hydroxy methyl) piperidine ) 0.5 mg of mixed homogenizer, and then the solution was filtered through a 0.45 μm filter, and the solution was spin-coated with a uniform film on a dry silicon wafer. The film was then dried at 130 ° C for 90 seconds, and a thickness of 317.6 nm was obtained. Then, a deep ultraviolet (DUV) with an energy of 15 to 35 mj / cm2 was irradiated at 193 nm. ° C on a hot plate for 90 seconds. Then, a 2.38% tetramethy hydroxide solution (tetramethyi ammonium li ydr ο χ 1 de · Τ '* a > r λ τ τ,, iMAH) was used to visualize the irradiated film, and the strip was washed with deionized water. The last name was Yu Ji_ Hard to dry. Scanning and analyzing the structure of this photoresist with an electron microscope revealed that 7F has a resolution structure of 015 arrays. The polymer monomers of this invention can be maturely applied to polymer polymers, and the gas photoresist is used in general lithography imaging processes, especially the 193nm 4 process, and has excellent resolution, contour and sensitivity. degree. In return to the stranger, the present invention, regardless of the purpose, means and effect, is shown here for the sake of knowing the technology < characteristics " but it should be noted that 'the above-mentioned many embodiments are only made by 4 # 于 " By way of example, the scope of the rights claimed in the present invention should be based on the patent scope, not just the above embodiments. _The scale is applicable (Please read the precautions on the back before filling this page) -------- Order ---------.

Claims (1)

1225571 A8 B8 C8 D8 VI. Patent application scope 〇 h3co σ 1-1 ο 7. If the compound in the first patent application scope is the compound of the following formula (1-2) 0 Η (Please read the precautions on the back before filling this page) H3C〇 〇 1-2 〇 8. The compound according to item 1 of the patent application scope is a compound of the following formula (1-3). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs c2h50, Η ----------------- line 丨, 〇 (1-3) 9. The compound is a compound of the following formula (1-4). The scale of the paper sores is applicable to 0 Chinese standards (CNS) A4 specifications (210 X 297 mm) 20 1225571 A8 B8 C8 D8 6. Scope of patent application 1-4 〇 10. The compound according to item 1 of the patent application scope is a compound of the following formula (1-5). 〇 > = 0 11. The compound according to item 1 of the scope of patent application is a compound of the following formula (1-6). Η0 > = 0 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 0 1-6 〇 12. The compound according to item 1 of the scope of patent application is a compound of the following formula (1-7). First | Mouth, n n n n n n n I I u n n n n n n n ϋ I I * n ϋ n n n n n n 1 1 n n I Private paper size applies to China National Standard (CNS) A4 (210 X 297 public) 21 1225571 A8 B8 C8 D8 -------II-— III-. I --- I-^ IIIII 1 1 I 1AWI (please read the notes on the back before filling out this page) Regulations 1 Regulation 4 i A ls) N (c quasi-standard home country i country | Medium scale for moderate use ¥ ¾ Male Γ / 9 2 X ο 22 1225571 No. 91105106, June 1993 revised page Scope of Patent Application 1. A compound represented by the following formula (I), R1 Wherein: R1 is Η or CVC4 alkyl; R2 is hydroxyl, CVC4 alkoxy or G; G is (CH2) n or oxygen 'where η is an integer from 0 to 4; Rc is a Lactone; m is an integer from 1 to 3. 2. The compound according to item 1 of the scope of patent application, wherein R1 is hydrogen or methyl. 3. As an integer among the compounds in the scope of the patent application. 4 · As for the compound in the scope of patent application, (3 is ((:: 112). N is an integer of 0, 1, or 2. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5) If the scope of patent application The compound of item 1, wherein G is oxygen. 6. The compound of item 丨 in the scope of application for a patent, which is a compound of the following formula (1_1). 19