TW513619B - Polymer and chemically amplified composition including silicon containing protecting group - Google Patents

Abstract

There is provided a polymer for use in a chemically amplified resist and represented by the following formula: where R' is one selected from the group consisting of: in which R1 is one selected from the group consisting of -H and -CH3, and m and n are integers, and where R2 is one selected from the group consisting of -H and -CH3, R3 is one selected from the group consisting of -H and -CH3, R4 is one selected from the group consisting of -H, -CH3 and -CH2CH2OH, p, q and r are integers, p/(p+q+r) is 0.1 to 0.7, q/(p+q+r) is 0.1 to 0.7, and r/(p+q+r) is 0.1 to 0.5.

Description

513619 V. Description of the invention (BACKGROUND OF THE INVENTION 1) Field of the Invention The present invention relates to a chemically amplified photoresist composition, and more particularly, to a chemically amplified photoresist composed of a silicon-containing polymer compound Composition. 2. Description of related technologies. As semiconductor devices become more highly integrated and more complex to manufacture, the formation of finer patterns is necessary. Accordingly, there are many new photoresists in lithography methods. What's more, because the capacity of semiconductor memory elements exceeds 1 Gbit, new photoresist materials that can be developed by ArF excimer laser (193 nm) become more necessary. Central Bureau of Standards, Ministry of Economic Affairs The printing of employee consumer cooperatives depends on the semiconductor manufacturing method. If the ArF photoresist is not a single layer resist (SLR), it is a double layer resist (13LR layer resist, BLR). Generally, If SLR is used, the photoresist patterning method is simpler than when using BLR. However, the photoresist pattern using SLR does not provide sufficient dry-feed etched impedance. That is, if the aspect ratio is increased The inclination of the photoresist pattern will change the photoresist pattern and cause difficulties in forming the photoresist pattern. BLR contains silicon. When using BLR to form photoresist patterns, the mapping method is more complicated than using SLR. However, During the dry etching with 02 plasma, the silicon atoms in the photoresist material were converted into silicon oxide to form a hardened layer on the surface of the photoresist layer. Because this hardened layer was used as an etching mask during the subsequent dry etching, Photoresist patterns are easy to form even at high aspect ratios. _____5 __ This paper size applies to China National Standard (CNS) A4 (210X297 mm) 513619 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Λ7 B7 V. Description of the invention The silicon content in the polymer can be used as an important factor in the manufacture of BLR. A silicon-containing polymer is disclosed in the document titled "Used as ArF excimer laser lithography. S ^ ontammg Positive Resist for ArF excimer Laser Lithography? Akiko Kotachi and his research colleagues, Journal of Photopolymer Science and Technology (J. Pliot opoiymer Science and Technology), Vol. 8, No. 4, p. 615, 1995, is a BLR that uses two ArF excimer laser lithography methods. However, the polymer silicon content disclosed in the above reference is about 8% by weight. Considering the need to achieve a high aspect ratio, at least 10% by weight of silicon is required. It is generally not possible to achieve a sufficiently high aspect ratio for the polymers disclosed in the above literature. Also, because of the polymerization The polymer does not have good adhesion properties, and the photoresist layer formed using the polymer may be detached from the lower layer. In order to solve the above-mentioned problems, an object of the present invention is to provide a polymer having a novel structure which contains sufficient silicon to be used in ArF excimer laser lithography. Another object of the present invention is to provide a chemically amplified photoresist composition containing the polymer. Accordingly, in order to achieve the first object, the present invention provides a polymer, which is used in a chemical amplification photoresist and is represented by the following formula: --------- Cloth 1T (Please read the precautions on the back first Fill out this page again) 513619 Λ7 B? V. Description of the invention (〇, II γκ--ow 111 ·-

(CH3) 3Si Si (CH3) 3 where R > is selected from the group consisting of:

Where R t is selected from the group consisting of -H and -CH3, and m and n are integers, and please read it. Read the notes and fill in this page f. —C- CH2 —CR2 —]-CH2 —CH —]- CH2 CR3—

P j Η I C = 〇

Cj I 〇

I R4 where R2 is selected from the group consisting of -H and -CH3, R3 is selected from the group consisting of -H and -CH3, R4 is selected from the group consisting of -Η, -CH; and -CHXPhOH, p, cl and r are integers , P / (p + Q + r) is 0 · 1-() · 7, q / (p + q + r) is 0 · 1-0 · 7 ', and r / (p + Q + r) is 0. 1-0 * 5 ° In order to achieve the second object, the present invention provides a photoresist composition having the above-mentioned polymer and a photoacid generator (PAG). The polymer has a weight average molecular weight of 3,00 ()-100,000. ___7 _ This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm)

I Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 513619 B7 5. Description of the Invention (f) The photoresist composition contains M5 weight percent PAG based on the weight of the polymer. The PAG is selected from the group consisting of a triarylsulfonium salt, a diaryl iodogun salt, a sulfonate, and any combination thereof. The photoresist composition further includes an organic base. The photoresist composition comprises an organic base in an amount of 0.0i-0.2% by weight based on the weight of the polymer, and the organic base is selected from the group consisting of triethylamine, diethylamine, triethanolamine, and any combination thereof. According to the present invention, it is provided a polymer having a silicon-containing acid labile group, and a photoresist composition using the polymer. Therefore, the polymer of the present invention has an extremely high content of silicon compared with conventional polymers, and has excellent adhesion to other films. The description of the preferred concrete window embodiment Next, the preferred embodiment of the present invention will be described in more detail. Example 1 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy, etc. Synthesis of Alcohol The synthesis reaction of bis (trimethylsilyl V2-propanol is represented by the following formula

(Chb) 3Si Si (CH3) 3 (I) (Please read the notes on the back before filling out this page) 4 HCOEt + CIMgCH2Si (CH3) 3 Trimethylsilyl methylmagnesium chloride (in ether solution ( ) · 3 Mol This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21〇 × 297mm) 513619 Λ7 B7 V. Description of the invention (, Γ)) was placed in a round bottom flask, and Ethyl formate was slowly added dropwise. Then, the obtained reactant was reacted under reflux conditions for about 12 hours. After the reaction was completed, the reaction product was poured into excess water and neutralized with HC1. Thereafter, the product material was extracted with diethyl ether, and the extract was dried over MgSCU. The resulting product was isolated and purified by vacuum distillation (yield 60%). Nuclear magnetic resonance (NMR) analysis and Fourier transform infrared radiation (FT-IR) were applied to the distillate. The results are as follows] H- NxMR (CDCb ^ ppm): 0 · 0 (18H, -CH3), 0 · 9 (4H, -CH >), 1 · 2 (1H, -OH), 4 · 0 (1H, -CH-) FT- IR (Naa, cm 1): 3300 (-OH), 2950 (OH), 1400 and 1260 (Si-C) Window Example 2 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Synthesis of methacrylic acid ester (BPMA) bis (trimethylsilyl) propylmethacrylate (BPMA) C Π) monomer synthesis reaction is represented by the following formula: χΗ3

CH3 ΠΗ I

(CH3) 3Si Si (CH3) 3

I _ + I 〇

(CH3) 3Si Si (CH3) 3 (Π)

CI This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 513619 A7 B7 V. Description of the invention 0.1 mol; bis (trimethylsilyl) -2-propanol (I) And 0.1 mol of triethylamine (TEA) were dissolved in methylene chloride in a round bottom flask, and 0.1 mol of isobutylene chloride was slowly added dropwise to the mixture. Then, the obtained reactant was reacted under reflux conditions for about 12 hours. After the reaction was completed, the reaction product was poured into excess water and neutralized with HC1. Thereafter, the product material was extracted with diethyl ether, and the extract was dried with MgSCu. The obtained product was separated and purified by vacuum distillation to obtain BPMA (acid 70%) having an acid-labile U-bis (trimethylsilyl) propyl group. Nuclear magnetic resonance (NMR) analysis and Fourier transform infrared radiation (FT-IR) were applied to the distillate as follows:! H-NMR (CDC13 ^ ppm) 0 · 0 (18H, S1-CH3), 1.0 (4H, -CH >), 1 · 9 (3H, -CH3), 5 · 2 (1Η, -CHO '5 * 5 and 6.0 · (2Η' = CH2) FT-IR (NaCi, cm'1): 2950 ( CH), 1720 (C = 0) '1600 (C = C)' 1400 and 1260 (Si-C) Example 3 Synthetic poly [bis (trimethylsilyl) propyl methacrylate-copolymerization-MA 10 This paper is in accordance with China National Standard (CNS) Α4 specification (21〇 × 297 issued) Please read the note first Please fill in this page again, printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, printed 513619 B7 V. Description of the invention ("]) f Anhydride] (1Π) The synthesis reaction of the monomer is expressed by the following formula:

_

(CH3) 3Si Si (CH3) 3 • CH2— c

(Please read the notes on the back before filling this page) 0.1 mol BPMA (n) monomer and 0.1 mol maleic aldehyde and 8 millimolar azobisisobutyronitrile synthesized in Example 2 (AIBN) was dissolved in tetrahydrofuran (THF) and washed with N 2 gas for about 2 hours. Then, the reactants were polymerized under reflux conditions for about 24 hours. After the polymerization was completed, the reaction product was slowly precipitated in an excess of n-hexane, and the precipitate was redissolved in THF and then precipitated with n-hexane. Thereafter, the product substance was extracted with diethyl ether, and the extract was dried over MgSO. The product printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs was maintained in a vacuum oven and dried at about 50 ° C for about 24 hours to obtain poly [bis (trimethylsilyl) propylmethacrylate-copolymerization. -Maleic anhydride] (III) monomer (yield 5 (λ%). The weight-average molecular weight and polydispersity of the obtained product were 6,500 and 2.5, respectively. Example 4 Poly (bis (trimethylsilyl) propyl) Synthesis of methylmethylpropionate-co-polymerization-N-vinylgfirolidone 1 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 513619 Λ7 B7 V. Description of the invention (t ) The synthesis of poly [bis (trimethylsilyl) propylmethacrylate_copolymerization-N · vinylpyrrolidone] (IV) is represented by the following formula: CH3 CH3 ΑΙΒΝ

(CK3) 3Si Si (CH3) 3

(CK5) 3Si Si (CH3) 3 (Please read the precautions on the back before filling this page) (IV) 0.1 mol BPMA (Π) monomer and 0.1 mol 1-ethylene synthesized in Example 2 The methyl-2-pyrrolidone and 8 mmol of AIBN were dissolved in an anhydrous THF solution, and washed with N 2 gas for about 2 hours. Then, the reactants were polymerized under reflux conditions for about 24 hours. After the polymerization was completed, the reaction product was slowly precipitated in an excess of n-hexane, and the precipitate was redissolved in THF and then precipitated with n-hexane. The resulting product was dried in a vacuum oven at about 5 CTC for about 24 hours to obtain poly [bis (trimethylsilyl) propylmethacrylate-copolymerized vinylpyrrolidone] (IV) monomer (yield 75%). The weight average molecular weight and polydispersity of the obtained product were 13,500 and 2.2, respectively. Example 5 Synthesis of terpolymer The synthesis reaction of terpolymer (V) is expressed by the following formula: _12____, 1T, printed by the Consumers' Cooperative of the Central Standards Bureau, Ministry of Economic Affairs, the paper is printed in accordance with the Chinese National Standard (CNS) A4 specification ( 210 × 297 mm) 513619 B7 V. Description of the invention CH: c = o I 〇 +

(CH3) 3Si. Si (CH3) j

+ 〇 h ό 〇 〇 (Please read the notes on the back before filling this page) 〇 〇

(CH3) 3Si Si (CH3) j

.CH2CH2OH Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (V) 40 mM BPMA (Π) monomer synthesized in Example 2 and 3 () -1 -vinyl-2-pyrrolidone of mol, And 30 millimoles of 2-hydroxyethyl methacrylate and 4 millimoles of AIBN were dissolved in an anhydrous THF solution, and washed with N2 gas for about 2 hours. Then, the reactants were polymerized under reflux conditions for about 24 hours. After the polymerization was completed, the reaction product was slowly precipitated in an excess of n-hexane, and the precipitate was redissolved in THF and then precipitated with n-hexane. The obtained product was dried in a vacuum box for about 24 hours to obtain a terpolymer (V) (yield 75%). The weight average molecular weight and polydispersity of the obtained terpolymer were 14,300 and 2.0, respectively.眚 Example 6 13 This paper size applies the Chinese National Standard (CNS) Α4 specification (210X 297 mm) 513619 Printed Λ7 B7 by the consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (丨 U) 1 g of the copolymer synthesized in Example 3 and 0.02 g of triphenylphosphonium trifluoromethanesulfonate as a photoacid generator were completely dissolved in 7 g of propylene glycol monomethyl ether acetate (PGMEA). Thereafter, the solution was filtered using a filter of 0.2 m to obtain a photoresist composition. 'The photoresist composition is then applied to a silicon wafer treated with hexamethyldisilazane (HMDS) to form a coating film having a thickness of about 0.3 microns on the wafer. The wafer with the coating film is pre-baked at a temperature of about 130 ° C for about 90 seconds and exposed using a KrF quasi-point with a numerical aperture of 0.45 on the laser 1 emitted. Then, post-exposure baking (PEB) is performed at a temperature of about 130 ° C. for about 90 seconds. Thereafter, the product substance was developed using a 2.38% by weight tetramethylammonium hydroxide (TMAH) solution. As a result, a sharp 0.3 micron line and space pattern can be obtained when the exposure dose is about 21 '. Example 7 Implementation of lithography 1 g of the copolymer synthesized in Example 4 and 0.02 g of triphenylphosphonium trifluoromethanesulfonate as a photoacid generator were completely dissolved in 7 g of PGMEA. Thereafter, the solution was filtered using a 0.2 micron filter to obtain a photoresist composition. Then, the photoresist composition is applied to an HMDS-treated silicon wafer to form a coating film having a thickness of about 0.3 micron on the wafer. The wafer having the coating film is pre-treated at a temperature of about 130 ° C. Bake for about 90 seconds and use light emitted from a KrF excimer laser with an aperture of 0.45 to expose -------- 14____ The paper size applies to the Chinese National Standard quasi-NS) A4 size (21〇297297mm) Li) L ------------- IT ------ A (Please read the notes on the back before filling in this page) 513619 Λ7 B7

5. Description of the invention (I. Then, the PEB is performed at a temperature of about 130 ° C for about 90 seconds. Thereafter, the product substance is developed using a 2.38% by weight TMAH solution for about 60 seconds. As a result, when the exposure dose is about 25 ml / cm2, a clear 0.3 micron line and space pattern can be obtained. The following formula represents the exposure mechanism of the terpolymer provided in Example 7: CH: CH:

NH 〇

(CH3) 3SS Si (CH3) 3

OH

COOH (CH3) 3Si Si (CH3) 3 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. As can be seen from the above formula, the 1,3-bis (trimethylsilyl) propyl group did not dissolve in the display before exposure. Like solution, but can be dissolved by active acid hydrolysis after exposure to acid. Example 8 Application of the stone 1 g of the terpolymer synthesized in Example 5 and 0.02 g of triphenylphosphonium trifluoromethanesulfonate as a photoacid generator were completely dissolved in 7 g of PGMEA. Thereafter, the solution was filtered using a 0.2 micron filter to obtain a photoresist composition. Then, the photoresist composition was applied to a HMDS-treated silicon wafer to form a coating film having a thickness of about 0.3 microns on the wafer 15 L --------------- -IT ------- φ (Please read the notes on the back before filling out this page) This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 513619 Λ7 B7 V. Description of the invention (ίν ) 〇 The wafer with the coating film is pre-baked at a temperature of about 13 ° C for about 90 seconds and exposed with light emitted by a KrF excimer laser with an aperture number of (X45.) Then, the PEB is at a temperature of about 130 ° It is carried out for about 90 seconds at C. After that, the product substance is developed using a 2.38% by weight TMAH solution for about 60 seconds. As a result, when the exposure dose is about 26 m / cm2, a clear 0.3 micron line and space pattern can be obtained Example 9 Implementation of lithography 1 g of the copolymer synthesized in Example 4 and 0.1 g of triphenylphosphonium trifluoromethanesulfonate and 0.01 g of N-hydroxybutyl trifluoromethanesulfonate as photoacid generators The diamidoimide was completely dissolved in 7 g of PGMEA. Thereafter, triethylamine C (20 mol% PAG) as an organic base was completely dissolved in the product substance. Then, the solution was filtered using a 0.2 micron filter to obtain a photoresist composition. Then, the photoresist composition was applied to a HMDS-treated silicon wafer to form a wafer having a thickness of about 0 J microns. Coated film. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The wafer with the coated film is pre-baked at a temperature of about 13 () ° C for about 90 seconds. And exposure using light emitted by a KrF excimer laser with a photon number of 0.45. Furthermore, PEB was performed at a temperature of about 130 ° C for about 90 seconds. Thereafter, the product substance was developed using a 2.38% by weight TMAH solution. About 60 seconds. As a result, when the exposure dose is about 3 (), a clear C13 micron line and space pattern can be obtained. As described above, according to the present invention, the _16____ paper having a silicic acid-containing labile group The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 513619 Λ7 B? 5. Description of the invention (p)) The polymer and the photoresist composition using the polymer are novel to the use of BLR material. Compared with the conventional polymer, the silicon-containing polymer of the present invention has a higher silicon content and better adhesion to film materials. Therefore, this polymer can be used as a very useful photoresist composition in the manufacture of next-generation semiconductor devices. Although the present invention has been described in detail by the preferred embodiments, the present invention is not limited thereby, and various modifications and changes by those skilled in the art may be within the spirit and scope of the present invention. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economy

Claims (1)

513619 A, soil; ",-application for patent scope A8 B8 C8 D8 1 · A polymer used in the following formula R. I C I 〇 (CM3) jS; S; (CH3) j- (Please read the notes on the back before writing this page) where R ’is: CH2 —CRt -J-r CH2 _ch Where Ri is selected from the group consisting of -H and -CH3, and m and n are integers, m / (m + m) = 0.1-0.6, and has a weight average molecular weight of 5,000 to 100,000 ° 2. Polymer used in chemically amplified photoresist and expressed by the following formula, Rr IC = 0 I 〇 (CKs) jSi Si. (CKj) j 1 This paper size is applicable to Chinese National Standard (CNS) A4 (210 χ 297 mm) 513619 A8 B8 C8 D8 Patent application scope where R ’is: Η C Μ C——C——〇——R4 R ο wherein R2 is selected from the group consisting of -Η and CH3, R3 is selected from the group consisting of -H and -CH3, and R4 is selected from the group consisting of- In the group consisting of H, -CH3 and -CH2CH2OH, p, q and r are integers, and p / (P + q + r) is 0.1 to 0.7 'q / (P + q + r) is 0.1 To 0.7 'and r / (p + q + i ·) are 0.1 to 0.5 and have a weight average molecular weight of 5,000 to 100,000. A photoresist composition. It comprises: suitable for chemically amplified photoresist Polymer with the following formula: R. 〇 (Please read the precautions on the back before filling this page) Line-CI 〇 (CHj) 3Si S; (CH3) j · where R ′ is: —f- ch2 —cri 4 · • CH; • CH -L M 2 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 513619 C8 D8 VI. Patent application scope where Ri is selected from the group consisting of -H and -CH3, and m and η are An integer, and m / (m + n) = 0.1-0.6, and 1 to 15 weight percent photoacid generator (PAG) based on the weight of the polymer, wherein the polymer has a weight average molecular weight of 5,000 to 100,000, and wherein The PAG is selected from the group consisting of triaryl salt, diaryl salt, sulfonate and combinations thereof. 4. A photoresist composition comprising: a polymer suitable for chemically amplified photoresist and represented by the following formula: f ·% " (Please read the precautions on the back before filling this page) R. IC = 0 I 〇 Where R 'is: [CH 2 —CR2 — ^ CH 2 —CH —- [CH 2 —CR j P 丨 q | ^ C = ο CT I 0 1 R4 3 This paper size applies to China National Standard (CNS) A4 specifications (210 x 297 mm) 513619 A8B8C8D8 6. Application scope of patent where R2 is selected from the group consisting of -H and CH3, R3 is selected from the group consisting of -H and -CH3, R4 is selected from In the group consisting of -CH3 and -CH2CH2〇H, p, q and r are integers, p / (p + q + r) is 0.1 to 0.7, q / (p + q +?) Is 0.1 to 0.7, And r / (p + q + r) is 0.1 to 0.5; and a photoacid generator (PAG) based on the weight of the polymer, wherein the polymer has a weight average molecular weight of 5,000 to 100,000, and wherein the PAG is selected From the group consisting of triarylsulfonium salt, diarylsulfonium salt, sulfonate and combinations thereof. 5. The photoresist composition according to item 3 of the scope of patent application, further comprising an organic base. 6. The photoresist composition according to item 5 of the scope of the patent application, wherein the photoresist composition comprises 0.01 to 0.2% by weight of an organic base based on the weight of the polymer. 7. The photoresist composition according to item 5 of the scope of patent application, wherein the organic base is selected from the group consisting of triethylamine, diethylamine, triethanolamine, and combinations thereof. 4 This paper Γ degree is applicable to the country @ 准 （CNS) A4 size (210 X 297 mm) f. 4-(Please read the precautions on the back before filling this page), 1TT