TWI222968B - Cross-linking monomers for photoresist, and process for preparing photoresist polymers using the same - Google Patents
Cross-linking monomers for photoresist, and process for preparing photoresist polymers using the same Download PDFInfo
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- TWI222968B TWI222968B TW088121653A TW88121653A TWI222968B TW I222968 B TWI222968 B TW I222968B TW 088121653 A TW088121653 A TW 088121653A TW 88121653 A TW88121653 A TW 88121653A TW I222968 B TWI222968 B TW I222968B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/10—Esters
- C08F22/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- Chemical Kinetics & Catalysis (AREA)
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- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
1222968 A7 B7 五、發明說明（I) 發明領域 本發明關於一種用於光阻劑聚合物的交聯單體，及使 用其製備光阻劑聚合物的方法。更特別的說，本發明關於 一種用於能明顯改善光姐劑共聚物聚合比例的光阻劑聚合 物的交聯單體，及關於使用其製備光阻劑共聚物的方法。 發明背景 近來，化學放大類型（chemical amplification) D U V (深紫外線）光阻劑已被證明在半導體製造之製備微 線路方法上具有非常高的敏感性。這些光阻劑是由混合光 酸產生劑和具有酸不安定結搆之聚合物基質巨分子製f而 得。 依據此一光阻劑的反應機制，當K 一光源照射光酸產 生劑會產生酸，聚合物基質的主鐽或支鐽上的曝光部份和 所產生的酸反應，因而解聚（decompose)或交聯（ cross-link)，如此聚合物的極性會明顯的改變。極性改 變會導致在顯像（developing)溶疲中曝光區或未曝光區 溶解度的不同，如此在一基板上的光罩形成一正或負圖像 〇 於一些光阻劑中，在一聚合物的主鏈或支鐽上的官能 基是和基質中其它聚合物的主鐽或支鏈產生交聯的，因此 ，可在光阻劑中加入一交_劑K提昇聚合物間的交聯。 然而，交聯單體也可用於提昇組成光阻劑聚合物單體 間的鐽结，如此可增加光阻劑聚合物的產率。例如，當在 一 4 - 本紙張尺度適用中國國家標準（CNS)A4規格（2】0 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -------訂---------線 經濟部智慧財產局員工消費合作社印製 ^22968 A7 B7 五、發明說明（> ) 聚合化反應時使用2 0克的單體，而沒有使用交聯劑，約 可產生分子量約6000的聚合物4 ♦ 8克（產率：24 % )。當單體的數量增加至4 0克時，所得聚合物的數量 只有約6克（亦即產率突然降低至約1 5 % )，如此，為 了大量製備光阻劑聚合物，必須使用一交聯單體，K增加 產率及可商業化生產光阻劑聚合物。發明概要本發明的目的是提供一種用於光阻劑聚合物的交聯單 體，其能明顯的改善光阻劑聚合物的聚合產率。 光 備— 製。 體物 單合 聯聚 交劑 該阻 用光 使的 種得 一 製 供所 提其 是由 的及 ΕΕΠ , 一 法 另方 的 的 明物 發合 本聚 劑 阻 形 所 體 單 聯 交 述 上 用 使 。 種物 一 成 供組 提劑 是阻 的光 目的 一 得 另而 的備 明製 發物 本合 聚 成 物 成 組 劑 阻 光 述 上 用 使 種1 供 提 為 的 巨1 另 又 明 發 本 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 元明得得說述 體說所所细上 導要 34 詳到：> 半簡例例的達體 1 的元實實明 了單式 得圖是是發為聯學 製 12 交化 所 圖1的 < 件 像 像 圖 圖 劑劑 阻阻 光光 之之 式 學 fh 述 下 種1 供 提 明 發 本 的 § 明的 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------訂---------線 1222968 A7 _____ B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（ • R· 个=〇 其中R '和R 〃互不相關的分別為 從1至1 0的數；及R是選自直鏈或含 氫或甲基； 支鐽的C i 畢1222968 A7 B7 V. Description of the Invention (I) Field of the Invention The present invention relates to a crosslinking monomer for a photoresist polymer and a method for preparing a photoresist polymer using the same. More specifically, the present invention relates to a crosslinking monomer for a photoresist polymer capable of significantly improving the polymerization ratio of a photosensitizer copolymer, and to a method for preparing a photoresist copolymer using the same. BACKGROUND OF THE INVENTION Recently, chemical amplification type D UV (deep ultraviolet) photoresists have been proven to have very high sensitivity in the fabrication of microcircuits for semiconductor manufacturing. These photoresists are obtained by mixing photoacid generators with polymer matrix macromolecules having an acid labile structure. According to the reaction mechanism of this photoresist, when the K-light source is irradiated with the photoacid generator, an acid is generated, and the exposed part on the main or branch of the polymer matrix reacts with the generated acid, and thus decomposes. Or cross-link, so the polarity of the polymer will change significantly. Polarity changes will cause differences in the solubility of exposed or unexposed areas during developing dissolution. Thus, a photomask on a substrate forms a positive or negative image. In some photoresist, a polymer The functional groups on the main chain or branch are cross-linked with the main chain or branch of other polymers in the matrix. Therefore, a cross-linking agent K can be added to the photoresist to improve cross-linking between polymers. However, cross-linking monomers can also be used to increase the bond between the monomers that make up the photoresist polymer, which can increase the yield of the photoresist polymer. For example, when a 4-this paper size applies Chinese National Standard (CNS) A4 specifications (2) 0 X 297 mm (Please read the precautions on the back before filling this page) ------- Order- -------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 22968 A7 B7 V. Description of the invention (>) 20 grams of monomers were used in the polymerization reaction without using a crosslinking agent. A polymer with a molecular weight of about 6000 can produce about 4 g (yield: 24%). When the number of monomers was increased to 40 grams, the amount of polymer obtained was only about 6 grams (that is, the yield suddenly decreased to about 15%). Thus, in order to prepare a large amount of photoresist polymer, one cross Bi-monomer, K increases yield and can be used commercially to produce photoresist polymers. SUMMARY OF THE INVENTION The object of the present invention is to provide a crosslinking monomer for a photoresist polymer, which can significantly improve the polymerization yield of the photoresist polymer. Light equipment-system. Monomer cross-linking and cross-linking agent of the body can be used to produce the seed for the reason and ΕΕΠ, and the other method is the Ming Wu Fa. Use. Seeds are used as a group extract to block the light. One purpose is to prepare a hair product. The aggregate is a composite product. (Please read the precautions on the back before filling out this page.) Printed by Yuan Mingde De Shuo De Shuo Shui Sui by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives. Details are as follows: > The elementary formula of 1 clearly shows that the single-type drawing is issued as a joint system. 12 The chemical formula in Figure 1 of the exchange is as follows: The formula for blocking light is described in fh. The paper size specified in this § applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------- order --------- line 1222968 A7 _____ B7 Intellectual Property Printed by the Consumer Cooperative of the Bureau of the People's Republic of China. 5. Description of the invention (• R · == 0, where R ′ and R 不 are unrelated to each other from 1 to 10; and R is selected from straight chain or hydrogen or methyl ; C i Bi
C 烷基’直鏈或含支鏈的Ci-Cl0酯，直鍵或含C alkyl ’straight or branched Ci-Cl0 ester, straight or branched
支鐽的CSupported C
CC
酮，直鏈或含支鍵的C 酸’直鍵或含支鐽的c i 一 C ί 〇縮醛 有至少一羥基之c i — C i 〇烷基，直 至少一羥基之Ci 一 Ci 0酯，直鐽或 一經基之Ci ~Ci 〇嗣，直鏈或含支 基之C i 一 C 1 〇狻酸，及直鏈或含支 基之C ί 一 C i 〇縮醛。 ，直鍵或含鐽的含 鏈或含支鐽的含有 含支鍵的含有至少 鏈的含有至少一羥 鐽的含有至少一羥 為了達成本發明的目的，提供一種製1一光阻劑共聚 物的方法，包括步驟（a )將兩種或多 化學式1的交聯單體溶解於一有機溶劑 一聚合化起始劑或聚合催化劑至结果溶 -6 一 種光阻劑共單體及 中，及（b )加入 液中，K誘發聚合 (請先閱讀背面之注意事項再填寫本頁)Ketones, straight-chain or branched C-acids' straight-chain or branched ci-C ο acetals having at least one hydroxyl ci-C i alkyl, straight at least one hydroxyl Ci-Ci 0 ester, Ci ~ Ci 〇 嗣, straight or trivalent, C i -C 1 〇 狻 acid straight or branched, and C 含 Ci i acetal straight or branched. Straight bond or fluorene-containing chain-containing or branched fluorene-containing branched-bond-containing branched-bond-containing containing at least one chain containing at least one hydroxyl hydrazone containing at least one hydroxyl In order to achieve the purpose of the present invention, a photoresist copolymer is provided. A method comprising the step (a) dissolving two or more cross-linking monomers of Chemical Formula 1 in an organic solvent, a polymerization initiator or a polymerization catalyst to a solution of -6 a photoresist comonomer and, and (B) K-induced polymerization in the solution (please read the precautions on the back before filling this page)
本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1222968 A7 __B7 _ 五、發明說明（ι|>) 化反應。 發明人投入大量的研究而達成上述本發明的目的，發 現了化學式1的化合物可使得光阻劑聚合物和另一聚合物 交聯，因而改善了聚合物的聚合化產率。本發明的交聯單 體於改善具有非環烯烴主鐽之共聚物的聚合化產率特別有 效。 化學式1化合物具有兩個雙鍵，且每一個雙鍵和其它 光阻劑單體结合形成交聯，因此提昇光阻劑聚合物的聚合 化產率。 較佳地，化學式1的交聯單體是化學式2的1 ，3 —This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1222968 A7 __B7 _ 5. Description of the invention (ι | >) Chemical reaction. The inventor has devoted a lot of research to achieve the above-mentioned object of the present invention, and found that the compound of Chemical Formula 1 can cause the photoresist polymer to crosslink with another polymer, thereby improving the polymerization yield of the polymer. The crosslinked monomer of the present invention is particularly effective for improving the polymerization yield of a copolymer having a non-cyclic olefin backbone. The compound of Chemical Formula 1 has two double bonds, and each double bond is combined with other photoresist monomers to form a cross-link, thereby improving the polymerization yield of the photoresist polymer. Preferably, the crosslinking monomer of Chemical Formula 1 is 1, 3 of Chemical Formula 2 —
I 丁二醇二丙烯酸酯或化學式3的1 ，4一丁二醇二丙烯酸 酯： <化學式2 > --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製I Butanediol diacrylate or 1,4-monobutylene glycol diacrylate of Chemical Formula 3: < Chemical Formula 2 > -------------------- Order- -------- Line (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
一 7 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 8 6 9 2 2 21 7-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 8 6 9 2 2 2
\1/ A7B7\ 1 / A7B7
> 3 式 學 化 V> Formula 3 V
『如—olsls丨L-J 姐 ♦光 統 傳 成 合 在 可 法 方 的 化 合 聚 劑 阻 備光 製 ， 的明 ¾發 合本 聚據 劑依 阻 光 詛 光 它 其 至 體 單 聯 交 的 ix 式 學 化 ! 入 加 中 。 序成 程達 的而 物中 聚體 共單 劑劑 經濟部智慧財產局員工消費合作社印製 述下一應應 下況及反反 如情物一化 由 的合入 合 在物化加聚 > , 聚的及發 4 如共 4 ，誘式 例劑式中 Μ 學 姐學劑中化 光化溶液 < 備 種 製多 物或 生種 衍兩 烴將 烯由 族是 環法 脂方 之的 4 化 式合 學聚 化， 機溶 有果 一 结 於述 解上 溶至 體媒 單觸 聯屬 交金 的或 1 劑 式始 學起 化基"Such as—olsls 丨 LJ sister ♦ The light-transmitting compound aggregating aggregating agent in the law can prevent the light system, the bright ¾ hair-integrating agent according to the light curse it's ix formula Turned! Into Canada. Xu Chengcheng's Polymers and Single Agents in the Intellectual Property Bureau of the Ministry of Economic Affairs, the Employees' Cooperatives, printed the next response, and the opposite is true. , Poly and hair 4 as a total of 4, inductive formula in the formula M Xuejie chemical agent in the chemical photochemical solution < preparation of multi-produce or germ-derived two hydrocarbons, the olefin from the family is the cyclic lipid formula 4 Chemical formulas are polymerized, and the organic solution has the fruit. Once the explanation is dissolved, it is dissolved to the body media, the one-touch contact is gold, or the 1-component formula is used to learn the chemical base.
3 .R 2 R 本紙張尺度適用中國國家標準（CNS)A4規格（2】0 X 297公釐） ------------- I I---— It---------線 (請先閱讀背面之注意事項再填寫本頁) 1222968 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（b ) 其中k和η互不相關的分別為1或2 ; p是0至5的 ^ , R 5和R s互不相關的分別代表氫或甲基，R ^ ， R 2 ，R 3和R 4互不相關的分別代表氫，直鐽或含支_ 的Ci —Ci 〇烷基，直鏈或含支鏈的Ci 一 Ci 〇酯， 直鏈或含支鐽的Ci 一 Ci 〇酮，直鐽或含支鏈的Ct〜 Ct 〇羧酸，直鏈或含支鏈的Ci —Ci 〇縮醛，直鐽或 含鐽的含有至少一羥基之Ci —Ct 〇烷基，直鏈或,支 鏈的含有至少一羥基之C 1 一 C i 〇酯，直鍵或含支鐽的 含有至少一羥基之Ci —Ci 〇酮，直鏈或含支鐽的含有 至少一羥基之Ci 一 Ci 〇羧酸，及直鏈或含支鐽的含有 至少一羥基之C i — C i 〇縮醛。 此聚合化反應需要在溫度在6 0 °C和1 3 0 °C間，& 在氮氣或氩氣氣氛壓力0 · 000 1和5a tm間進行反 應。 體聚合反應或溶液聚合反應也可用作聚合化的方丨去， 及環己_，甲基乙基嗣，苯，甲苯，二噁烷，四氫呋0南， 丙二醇甲基醚乙酸酯，及/或二甲基甲醯胺，或其混合勸 可用作聚合化溶劑。聚合化起始劑可為苯甲醯過氧化物， 2，2’ 一偶氮雙異丁膳（AIBN)，乙醯過氧化物， 月桂基過氧化物，叔一 丁基過乙酸酯，叔一 丁基過氧化氮 — — — — — — — — — — — — ·1111111 ^ « — — — — — — I— (請先閱讀背面之注音？事項再填寫本頁} -9- 1222968 A7 __B7 _五、發明說明（7 ) ，二一叔丁基過氧化物，或類似物。 依據本發明的聚合化方法製得的所欲光阻劑聚合物可 由下述化學式5所代表： <化學式5 >3 .R 2 R This paper size is applicable to China National Standard (CNS) A4 specification (2) 0 X 297 mm ------------- I I ---- It ---- ----- line (please read the precautions on the back before filling this page) 1222968 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (b) where k and η are independent of each other and are 1 Or 2; p is ^ from 0 to 5, R 5 and R s independently of each other represent hydrogen or methyl, R ^, R 2, R 3 and R 4 independently of each other represent hydrogen, straight or containing Ci_Ci_ alkyl, branched, Ci-Ci 0 esters, straight or branched, Ci-Ci 0 ketones, straight or branched, Ct ~ Ct 0 carboxylic acids, or Straight or branched Ci-Ci 0 acetals, straight or branched Ci-Ct 0 alkyl groups containing at least one hydroxyl group, straight or branched C 1-C i 〇 groups containing at least one hydroxyl group Esters, linear or branched fluorinated Ci-Ci 0 ketones containing at least one hydroxyl group, linear or branched fluorinated Ci-Ci 0 carboxylic acids containing at least one hydroxyl group, and linear or branched fluorinated groups containing at least one Ci-Ci acetal of hydroxyl group. This polymerization reaction needs to be carried out at a temperature between 60 ° C and 130 ° C, & under a nitrogen or argon atmosphere pressure of 0 · 000 1 and 5a tm. Bulk polymerization or solution polymerization can also be used as polymerization methods, and cyclohexyl, methyl ethyl hydrazone, benzene, toluene, dioxane, tetrahydrofuran, propylene glycol methyl ether acetate, And / or dimethylformamide, or a mixture thereof, may be used as a polymerization solvent. The polymerization initiator may be benzamidine peroxide, 2,2'-azobisisobutyrate (AIBN), acetamidine peroxide, lauryl peroxide, tert-butyl peracetate, Tert-Butylperoxide— — — — — — — — — — — — 1111111 ^ «— — — — — — I— (Please read the note on the back? Matters before filling out this page} -9- 1222968 A7 __B7 _V. Description of the invention (7), di-tert-butyl peroxide, or the like. The desired photoresist polymer prepared according to the polymerization method of the present invention can be represented by the following chemical formula 5: < Chemical formula 5 >
ch2- R2 R3 Γ c 0 =0 (請先閱讀背面之注意事項再填寫本頁)ch2- R2 R3 Γ c 0 = 0 (Please read the precautions on the back before filling this page)
ch2- R2 r3 R.. 經濟部智慧財產局員工消費合作社印製 其中k和n互不相關的分別代表1或2 ; m代表一從 1至1 0的數；p代表從0至5的數；R ' ，R 〃 ，R s 和R 6互不相關的分別為氫或甲基；R是選自直鏈或含支 鏈的Ci 一 Ci 〇烷基，直鐽或含支鐽的Ci —Ct。酯 ，直鐽或含支鏈的Ci — Ci 〇酮，直鏈或含支鐽的Ci 一 Ci 〇狻酸，直鏈或含支鐽的Ci 一 Ci 〇縮醒，直鐽 或含鏈的含有至少一羥基之C i 一 C i 〇烷基，直鏈或含 支鐽的含有至少一羥基之Ci 一 Ci 〇酯，直鐽或含支鐽 的含有至少一羥基之C i 一 C i 〇酮，直鏈或含支鐽的含 一 10 - I I I I--—訂1111111 ^^ 本紙張尺度適用中國國家標準（CNS)A4規格（2】0 X 297公釐） 1222968 A7 B7 五、發明說明（I) 有至少一羥基之Ci 一 Ci 〇狻酸，及直鏈或含支鍵的含 有至少一羥基之C i 一 C i 〇縮醛；R 1 ，R 2 ，R 3和 (請先閱讀背面之注意事項再填寫本頁) R 4互不相關的分別選自氫，直鐽或含支鐽的C 1 一ch2- R2 r3 R .. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where k and n are independent of each other and represent 1 or 2; m represents a number from 1 to 10; p represents a number from 0 to 5. R ′, R 〃, R s and R 6 are independently hydrogen or methyl; R is selected from the group consisting of straight or branched Ci-Cio alkyl, straight or branched Ci— Ct. Esters, straight or branched Ci-Cio ketones, straight or branched Ci-Cio acids, straight or branched Ci-Cio acids, straight or chain containing Ci-Cio alkyl with at least one hydroxyl group, linear or branched Ci-Cio ester containing at least one hydroxyl group, straight or branched Ci-Cio ketone containing at least one hydroxyl group ， Straight chain or support containing a 10-III I --- order 1111111 ^^ This paper size applies Chinese National Standard (CNS) A4 specifications (2) 0 X 297 mm 1222968 A7 B7 V. Description of the invention ( I) Ci-Cio oxalic acid with at least one hydroxyl group, and Ci-Ci acetal with linear or branched chain containing at least one hydroxyl group; R 1, R 2, R 3 and (Please read the back first Please note this page and fill in this page again) R 4 is not related to each other from the group consisting of hydrogen, straight or C 1-
Ci 〇烷基，直鐽或含支鐽的Ci 一 Ci 〇酯，直鐽或含 支鏈的Ci 一 Ci 〇嗣，直鏈或含支鐽的Ci —Ci 〇羧 酸，直鍵或含支鏈的C i 一 C i 〇縮醛，直鐽或含鐽的含 有至少一羥基之Ci 一 Ci 〇烷基，直鏈或含支鐽的含有 至少一羥基之Ci -Ci 〇酯，直鐽或含支鐽的含有至少 一羥基之Ci 一 Ci 〇嗣，直鏈或含支鍵的含有至少一羥 基之Ci 。羧酸，及直鏈或含支鐽的含有至少一羥 ♦ 基之C Γ 一 C i 〇縮醛；及a : b : c的比例較佳的是1 一 5 0 莫耳 ％ : 1 0 — 5 0 莫耳％ : 0 ♦ 1 — 2 0 莫耳 ％ 〇 化學式5所代表光阻劑聚合物的分子量較佳的是從 3000 至 100000 之間。 經濟部智慧財產局員工消費合作社印製 依據本發明所製得的光阻劑聚合物在照像製版的效能 上和沒有交聯單體所形成的聚合物差別不大，然而，當使 用本發明的交聯單體時，聚合化的產率明顯的增加。 例如，在聚合化反應時，當使用2 0克的共單體而沒 有使用交聯劑，可得約4 ♦ 8克之具有分子量6 0 0 0的 聚合物（產率：2 4 % )。當所使用的共單體的數量增加 至4 0克時，所得聚合物的量只有約6克（亦即，當使用 更大量的反應物時，產率突然降低至約1 5 % )。因此， -11 一 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 1222968 A7 B7 五、發明說明) 單純的只增加反應物的量並不適合大量製造共聚物的方法 〇 換句話說，在使用本發明的交聯單體操作相同的聚合 化方法的情況下，聚合化時使用2 0克的共單體’可得約 7克具有分子量約1 2 0 0 0的聚合物（產率·♦ 3 5 % ) ，當共單體增加至4 0克時，所得聚合物的量為約1 4克 (產率：3 5 %，亦即在聚合化產率上沒有明顯的變化） 。所得光阻劑共聚物的分子量為1 2000，及其聚分散 度（Ρ ο 1 y d i s p e r s i t y)約為 2。 如上所述，當使用本發明的交聯單體操作聚合化f應 時可得到較高的產率，因此可大規模的製備光阻劑聚合物 0 光阻劑組成锪的製備 依據本發明，光詛劑組成物可由混合本發明的光阻劑 聚合物和一有機溶劑製備而得，可使用的溶劑為環己_， 甲基3 —甲氧基丙酸酯，乙基3 —乙氧基丙酸酯，丙二醇 甲基醚乙酸酯，2 —甲氧基乙酸乙酯，2 —庚酮，異丁基 甲基酮，或其它傳統有機溶劑。Ci 〇 alkyl, straight or branched Ci-Ci 0 ester, straight or branched Ci-Ci 0 嗣, straight or branched Ci-Ci 0 carboxylic acid, straight or branched Chain C i -C i 0 acetals, straight or fluorene-containing Ci-Ci 0 alkyl groups containing at least one hydroxyl group, straight-chain or branched fluorene-containing Ci-Ci 0 esters containing at least one hydroxyl group, straight or Ci-Ci 0 嗣 containing at least one hydroxyl group containing branched fluorene, Ci or Ci containing at least one hydroxyl group having straight chain or branching bond. Carboxylic acids, and linear or branched fluorinated C Γ -C i acetals containing at least one hydroxyl group; and the ratio of a: b: c is preferably 1 to 50 mole%: 1 0 — 50 mole%: 0 ♦ 1-2 0 mole% 〇 The molecular weight of the photoresist polymer represented by Chemical Formula 5 is preferably from 3000 to 100,000. The photoresist polymer produced according to the present invention by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has little difference in the performance of photoengraving and platemaking with the polymer formed without cross-linking monomers. However, when the present invention is used, When crosslinking monomers were used, the polymerization yield increased significantly. For example, in the polymerization reaction, when 20 g of a comonomer is used without using a cross-linking agent, about 4 ♦ 8 g of a polymer having a molecular weight of 60,000 (yield: 24%) can be obtained. When the number of comonomers used was increased to 40 grams, the amount of polymer obtained was only about 6 grams (that is, when a larger amount of reactants were used, the yield suddenly dropped to about 15%). Therefore, -11 a paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1222968 A7 B7 V. Description of the invention) Simply increase only the amount of reactants It is not suitable for a method for producing a copolymer in a large amount. In other words, in the case of operating the same polymerization method using the crosslinking monomer of the present invention, using 20 g of a comonomer at the time of polymerization can obtain about 7 g of A polymer with a molecular weight of about 1 2 0 0 (yield: ♦ 35%). When the comonomer is increased to 40 g, the amount of polymer obtained is about 14 g (yield: 35%, also That is, there is no significant change in the polymerization yield). The molecular weight of the obtained photoresist copolymer was 1 2000, and its polydispersity (P ο 1 y d i s p er s i t y) was about 2. As mentioned above, a higher yield can be obtained when the polymerization f is performed using the crosslinking monomer of the present invention, and thus the photoresist polymer can be prepared on a large scale. The photoresist composition 锪 is prepared according to the present invention. The photocuring agent composition can be prepared by mixing the photoresist polymer of the present invention and an organic solvent. The solvents that can be used are cyclohexyl, methyl 3-methoxypropionate, and ethyl 3-ethoxy. Propionate, propylene glycol methyl ether acetate, 2-methoxy ethyl acetate, 2-heptanone, isobutyl methyl ketone, or other traditional organic solvents.
少量的光酸產生劑也可加至此光阻劑組成物中。合適 光酸產生劑的例子包括：硫化物或鑰型式的光酸產生劑， 像二苯基碘化物六氟磷酸鹽，二苯基碘化物六氟砷酸鹽， 二苯基碘化物六氟綈酸鹽，二苯基p -甲氧基苯基三氟甲 烷磺酸鹽，二苯基p —甲苯基三氟甲烷磺酸鹽，二苯基P 本紙張尺度適用中國國家標準（CNS)A4規格（2]0 X 297公釐） --------tr---------^· (請先閱讀背面之注意事項再填寫本頁) 1222968 A7 B7 五、發明說明（丨C) 一異丁基苯基三氟甲烷磺酸鹽，二苯基ρ —叔一丁基苯基 二氣甲院碼酸鹽，三苯基銃六氟磷酸鹽，三苯基銃六氟砷 酸鹽’三苯基銃六氟銻酸鹽，三苯基銃三氟甲烷磺酸鹽， 二丁基蔡基銃三氟甲烷磺酸鹽，及類似物。 光阻劑圖像的形成 $據本發明所製得的光阻劑組成物可旋轉塗覆至矽晶 元上’ Μ形成一薄光阻劑薄膜，然後在一烤箱或熱盤上κ 溫度7 0 °C至2 0 0 1C，較佳地8 Ο υ至1 5 0 °C 〃軟烤 (soft-baked) " 1至5分鐘，之後使用深紫外線曝光器 或激發雷射曝光器之經圖像化的光源曝躧。所使用的#源 也可為ArF ，KrF ，E —光束，X —射線，EUV ( 極紫外線），D U V (深紫外線），或類似光源，曝光光 源的能量較佳的是從1至1 OOrnj/ cm2 ϋ 然後，將此薄光阻劑薄膜在溫度1 0 t至2 0 0 1C間 (請先閱讀背面之注意事項再填寫本頁) 後一烘烤（post-baked 較佳的是在1 0 0 °C至 經濟部智慧財產局員工消費合作社印製 2 0 0 Ό間，结果所得物質再K 2 ♦ 3 8 w t %或2 · 5 w t %的T M A Η顯像水溶液浸漬一預定的時間，較佳的 是4 0秒鐘，如此可得一超微圖像。 具有高度整合性的半導體元件可使用本發明的光阻劑 圖像製造。 上述的說明只是揭示相關於使用一交聯單體製備一光 姐劑共聚物或光阻劑組成物方法的特定實施例，必須了解 的是本發明並不局限於這些例子，同時也包括了使用本發 -13- 本紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 1222968 A7 __B7 五、發明說明（（I) 明的交聯單體於製備傳統光阻劑共聚物或光阻劑組成物的 任何方法。 較佳實施例的詳细描述 本發明將κ下述實例更詳細的描述，但必須提醒的是 本發明並不局限於這些實例。 實例1 :聚（順丁烯二酸酐/ 2 —羥基乙基5 —原冰片烯 一2—狻酸酯/叔一丁基5—原冰片烯一2—羧酸酯/5 一原冰片烯一 2 —羧酸/1 ，3 —丁二醇二丙烯酸酯）的 合成 首先將（i ) 2 —羥基乙基5 —原冰片烯一 2 —濟酸 酯（〇♦1莫耳），（i丨）叔一丁基5—原冰片烯一2 一羧酸酯（0*85莫耳），（i i i) 5 —原冰片烯一 2—羧酸（0.05莫耳），（iv)1，3-丁二醇二 丙烯酸酯（0·1莫耳）〔其是化學式2範園内的交聯單 體〕，及（ν )順丁烯二酸酐（1 ♦ 〇莫耳）溶於四氫呋 喃中。 加入2，2 ' —偶氮雙異丁膳（A I Β Ν )( 6 · 1 6克）至结果溶液中當作聚合化反應起始劑’接著 在氮氣或氬氣氣氛之下，K溫度6 7 °C使混合物反應1 0 小時，所得聚合物由乙醚或己烷中沈澱，乾燥後可得化學 式6的聚（順丁烯二酸酐/ 2 —羥基乙基5 —原冰片烯一 2 —羧酸酯/叔一丁基5 —原冰片烯一 2 —羧酸酯/ 5 — 原冰片烯一 2 —羧酸/1，3 —丁，二醇二丙燏酸酯）（產 - 1 4 - 本紙張尺度適用中國國家標準（CNS)A4規格（2]0 X 297公釐) ---------------------^---------00 (請先閱讀背面之注意事項再填寫本頁) A7 五、發明說明（I、 率：以％): ^化擧式β >A small amount of a photoacid generator can also be added to the photoresist composition. Examples of suitable photoacid generators include: sulfide or key type photoacid generators, such as diphenyliodide hexafluorophosphate, diphenyliodide hexafluoroarsenate, diphenyliodide hexafluorophosphonium Acid salt, diphenyl p-methoxyphenyl trifluoromethane sulfonate, diphenyl p —tolyl trifluoromethane sulfonate, diphenyl P This paper is sized for China National Standard (CNS) A4 (2) 0 X 297 mm) -------- tr --------- ^ · (Please read the notes on the back before filling in this page) 1222968 A7 B7 V. Description of the invention (丨 C) Isobutylphenyl trifluoromethanesulfonate, diphenylρ-tert-butylphenyl dicarbonate, acid salt, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoride Arsenate 'triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, dibutylzaicylsulfonium trifluoromethanesulfonate, and the like. Formation of Photoresist Image The photoresist composition prepared according to the present invention can be spin-coated on silicon wafers to form a thin photoresist film, and then be placed on an oven or hot plate at a temperature of 70 ° C to 2 0 0 1C, preferably 8 Ο υ to 15 0 ° C soft soft-baked " 1 to 5 minutes, and then using a deep ultraviolet exposure device or an excitation laser exposure device to pass the image Exposed light source. The # source used can also be ArF, KrF, E-beam, X-ray, EUV (extreme ultraviolet), DUV (deep ultraviolet), or similar light source. The energy of the exposure light source is preferably from 1 to 1 OOrnj / cm2 ϋ Then, bake this thin photoresist film at a temperature between 1 0 t and 2 0 0 1C (please read the precautions on the back before filling in this page) and then bake (post-baked preferably at 1 0 0 ° C printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs for 200 hours, and the resulting material was K 2 ♦ 3 8 wt% or 2 · 5 wt% TMA 水溶液 Imaging solution immersion for a predetermined time, preferably It is 40 seconds, so that an ultra-fine image can be obtained. A semiconductor device with high integration can be manufactured using the photoresist image of the present invention. The above description only discloses the use of a cross-linking monomer to prepare a light. For specific examples of the method for the formulation of the copolymer or photoresist composition, it must be understood that the present invention is not limited to these examples, but also includes the use of this paper-13- This paper size is applicable to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) Intellectual Property Bureau, Ministry of Economy Printed by the Industrial and Commercial Cooperatives 1222968 A7 __B7 V. Description of the Invention ((I) Any method of preparing a crosslinked monomer as described in conventional photoresist copolymers or photoresist compositions. Detailed description of preferred embodiments of the present invention The following examples of kappa will be described in more detail, but it must be reminded that the present invention is not limited to these examples. Example 1: Poly (maleic anhydride / 2-hydroxyethyl 5 -orbornenene- 2-arsanoic acid Ester / tert-butyl 5-orthobornene-2-carboxylic acid ester / 5-ortho-norbornene- 2-carboxylic acid / 1,3-butanediol diacrylate) Synthesis of (i) 2-hydroxyl Ethyl 5 -orbornenyl-2-oleate (〇 ♦ 1 mol), (i 丨) tert-butyl 5-orthobornyl-2 -carboxylic acid ester (0 * 85 mol), (iii ) 5 —orbornenene-2-carboxylic acid (0.05 mole), (iv) 1,3-butanediol diacrylate (0.1 mole) [which is a cross-linking monomer in the range of chemical formula 2] , And (ν) maleic anhydride (1 ♦ 〇mol) was dissolved in tetrahydrofuran. 2,2'-Azobisisobutyric acid (AI Β Ν) (6.16 g) was added to the resulting solution As a polymerization initiator, the mixture was reacted for 10 hours at a K temperature of 6 7 ° C under a nitrogen or argon atmosphere. The resulting polymer was precipitated from ether or hexane. Poly (maleic anhydride / 2 -hydroxyethyl 5 -orbornene-1 -carboxylic acid ester / tert-butyl 5 -orbornylene-2 -carboxylic acid ester / 5 -orbornenyl-2 -carboxyl Acid / 1,3-butanediol diol dipropionate) (Production-1 4-This paper size applies to China National Standard (CNS) A4 (2) 0 X 297 mm) ------- -------------- ^ --------- 00 (Please read the notes on the back before filling this page) A7 V. Description of the invention (I. Rate:% ): ^ Formation β >
莫耳比例 a 1 : a 2 : a 3 : b : c 為 0 ♦ 4 0 5 : 〇·〇48:〇*〇24:0·476:0*〇47〇 (請先閱讀背面之注意事項再填寫本頁) 訂---------線一 經濟部智慧財產局員工消費合作社印製 實例2 :聚（順丁烯二酸酐/ 2 —羥基乙基5 —原冰片烯 一 2 —羧酸酯/叔一丁基5 —原冰片烯一 2 —羧酸酯/ 5 一原冰片烯一 2 —羧酸/ 1 ，4 一丁二醇二丙烯酸酯）的 合成 重覆實例1的步驟，但使用1 ，4 一丁二醇二丙烯酸 酯代替1 ，3 —丁二醇二丙烯酸酯，如此可得化學7的聚 (順丁烯二酸酐/ 2 —羥基乙基5 —原冰片烯一 2 —狻酸 酯/叔一丁基5 —原冰片烯一2 —羧酸酯/ 5 —原冰片烯 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） 1222968 Α7 __ ' Β7 五、發明說明（D ) 一2-羧酸/1，4一丁二醇二丙烯酸酯）： <化學式7 >Moire ratio a 1: a 2: a 3: b: c is 0 ♦ 4 0 5: 〇 · 〇48: 〇 * 〇24: 0 · 476: 0 * 〇47〇 (Please read the precautions on the back before (Fill in this page) Order --------- Line 1 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Example 2: Poly (maleic anhydride / 2 —hydroxyethyl 5 —orthobornene 2 — Carboxylic acid ester / tert-butyl 5-ortho-norbornene-1 2-carboxylic acid ester / 5-orthonorbornene-1 2-carboxylic acid / 1,4-butanediol diacrylate) Repeat the procedure of Example 1 However, instead of 1,3-butanediol diacrylate, 1,4-butanediol diacrylate is used, so that the chemical poly (maleic anhydride / 2-hydroxyethyl 5-orthobornene-1) can be obtained. 2 —Phenyl ester / tert-butyl 5 —orbornene-1 —carboxylic acid ester / 5 —orbornene This paper size is applicable to China National Standard (CNS) A4 (210 χ 297 mm) 1222968 Α7 __ ' Β7 5. Description of the Invention (D) Mono-2-carboxylic acid / 1,4-butanediol diacrylate: < Chemical Formula 7 >
莫耳比例 a 1 : a 2 : a 3 : b : c 為 0 ♦ 4 0 5 : 0*048：0*024： 0*476： 0*047 ^ (請先閱讀背面之注意事項再填寫本頁) #衣 -------訂---------線 實例3 : 經濟部智慧財產局員工消費合作社印製 將實例1所得的化學式6光姐劑聚合物（3 ♦ 5 7克 )溶解於乙基3—乙氧基丙酸酯中（25克），加入三苯 基銃三氟甲烷磺酸鹽（〇，02克）當作光酸產生劑，且 Μ 0 ♦ 1 0 /i m的過濾器過濾结果混合物，K製得一光咀 劑組成物。 上述所製得的光阻劑組成物旋轉塗覆於矽晶元上，且 K 1 1 0 υ的溫度〃軟一烤"9 0秒鐘，然後K具有能量 -16 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1222968 A7 B7 五、發明說明（ ο 以 後 之完 ， 烤 光烘 照| 器後 光當 曝。 射秒 雷 ο F 9 Γ 元 Α 晶 的烤 m I C 後 \ 度 J 溫 m的 o P 4 0 至 1 像 顯。 中 } 液 1 溶 圖 水 ί Η 像 Α 圖 Μ 的 T S 的/ % L t wrn 8/i 3 4 • 1 2 ♦ 於 ο 置得 其可 將 ， ， 秒 後 ο 成 4 實 : 覆 4 重 例 實 的 3 光 7 式 學 ib 的 得 製 2 Hy 實 用 使 但 驟 圖 劑 阻 光 。 一 像 成圖 形微 可超 ， 的 物 S 合 \ 聚 L 的 得Γη 所 α 1 4 例 ^_ 實 ♦ 替 ο 代一 物為 合 2 聚圖 劑。 阻像 (請先閱讀背面之注意事項再填寫本頁) I I I I---訂---------. 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（2】0 X 297公釐）Moire ratio a 1: a 2: a 3: b: c is 0 ♦ 4 0 5: 0 * 048: 0 0024: 0 * 476: 0 * 047 ^ (Please read the notes on the back before filling this page ) # 衣 ------- Order --------- Line Example 3: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the chemical formula 6 obtained from Example 1 polymer (3 ♦ 5 7 g) was dissolved in ethyl 3-ethoxypropionate (25 g), and triphenylsulfonium trifluoromethanesulfonate (0.02 g) was added as a photoacid generator, and M 0 ♦ 1 A 0 / im filter filters the resulting mixture, and K produces a smooth nozzle composition. The photoresist composition prepared above is spin-coated on silicon wafers, and the temperature of K 1 1 0 υ is softened and baked for 90 seconds, and then K has energy -16-This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1222968 A7 B7 V. Description of the invention (ο Afterwards, the light will be baked and baked | The light will be exposed after the device. Shooting seconds ο F 9 Γ 元 Α crystal baking m IC after \ degree J temperature m o P 4 0 to 1 image display. Medium} Liquid 1 solution map water Η image Α map M of the TS /% L t wrn 8 / i 3 4 • 1 2 ♦ in ο Set it as it is, and after a second, it will become 4 solids: covering 4 examples of real 3 light 7 formulas of ib 2 Hy practical so that the photo-blocking agent blocks light. It looks like a pattern that can be super-superior. The results of S and \ L are obtained by Γη α 1 4 cases ^ _ Reality ♦ Substitute ο for one thing as He 2 polyimaging agent. Image blocking (please read the precautions on the back before filling this page) III I --- Order ---------. The paper size printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to Chinese National Standard (CNS) A4 (2) 0 X 297 mm
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-1998-0063793A KR100362937B1 (en) | 1998-12-31 | 1998-12-31 | Novel photoresist crosslinkers, photoresist polymers and photoresist compositions comprising them |
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| Publication Number | Publication Date |
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| TWI222968B true TWI222968B (en) | 2004-11-01 |
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| TW088121653A TWI222968B (en) | 1998-12-31 | 1999-12-10 | Cross-linking monomers for photoresist, and process for preparing photoresist polymers using the same |
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| Country | Link |
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| JP (1) | JP4001445B2 (en) |
| KR (1) | KR100362937B1 (en) |
| CN (1) | CN1303114C (en) |
| DE (1) | DE19960506A1 (en) |
| FR (1) | FR2788062B1 (en) |
| GB (1) | GB2345286B (en) |
| IT (1) | IT1308679B1 (en) |
| NL (1) | NL1013916C2 (en) |
| TW (1) | TWI222968B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7208260B2 (en) * | 1998-12-31 | 2007-04-24 | Hynix Semiconductor Inc. | Cross-linking monomers for photoresist, and process for preparing photoresist polymers using the same |
| KR100557608B1 (en) * | 1999-02-10 | 2006-03-10 | 주식회사 하이닉스반도체 | Novel photoresist crosslinker and photoresist composition using the same |
| KR100557609B1 (en) * | 1999-02-22 | 2006-03-10 | 주식회사 하이닉스반도체 | Novel photoresist crosslinker and photoresist composition using the same |
| US6818376B2 (en) | 1999-08-23 | 2004-11-16 | Hynix Semiconductor Inc. | Cross-linker monomer comprising double bond and photoresist copolymer containing the same |
| KR100520183B1 (en) * | 1999-08-23 | 2005-10-10 | 주식회사 하이닉스반도체 | Photoresist copolymer containing crosslinker which has two double bonds |
| KR100546110B1 (en) * | 2000-01-21 | 2006-01-24 | 주식회사 하이닉스반도체 | Photoresist Crosslinking Agent and Photoresist Composition Containing the Same |
| US6664022B1 (en) * | 2000-08-25 | 2003-12-16 | Shipley Company, L.L.C. | Photoacid generators and photoresists comprising same |
| KR20020082006A (en) * | 2001-04-23 | 2002-10-30 | 금호석유화학 주식회사 | Novel acid-labile polymer and formulation material using an acid-labile polymer |
| US7138218B2 (en) | 2001-12-18 | 2006-11-21 | Hynix Semiconductor Inc. | Process for forming an ultra fine pattern using a bottom anti-reflective coating film containing an acid generator |
| US7338742B2 (en) | 2003-10-08 | 2008-03-04 | Hynix Semiconductor Inc. | Photoresist polymer and photoresist composition containing the same |
| US7270937B2 (en) | 2003-10-17 | 2007-09-18 | Hynix Semiconductor Inc. | Over-coating composition for photoresist and process for forming photoresist pattern using the same |
| KR100680405B1 (en) | 2003-11-19 | 2007-02-08 | 주식회사 하이닉스반도체 | Photoresist Composition for EUV and Method for forming Photoresist Pattern using the same |
| JP4979477B2 (en) * | 2004-03-08 | 2012-07-18 | 三菱レイヨン株式会社 | Resist polymer, resist composition, pattern manufacturing method, and resist polymer raw material compound |
| EP1750176A3 (en) * | 2005-08-03 | 2011-04-20 | JSR Corporation | Positive-type radiation-sensitive resin composition for producing a metal-plating formed material, transcription film and production method of a metal-plating formed material |
| US7745339B2 (en) | 2006-02-24 | 2010-06-29 | Hynix Semiconductor Inc. | Method for forming fine pattern of semiconductor device |
| KR100694412B1 (en) | 2006-02-24 | 2007-03-12 | 주식회사 하이닉스반도체 | Method for forming fine patterns of semiconductor devices |
| EP2133747A4 (en) * | 2007-02-26 | 2011-01-12 | Jsr Corp | Resin composition for micropattern formation and method of micropattern formation |
| US10768528B2 (en) | 2015-09-28 | 2020-09-08 | 3M Innovative Properties Company | Patterned film article comprising cleavable crosslinker and methods |
| CN116102938B (en) * | 2021-11-09 | 2023-10-20 | 上海新阳半导体材料股份有限公司 | Bottom anti-reflection coating for deep ultraviolet lithography and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1275471A (en) * | 1969-06-04 | 1972-05-24 | Du Pont | Improvements relating to photo-resists |
| GB1277674A (en) * | 1969-08-04 | 1972-06-14 | Ford Motor Co | Painting of polyolefins |
| JPS5713444A (en) * | 1980-06-27 | 1982-01-23 | Tamura Kaken Kk | Photosensitive composition |
| US4329419A (en) * | 1980-09-03 | 1982-05-11 | E. I. Du Pont De Nemours And Company | Polymeric heat resistant photopolymerizable composition for semiconductors and capacitors |
| WO1992007022A1 (en) * | 1990-10-23 | 1992-04-30 | Atomic Energy Of Canada Limited | Process for the preparation of cellulosic fibre-reinforced thermoplastic composite materials |
| US5777068A (en) * | 1994-09-13 | 1998-07-07 | Nippon Zeon Co., Ltd. | Photosensitive polyimide resin composition |
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- 1999-12-10 TW TW088121653A patent/TWI222968B/en not_active IP Right Cessation
- 1999-12-15 DE DE19960506A patent/DE19960506A1/en not_active Withdrawn
- 1999-12-15 GB GB9929650A patent/GB2345286B/en not_active Expired - Fee Related
- 1999-12-21 IT IT1999TO001137A patent/IT1308679B1/en active
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- 1999-12-22 JP JP36514699A patent/JP4001445B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| ITTO991137A0 (en) | 1999-12-21 |
| GB9929650D0 (en) | 2000-02-09 |
| IT1308679B1 (en) | 2002-01-09 |
| KR20000047041A (en) | 2000-07-25 |
| CN1258670A (en) | 2000-07-05 |
| NL1013916A1 (en) | 2000-07-03 |
| CN1303114C (en) | 2007-03-07 |
| FR2788062A1 (en) | 2000-07-07 |
| NL1013916C2 (en) | 2002-12-03 |
| GB2345286B (en) | 2004-06-30 |
| GB2345286A (en) | 2000-07-05 |
| JP2000199951A (en) | 2000-07-18 |
| FR2788062B1 (en) | 2004-09-10 |
| JP4001445B2 (en) | 2007-10-31 |
| ITTO991137A1 (en) | 2001-06-21 |
| DE19960506A1 (en) | 2000-09-07 |
| KR100362937B1 (en) | 2003-10-04 |
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