TWI278458B - Novel photoresist monomers having stability to post exposure delay, polymers thereof and photoresist compositions containing the same - Google Patents

Novel photoresist monomers having stability to post exposure delay, polymers thereof and photoresist compositions containing the same Download PDF

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TWI278458B
TWI278458B TW089115682A TW89115682A TWI278458B TW I278458 B TWI278458 B TW I278458B TW 089115682 A TW089115682 A TW 089115682A TW 89115682 A TW89115682 A TW 89115682A TW I278458 B TWI278458 B TW I278458B
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photoresist
group
compound
formula
cns
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Keun-Kyu Kong
Jae-Chang Jung
Geun-Su Lee
Ki-Ho Baik
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Hyundai Electronics Ind
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00Ethers; Compounds having groups, groups or groups
    • C07C43/30Compounds having groups
    • C07C43/305Compounds having groups having acetal carbon atoms as rings members or bound to carbon atoms of rings other than six-membered aromatic rings
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00Systems containing two condensed rings
    • C07C2602/36Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055Radiation sensitive composition or product or process of making
    • Y10S430/106Binder containing

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Polymerisation Methods In General (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerization Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Description

1278458 A7 B7 五、發明說明(/ ) 發明背景 1. 發明領域 本發明係關於一種光阻劑單體,衍生自該單體之聚合 物及含該聚合物之光阻劑組成物。尤其是,本發明係關於 一種光阻劑聚合物及含該聚合物之光阻劑組成物,當製造 高整合半導體裝置之微細電路時,其對光學微影程序(或使 用紫外光源)中之環境胺污染物不敏感,且本發明亦提供一 種製備該光阻劑聚合物及光阻劑組成物之方法。 2. 背景技藝之說明 近來,已硏究使用化學放大類型之光阻劑(亦即光阻劑 組成物)以達到在製造半導體裝置之中微細成像之高敏感性 。該光阻劑可藉由摻混光酸產生劑及含酸不安定基之母質 樹脂聚合物(亦即,光阻劑聚合物)以製備之。· 在製造半導體裝置之光學微影程序中,成像之解析度 是取決於所使用之波長。因此,較短之波長,較高之解析 度,亦即,較短波長可有較小圖案生成。 經濟部智慧財產局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 爲了使光阻劑(PR)有用於光學微影程序中,光阻劑必 須具有極佳抗蝕刻性及黏著性。再者,爲了降低製造半導 體裝置之成本,PR應能在常用之顯影溶液中顯影,例如 2.38重量%四甲基氫氧化銨(TMAH)水溶液中顯影。這些特 性在利用短波長光源,包括KrF (248 nm)、ArF (193 nm) 、VUV (157nm)及EUV (13nm))之光學微影程序中爲尤其重 要。 然而,要合成能滿足所有要求之光組劑組成物爲相當 4 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 1278458 A7 ___B7_ 五、發明說明(> ) 困難的,已發展具有經改良抗蝕刻性、黏著性及解析度之 各種不同光阻劑聚合物。然而,不幸地,大部分現今可得 之化學放大光阻劑具有相當短後曝光延遲(PED)安定性。一 般,當對光曝光之光阻劑及經曝光之光阻劑之顯影之間有 延遲時,產生於經曝光之區域中之酸會被可能存在於生產 環境中之胺所中和。因爲圖案生成是取決於曝光所產生之 酸,所以用來降低、避免或改變圖案生成,例如T-頂現象 之環境胺化合物中和酸可能會發生於圖案頂部部分形成T-形之處。 發明摘述 因此,本發明之目的爲提供一種具有經增強PED安定 性之光阻劑單體。 本發明之另一目的爲提供使用前述PR單體之聚合物 ,及其製備方法。 本發明之另一目的爲提供使用前述PR聚合物之光阻 劑組成物,及其製備方法。 本發明之又一目的爲提供一種使用前述PR組成物所 生產之半導體裝置。 圖式簡單說明 圖1爲顯示使用沒有後曝光延遲(PED)之光阻劑組成物 ,所獲得之圖案之照片; 圖2顯示使用本發明之光阻劑組成物並在顯影之前留 著經曝光之光阻劑組成物歷30分鐘,所獲得之圖案之照片 f 5 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -· n n 01 ϋ n n n )5J· n n n ϋ n 1 I- 1 n ·
I -n n I «I n n n n < 1278458 A7 五、發明說明(3 ) 圖3顯示使用本發明之光阻劑組成物並在顯影之前胃 著經曝光之光阻劑組成物歷60分鐘,所獲得之圖案之照片 ;及 圖4顯示使用本發明之光阻劑組成物並在顯影之前胃 著經曝光之光阻劑組成物歷120分鐘,所獲得之圖案之照 片; 較佳具體實施例詳述 本發明將以有助於說明本發明之特徵之圖式來說明。 所提供之圖式爲說明本發明實施之目的用,並不構成限制 其範疇。 本發明之一方面爲提供一種下式光阻劑單體·/=£ ' w i / \ t η
(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 其中每個Ζι及Ζ2分別爲CH2,CH2CH2,〇或s; 每個Ri及R2分別爲經取代或未經取代之(Ci-C5)直鏈 或支鏈烷基; 每個R;及R4分別爲氫或經取代或未經取代之(〇τ5) 直鏈或支鏈烷基; R5爲氫或甲基;且 P爲0至5之整數。 較佳地,本發明之PR單體爲選自下式la至ld之化 合物所組成之族群中。 6 t · n n if n n ϋ ϋ^tfJI MV MM W MM am 蜃 線丨 — — — III, -II n n ϋ n I· n 11 n < 本紙張尺度適用令國國家標準(CNS)A4規格(21〇 x 297公釐) n 278458
五、發明說明(¥ )
〇 〇 Ο
1h3Γ I
ch3 1 a, L3 ch3 lb 1 叫 CHj 1 c 及 ch, ch» 1 d 雖然式1化合物可由各種不同之方法以製備’在本胃 明之一特別具體實施例中,式1化合物,其中p爲0 ’是 藉由下述所製備; (a)反應下式化合物: (請先閱讀背面之注意事項再填寫本頁) 2 與下式醛化合物醛化合物: 以產生下式環醛化合物:
經濟部智慧財產局員工消費合作社印製 4 (b)在觸媒存在下,並在足以產生式.丨(其中Rl,r2, R3 ’仏及R5爲先前所定義,且Z指Z2)化合物之條件下, 反應式4化合物與醇。 本方法包括步驟(c):中和存在於反應混合物中之酸與鹼 (亦即,驗化合物)。 在一方面,在前述製備方法之步驟⑷中,式2化合物 被加到有機溶劑中’且所得溶液被冷卻到45至-25。(:之溫 *. -- I I l· I I I I ·1111111! I —AVI — — — — — — — III — — — — — — — — — — — . 1278458 A7 B7 五、發明說明(cT) ✓ 度範圍。然後,式3化合物被逐滴加到反應混合物中,且 攪拌所得混合物歷8至12小時。式4化合物的獲得可藉由 濃縮反應混合物並在減壓下蒸餾式4化合物。 在步驟(b)及.(c)中,在酸觸媒存在下,將式4化合物與 醇(例如,lOH,R2〇H或其混合物)反應,較佳具有回流。 存在於反應混合物中之任何酸然後以鹼化合物中和(亦即, 鹼化合物)。在反應中所產生之式1化合物可在減壓下藉由 蒸餾以從反應混合物中獲得。在步驟(b)中之較佳酸觸媒包 括三氟甲烷磺酸。 本發明亦提供一種衍生自含式1化合物之單體的光阻 劑聚合物。光阻劑聚合物可進一步包括下式之第二單體:
Re OH 5 (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 第 其中每個1及Y2分別爲CHb,CH2CH2,0或S ; r6爲氫或甲基; Rs爲氫或經取代或未經取代之(G-G)直鏈或支鏈烷基 R!◦爲經取代或未經取代之(CVG)直鏈或支鏈烷基;且 Q爲0至5之整數。 本發明之聚合物可進一步包括具有酸不安定保護基之 .單體。示範性酸不安定保護基包括特丁基,四氫呋喃- _ · I I I I I 1 -1 — — — 1 — — · — — — — —I1I11IIIIII — I1 — — · 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1278458 A7 B7 五、發明說明( 2-基,四氫吡喃-2-基,2-乙氧基乙基及特丁氧基乙基。 尤其是,含酸不安定基之化合物較佳爲下式之化合物 .^7
6 其中每個幻及X2分別爲CH2,CH2CH2,〇或S ; R7爲氮或甲基; R9爲氫’或經取代或未經取代之(G-G)直鏈或支鏈烷 基;及 r爲0至5之整數。 在一特別具體實施例中,本發明之聚合物爲下式 ^―〇 r8 c=o
(請先閱讀背面之注意事項再填寫本頁) t 訂i 經濟部智慧財產局員工消費合作社印製 ^to 7 其中
Xi,χ2,Yi,γ2,z!,z2,Ri,R2,R3,R4,r5,r6,R7 ’ R8 ’ R9 ’ Rio ’ p ’ q及r爲先前所定義;及 a,b,c及d代表每個單體之相對量,其中a : b : c : d •線丨#-------------1--------- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 1278458 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(j) 之莫耳比例=0.50 : 0.125〜0.40 : 0.025〜0.10 : 0.05〜0.35。 在式7之聚合物中之每個單體單元代表每個單體之總 相對比例。因此,式7並不意圖要被指定爲每個單體單元 之任何特別順序。例如衍生自馬來酐之單元的總量“a”可分 散於聚合物中或可被集中在聚合物之一特別位置上。 傾相信用於改良光阻劑組成物之PED安定性之方法爲 改變在光阻劑組成物中之聚合物之形狀。改變在光阻劑組 成物中之聚合物之形狀的方法爲使用剪切稀釋之光阻劑。 剪切稀釋之光阻劑的製備可藉由⑴使用非牛頓剪切稀釋之 溶劑作爲光阻劑組成物之成分;(U)改變聚合物之結構;及 /或(iii)當光阻劑組成物被塗覆於半導體基板上時,控制光 阻劑組成物之溫度。 因此,本發明之另一具體實施例爲關於藉由改變聚合 物之結構以製備剪切稀釋光阻劑。本發明之聚合物作用爲 剪切稀釋劑,不似傳統光阻劑聚合物。在不被任何理論束 縛下,傾相信本發明之聚合物爲剛性棒或橢圓形並對剪切 方向定位平行,以在經塗覆層之分子間提供具有很小或無 間隙之更緊密塡充結構。傾相信該緊密塡充結構可預防在 光學微影程序中所產生之酸被環境胺所中和。結果,本發 明之光阻劑聚合物提供良好光阻劑圖案,即使有後曝光延 遲。 較佳地,本發明聚合物之分子量在約4000至約12000 之範菌內。 本發明較佳聚合物包括下式7a及7b之聚合物。 10 (請先閱讀背面之注意事項再填寫本頁) •f 訂· 1 λ 丨·11 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1278458 A7 B7 五、發明說明(t)
Γ OH Γ
(請先閱讀背面之注意事項再填寫本頁) t 經濟部智慧財產局員工消費合作社印製 其中,a,b,c及d爲先前所定義。 本發明之聚合物可藉由具有傳統自由基聚合引發劑之 自由基聚合單體以製·備之。一種用於製備本發明之聚合物 的示範性程序包括下列步驟: (a) 較佳在有機溶劑中,混合 ⑴式1化合物, (ii) 式5化合物, (iii) 視需要式6化合物, (iv) 馬來酐,及 (iv)聚合引發劑;及 (b) 在鈍氣環境下,聚合該混合物。 適用於聚合反應之有機溶劑爲選自由四氫呋喃,甲苯 ,苯,甲基乙基酮及二噁烷所組成之族群中。 示範性聚合引發劑包括任何傳統自由基聚合引發劑, 例如苯醯化過氧,2,2f-偶氮異丁腈(AIBN),乙醯化過氧, 訂----- -----線丨♦----------------------- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1278458 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(f) 月桂基化過氧,特丁基過醋酸酯,特丁基氫過氧化物及= 特丁基過氧。 本發明亦提供一種光阻劑組成物,其包括本發明之光 阻劑聚合物,有機溶劑及光酸產生劑。 較佳光酸產生劑包括硫化物或鎗類型之化合物。在本 發明之一特別具體實施例中,光酸產生劑爲選擇自由二苯 基碘六氟磷酸鹽,二苯基碘六氟砷酸鹽,二苯基碘六氟銻 酸鹽,二苯基對-甲氧基苯基三氟甲烷磺酸鹽,二苯基對-甲苯基三氟甲烷磺酸鹽,二苯基對-異丁基苯基三氟甲烷磺 酸鹽,二苯基對-特丁基苯基三氟甲烷磺酸鹽,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及二丁基萘基銃三氟甲烷_鹽 所組成之族群中。典型地,所使用之光酸產生劑之份量爲 所使用之光阻劑樹脂的約0.1重量%至約10重量%。 傾發現當光酸產生劑以少於約0.1%使用時,其會降低 PR組成物之光敏感性,且當光酸產生劑以大於約10%使用 時,其會因吸收較多DUV(深紫外線)而導致較差圖案生成 〇 適用於本發明之PR組成物中之示範性有機溶劑包括 甲基3-甲氧基丙酸酯,乙基3-乙氧基丙酸酯,丙二醇甲基 醚醋酸酯,環己酮,環戊酮,2-庚酮及(2-甲氧基)乙基醋酸 酯。所使用之溶劑的份量較佳地爲PR樹脂(亦即,共聚物) 之約200重量%至約800重量%。當光阻劑被塗覆於產生半 導體兀件之合適基板,例如砂晶圓上時,該比例被發現特 12 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) # *111 -線丨#! 1278458 A7 B7 五、發明說明(丨ύ) 別適用於獲得所欲厚度之光阻層。 由本發明製備之PR組成物具有極佳抗蝕刻性、黏著 性及抗熱性。同時,明顯地,經增強PED安定性使其更適 用於例如ArF光阻劑膜上。 本發明亦提供一種用於形成PR圖案之方法,其包括 下列步驟:(a)塗覆先前所述之光阻劑組成物於半導體元件 之基板上以形成光阻劑膜;(b)使用光源將光阻劑膜曝光; 及(c)使用鹼性溶液,例如2.38重量%TMAH溶液以顯影經 曝光光阻劑膜。視需要地,光阻劑膜可較佳在步驟(b)之前 及/或之後,在約70 °C至約200 °C之溫度下被加熱(亦即 ,烘烤)。 適用於形成PR圖案之示範性光源包括ArF(193nm)、 KrF(248nm)、VUV(157nm)、EUV、E-束、X-射線或離子束 。照射能量較佳爲約lmJT/cm2至約100 mT/cm2。 本發明亦提供一種由使用先前所述之光阻劑組成物所 製造出之半導體裝置。 本發明之額外目的,優點及新穎特徵在取決於審查下 述不意圖作爲限制用之實施例,而使熟於此技藝者更佳明 白。 I.單體的製備 實施例1:式la之單體的合成 在1000毫升圓頸燒瓶中,加入1莫耳式2a環戊二烯 及100克THF。溶液被冷卻至-20°C,且逐滴加入1.2莫耳 式3a丙烯醛。攪拌反應混合物歷10小時,且使用真空蒸 13 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注音?事項再填寫本頁) ;鲁·--------訂i 線 經濟部智慧財產局員工消費合作社印製 A7 B7
1278458 五、發明說明(“) 發器濃縮。所得殘餘物在40°C之減壓下蒸餾以提供式4 a 單體(產率:80%,106克)。 在1000毫升圓頸燒瓶中,加入106克式4a單體,400 克甲醇,及0.1莫耳三氟甲烷磺酸。混合物被回流歷10小 時。此後,藉由加入KOH以中和反應混合物至約pH 7, 且在50°C之減壓下蒸餾以提供式式la單體(產率:70%,74 克)。 Ο r。 實旆例2:式lb單體的合成 重複實施例1之步驟,但使用乙醇取代甲醇以提供式lb單 體。 .II.聚合物的製備 f施例3:式7a聚合物的备成 在250cc燒瓶中’加入0.1莫耳馬來酐,〇·〇6莫耳式 6a單體,〇·〇1莫耳式5a單體,0.03莫耳式la單體(於實施 例1中製備),作爲聚合引發劑之0·5克AIBN及20克四氫 呋喃,在65°C下,及在氮氣或氬氣環境下,攪拌混合物歷 10小時。乙基醚被加入到反應混合物中,且式7a聚合物 以沉澱物獲得(產率:30%,8.5克)。 14 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---------------------訂---------^ 4 IAW. (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 1278458 A7 B7
五、發明說明((i)
c=o 〇H 5a 5 6a ’ 實施例學式7b聚合物的合疫 重複實施例3之步驟,但使用實施例2製備之式1b單 體以取代式la單體以獲得式7b聚合物。 III.光阻劑組成物的製備及圖案的生成 實施例5: 光阻劑組成物可藉由添加20式7a聚合物(在實施例3 中製備)及0.24克三苯基銃三氟甲烷磺酸鹽到丨6〇克丙二醇 甲基醚醋酸酯中以製備之。 將組成物塗覆於矽晶圓上。經塗覆晶圓於150°C下軟 烤歷90秒,使用ArF曝光機對光曝光,在H〇°C下後烘烤 歷90秒,並在2.38重量%TMAH顯影溶液中顯影以獲得 〇·13 μιη L/S之超微圖案。 實施例6: 重複實施例5之步驟,但使用實施例4製備之式7b聚 合物以取代式7a聚合物。 7: PED安宙件的實驗 在使用實施例5及6製備之光阻劑組成物以形成圖案 之方法中,爲模擬後曝光延遲,在顯影經曝光矽晶圓之前 ’經曝光矽晶圓被置於含超過30ppb胺之環境下歷0,30, 60及120分鐘。圖1至4顯示圖案大小變化之結果,而表 15 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 X 297公爱) (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 ϋ n H ϋ n n i I I n n n ϋ ϋ n I I ϋ n n n ϋ 1· n 1 ϋ ϋ n i n n « 五、發明說明U、) 1顯示由於時間延遲所導致之臨界大小(CD)的變化。 表1由於PED所導致之臨界大小(CD)之變化。 1278458 A7 B7 時間(分鐘) 聚合物 — 0 30 60 120 實施例3 ί 式 7a) . CD(nm) 150nm 150 151 153 170 實施例4 (式 7b) CD(nm) 150nm 151 152 153 169 沒有式1單體之聚合物 CD(nm) 150nm 170 (T-頂發生) *T-頂 *T-頂 *T-頂 *因爲T-頂,因此所生成之圖案不佳 由圖1至4及表1中所顯示,本發明之光阻劑組成物 在相對於傳統光阻劑組成物下,對於環境胺不敏感。因此 ,可不管後曝光延遲,而生成微細圖案。如前述所討論, 本發明之光阻劑組成物具有極佳PED安定性,而結果適用 於使用超短波長區域,例如ArF(193nm)光源之光源的光學 微影程序中。 (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 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 X 297公爱)

Claims (1)

  1. [218458 A8 B8 C8 D8 申請專利範圍 1. 一種光阻劑聚合物,其爲衍生自含有下式化合物之 1¾¾ 単體: #5
    傾.¾..灰—¾示,本繫^Ji. ’P'? 其中 每個Zj z2分別爲CH2,CH2CH2 ’ 〇或S ; 每個1及R2分別爲經取代或未經取代之(ChCO直鏈 或支鏈烷基·, 每個1及R4分別爲氫,或經取代或未經取代之(G-C5)直鏈或支鏈烷基; R5爲氫或甲基;且 P爲0至5之整數。 2.根據申請專利範圍第1項之光阻劑聚合物,其中該 單體進一步包括下式化合物: ---------……ί!-------------------IT---------……-t·· (請先閲讀背面之注意事項再填寫本頁)
    Re ^10 OH 其中每個Yl及Y2分別爲CH2,CH2CH2,〇或S ; R6爲氫或甲基; R8爲氫,或Μ代料,細代之(Gi_G5)麵或支鏈院 適用中國國家標準(CNS)A4規格 W
    1278458 A8 B8 _ C8 '' --—^_ 六、申請專利範圏 基; Rl°胃&取代或未經取代之(CVG)直鏈或支鏈烷基;且 Q爲0至5之整數。 _ 請專利範圍第2項之光阻劑聚合物,其中該 早體進一步包括具有酸不安定保護基之化合物。 4.根據申請專利範圍第3項之光阻劑聚合物,其中該 酸不女疋保護基爲選擇自由特丁基,四氫呋喃_2_基,四氫 Dtt喃-2-基’ 2-乙氧基乙基及特丁氧基乙基所組成之族群中 〇 5·根據申請專利範圍第3項之光阻劑聚合物,其中該 具有酸不专定保護基之化合物爲下式化合物: 其中母個Χι及X2分別爲CH2,CH2CH2,〇或s; R?爲氫或甲基; R9爲氫,或經取代或未經取代之(Ci_C5)直鏈或支鏈烷 基;及 r爲0至5之整數。 6.根#申請專利範圍第5項之光阻劑聚合物,其爲下 式: 用中國國家標準(CNS)A4規格(210 X 297公愛) ---------------f ! {請先閱讀背面之注意事項再塡寫本頁) 、-'α A8B8C8D8 1278458 六、申請專利範圍
    其中 a : b : c : d 之莫耳比例=〇·5〇 : 0.125〜0.40 : 0.025〜〇.1〇 : 0.05-0.35 ° 7·根據申請專利範圍第6項之光阻劑聚合物,其爲下 (請先閲讀背面之注意事項再填寫本頁)
    ΓΓΟΗ
    或 、\呑 線·- 8.根據申請專利範圍第1項之光阻劑聚合物’其中該 光阻劑聚合物之分子量在約4000至約12000之範圍內。 9·一種製備申請專利範圍第6項之光阻劑聚合物之方 法’其包括下列步驟: (a)在有機溶劑中,混合 (0下式化合物: 紙張尺度適$ t國ϋ家標準(CNS)A4;%格(210 X 297]公爱) """"" 1278458 A8 B8 C8 D8 申請專利範圍
    (η)下式化合物 W
    ^10 OH (iii)下式化合物 ,/ \ , r
    R9 (iv)馬來酐,及 (iV)聚合引發劑,且 (b)在鈍氣環境下,聚合該混合物。 10. 根據申請專利範圍第9項之方法,其中該有機溶劑 爲選自由四氫呋喃,甲苯,苯,甲基乙基酮及二噁烷所組 成之族群中。 11. 根據申請專利範圍第9項之方法,其中該聚合引發 劑爲選擇自苯醯化過氧,2,2M禺氮異丁腈(AIBN),乙醯化 過氧,月桂基化過氧,特丁基過醋酸酯,特丁基氫過氧化 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閲讀背面之注意事項再塡寫本頁) 1278458 韶 C8 D8 六、申請專利範圍 物及二特丁基過氧所組成之族群中。 (請先閲讀背面之注意事項再塡寫本頁) 12. —種光阻劑組成物,其包括申請專利範圍第1項之 光阻劑聚合物,有機溶劑及光酸產生劑。 13. 根據申請專利範圍第12項之光阻劑組成物,其中 該光酸產生劑包括硫化物或鎗類型之化合物。 14. 根據申請專利範圍第12項之光阻劑組成物,其中 該光酸產生劑爲選擇自由二苯基碘六氟磷酸鹽,二苯基碘 六氟砷酸鹽,二苯基碘六氟銻酸鹽,二苯基對-甲氧基苯基 三氟甲烷磺酸鹽,二苯基對-甲苯基三氟甲烷磺酸鹽,二苯 基對-異丁基苯基三氟甲烷磺酸鹽,二苯基對-特丁基苯基 三氟甲烷磺酸鹽,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及 二丁基萘基銃三氟甲烷磺酸鹽所組成之族群中。 15. 根據申請專利範圍第12項之光阻劑組成物,其中 所使用之該光酸產生劑之份量爲所使用之該光阻劑樹脂的 0.1重量%至10重量%。 16. 根據申請專利範圍第12項之光阻劑組成物,其中 該有機溶劑爲選擇自甲基3-甲氧基丙酸酯,乙基3-乙氧基 丙酸酯,丙二醇甲基醚醋酸酯,環己酮,及2-庚酮所組成 之族群中。 17. 根j靡申請專利範圍第12項之光阻劑組成物,其中 所使用之有機溶劑的份量爲該光阻劑聚合物之200重量% 至800重量%。 18. —種用於形成光阻劑圖案之方法,其包括下列步驟 ________§---- 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐) 1278458 頌 C8 D8 六、申請專利範圍 (a) 塗覆申請專利範圍第12項之光阻劑組成物於半導 體元件之基板上以形成光阻劑膜; (b) 使用光源將光阻劑膜曝光;及 (c) 顯影經曝光光阻劑膜。 19. 根據申請專利範圍第18項之方法,其在步驟(b)之 前及/或之後,進一步包括一烘烤步驟。 20. 根據申請專利範圍第19項之方法,其中該烘烤步 驟在約70 °C至約200 °C之溫度下進行。 21. 根據申請專利範圍第18項之方法,其中該光源爲 ArF、KrF、VUV、EUV、E-束、X-射線或離子束。 22. 根據申請專利範圍第18項之方法,其中該光阻劑 膜在1至100 irJ/cm2之曝光能量下被照射。 23. —種半導體元件,其係由申請專利範圍第18項之 方法所製造出。 ........... ! -------------1T:·...........線· (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐)
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