TWI672289B - 聚合性單體、聚合物、光阻材料及圖案形成方法 - Google Patents
聚合性單體、聚合物、光阻材料及圖案形成方法 Download PDFInfo
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- TWI672289B TWI672289B TW107131797A TW107131797A TWI672289B TW I672289 B TWI672289 B TW I672289B TW 107131797 A TW107131797 A TW 107131797A TW 107131797 A TW107131797 A TW 107131797A TW I672289 B TWI672289 B TW I672289B
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- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
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- CSYSRRCOBYEGPI-UHFFFAOYSA-N diazo(sulfonyl)methane Chemical compound [N-]=[N+]=C=S(=O)=O CSYSRRCOBYEGPI-UHFFFAOYSA-N 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000001033 ether group Chemical group 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- MBAHGFJTIVZLFB-UHFFFAOYSA-N methyl pent-2-enoate Chemical compound CCC=CC(=O)OC MBAHGFJTIVZLFB-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
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- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
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- 150000002907 osmium Chemical class 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N para-hydroxystyrene Natural products OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GXOHBWLPQHTYPF-UHFFFAOYSA-N pentyl 2-hydroxypropanoate Chemical compound CCCCCOC(=O)C(C)O GXOHBWLPQHTYPF-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- DFOXKPDFWGNLJU-UHFFFAOYSA-N pinacolyl alcohol Chemical group CC(O)C(C)(C)C DFOXKPDFWGNLJU-UHFFFAOYSA-N 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 108010001861 pregnancy-associated glycoprotein 1 Proteins 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical class S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
- C08F212/24—Phenols or alcohols
-
- 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
- C08F12/00—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 an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/373—Halogenated derivatives with all hydroxy groups on non-condensed rings and with unsaturation outside the aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/235—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring and to a carbon atom of a ring other than a six-membered aromatic ring
- C07C43/247—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring and to a carbon atom of a ring other than a six-membered aromatic ring containing halogen
-
- C—CHEMISTRY; METALLURGY
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Abstract
本發明提供在利用高能射線尤其利用EUV所為之曝光有高感度之光阻材料、使用該光阻材料之圖案形成方法、成為該光阻材料之基礎樹脂之聚合物、及可作為該聚合物之原料使用之聚合性單體。
一種下式(A)表示之聚合性單體。
式中,RA 為氫原子、甲基或三氟甲基。X1 為單鍵、醚鍵、酯鍵或醯胺鍵。Ra 為碳數1~20之1價烴基,有2個以上之Ra 存在時,相鄰的2個Ra 也可互相鍵結並和它們所鍵結之碳原子一起形成脂環結構,構成前述1價烴基之亞甲基也可取代為醚鍵或羰基。Rb 為氫原子或酸不安定基。X為鹵素原子。n及m為符合1≦n≦4、0≦m≦3及1≦n+m≦4之整數。
一種下式(A)表示之聚合性單體。
式中,RA 為氫原子、甲基或三氟甲基。X1 為單鍵、醚鍵、酯鍵或醯胺鍵。Ra 為碳數1~20之1價烴基,有2個以上之Ra 存在時,相鄰的2個Ra 也可互相鍵結並和它們所鍵結之碳原子一起形成脂環結構,構成前述1價烴基之亞甲基也可取代為醚鍵或羰基。Rb 為氫原子或酸不安定基。X為鹵素原子。n及m為符合1≦n≦4、0≦m≦3及1≦n+m≦4之整數。
Description
本發明係關於聚合性單體、聚合物、含有該聚合物之光阻材料、及使用了該光阻材料之圖案形成方法。
伴隨LSI之高整合化及高速化,圖案規則的微細化正急速進展。尤其,智慧手機等使用之邏輯器件牽引著微細化,已使用利用ArF微影之多重曝光(多圖案化微影)處理進行10nm節點之邏輯器件的量產。
之後之7nm節點、5nm節點之微影,已顯見由於多重曝光所致之高成本、在多重曝光之重疊精度之問題,期待能夠減少曝光次數之極紫外線(EUV)微影之來臨。
波長13.5nm之EUV相較於波長193nm之ArF微影,波長為1/10以下之短,故光之對比度高,可期待高解像性。EUV為短波長且能量密度高,故少量光子會使酸產生劑感光。EUV曝光中之光子數,據說是ArF曝光之1/14。EUV曝光中,由於光子的變異導致線之邊緣粗糙度(LWR)、孔之尺寸均勻性(CDU)劣化的現象被視為問題。
為了要減小光子的變異,有人提出提高光阻之吸收並增加被吸收到光阻內的光子數之提案。
自以前已有人研究經鹵素原子取代之苯乙烯系之樹脂(專利文獻1)。尤其,鹵素原子之中,碘原子對於波長13.5nm之EUV光有高吸收,故近年已有人提出使用具有碘原子作為EUV光阻材料之樹脂之提案(專利文獻2、3)。但是並不是若含有碘原子則被吸收之光子數增加便會成為高感度,據報告在EUV曝光之酸發生效率方面,碘化苯乙烯僅為羥基苯乙烯之14%(非專利文獻1)。
[先前技術文獻]
[專利文獻]
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開平5-204157號公報
[專利文獻2]日本特開2015-161823號公報
[專利文獻3]國際公開第2013/024777號
[非專利文獻]
[專利文獻2]日本特開2015-161823號公報
[專利文獻3]國際公開第2013/024777號
[非專利文獻]
[非專利文獻1]Jpn.J.Appl.Physics Vol.46, No.7, pp. L142-L144, 2007
[發明欲解決之課題]
希望開發出以酸作為觸媒之化學增幅光阻中,高感度且能減小LWR、孔圖案之CDU之光阻材料。
本發明有鑑於前述情事,目的在於提供於利用高能射線尤其利用EUV所為之曝光有高感度之光阻材料、及使用此光阻材料之圖案形成方法。又,本發明之目的為提供成為前述光阻材料之基礎樹脂之聚合物、及可作為該聚合物之原料使用之聚合性單體。
[解決課題之方式]
[解決課題之方式]
本案發明人等為了達成前述目的而努力研究,結果發現藉由使用含有在聚合物之主鏈所鍵結之芳香環上之碳原子之鄰位具苯酚性羥基或該苯酚性羥基經酸不安定基保護之結構且該芳香環上有鹵素原子之聚合物作為基礎樹脂之光阻材料,則可獲得在利用高能射線尤其利用EUV所為之曝光中,感度高且CDU小、處理寬容度廣的光阻材料,乃完成本發明。
因此本發明提供下列聚合性單體、聚合物、光阻材料及圖案形成方法。
1.一種下式(A)表示之聚合性單體;
[化1]
式中,RA 為氫原子、甲基或三氟甲基;
X1 為單鍵、醚鍵、酯鍵或醯胺鍵;
Ra 為碳數1~20之1價烴基,存在有2個以上之Ra 時,相鄰的2個Ra 也可以互相鍵結並和它們所鍵結之碳原子一起形成脂環結構;又,構成該1價烴基之亞甲基也可取代為醚鍵或羰基;
Rb 為氫原子或酸不安定基;
X為鹵素原子;
n及m為符合1≦n≦4、0≦m≦3及1≦n+m≦4之整數。
2.如1.之聚合性單體,其中,X1 為單鍵。
3.如1.或2.之聚合性單體,其中,X為碘原子。
4.一種聚合物,含有於側鏈具下式(B)表示之次結構之重複單元;
[化2]
式中,X1 為單鍵、醚鍵、酯鍵或醯胺鍵;
Ra 為碳數1~20之1價烴基,存在2個以上之Ra 時,相鄰的2個Ra 也可互相鍵結並和它們所鍵結之碳原子一起形成脂環結構;又,構成該1價烴基之亞甲基也可取代為醚鍵或羰基;
Rb 為氫原子或酸不安定基;
X為鹵素原子;
n及m為符合1≦n≦4、0≦m≦3及1≦n+m≦4之整數;
虛線係指和聚合物之主鏈之原子鍵結。
5.如4.之聚合物,其中,該重複單元以下式(a)表示;
[化3]
式中,Ra 、Rb 、X1 、X、n及m同前所述;RA 為氫原子、甲基或三氟甲基。
6.如4.或5.之聚合物,其中,X1 為單鍵。
7.如4.至6.中任一項之聚合物,其中,X為碘原子。
8.如4.至7.中任一項之聚合物,更含有具因酸而改變極性之基之重複單元。
9.如8.之聚合物,其中,具有因酸而改變極性之基之重複單元以下式(b1)或(b2)表示;
[化4]
式中,RA 各自獨立地為氫原子、甲基或三氟甲基;
Y1 為單鍵、伸苯基或伸萘基、或含有醚鍵、酯鍵或內酯環之碳數1~12之連結基;
Y2 為單鍵、酯鍵或醯胺鍵;
R1 及R2 各自獨立地為酸不安定基;
R3 為氟原子、三氟甲基、氰基、碳數1~6之烷基、碳數1~6之烷氧基、碳數2~7之醯基、碳數2~7之醯氧基、或碳數2~7之烷氧基羰基;
R4 為單鍵、或碳數1~6之伸烷基,且其碳原子之一部分也可以取代為醚鍵或酯鍵;
p為1或2;
q為0~4之整數。
10.如4.至9.中任一項之聚合物,更含有至少1種含選自羥基、羧基、內酯環、碳酸酯基、硫碳酸酯基、羰基、環狀縮醛基、醚鍵、酯鍵、磺酸酯鍵、氰基、醯胺基、-O-C(=O)-S-及-O-C(=O)-NH-中之密合性基之重複單元。
11.如4.至10.中任一項之聚合物,更含有選自下式(d1)~(d3)表示之重複單元中之至少1種;
[化5]
式中,RA 各自獨立地為氫原子、甲基或三氟甲基;
R11 及R12 各自獨立地為也可以含有雜原子之碳數1~20之1價烴基;R11 與R12 也可互相鍵結並和它們所鍵結之硫原子一起形成環;
L1 為單鍵、伸苯基、-C(=O)- L11 - L12 -或-O- L12 -,L11 為-O-或-NH-,L12 為碳數1~6之2價脂肪族烴基、或伸苯基,該2價脂肪族烴基也可以含有羰基、酯鍵、醚鍵或羥基;
L2 為單鍵、或-L21 -C(=O)-O-,L21 為也可以含有雜原子之碳數1~20之2價烴基;
L3 為單鍵、亞甲基、伸乙基、伸苯基、氟化伸苯基、-C(=O)- L31 - L32 -或-O- L32 -,L31 為-O-或-NH-,L32 為碳數1~6之2價脂肪族烴基、或伸苯基,該2價脂肪族烴基也可以含有羰基、酯鍵、醚鍵或羥基;
M- 為非親核性相對離子;
Q+ 為下式(d4)表示之鋶陽離子、或下式(d5)表示之錪陽離子;
[化6]
式中,R13 ~R17 各自獨立地為也可以含有雜原子之碳數1~20之1價烴基;R13 、R14 及R15 中之任二者也可互相鍵結並和它們所鍵結之硫原子一起形成環。
12.一種光阻材料,包含:含有如4.至10.中任一項之聚合物之基礎樹脂、有機溶劑、及酸產生劑。
13.一種光阻材料,包含:含有如11.之聚合物之基礎樹脂、及有機溶劑。
14.如12.或13.之光阻材料,更含有淬滅劑。
15.如12.至14.中任一項之光阻材料,更含有界面活性劑。
16.一種圖案形成方法,包括下列步驟:
將如12.至15.中任一項之光阻材料塗佈在基板上,進行加熱處理而形成光阻膜;將該光阻膜以高能射線進行曝光;及使用顯影液將已曝光之光阻膜進行顯影。
17.如16.之圖案形成方法,其中,該高能射線係i射線、KrF準分子雷射、ArF準分子雷射、電子束、或波長3~15nm之極紫外線。
[發明之效果]
1.一種下式(A)表示之聚合性單體;
[化1]
式中,RA 為氫原子、甲基或三氟甲基;
X1 為單鍵、醚鍵、酯鍵或醯胺鍵;
Ra 為碳數1~20之1價烴基,存在有2個以上之Ra 時,相鄰的2個Ra 也可以互相鍵結並和它們所鍵結之碳原子一起形成脂環結構;又,構成該1價烴基之亞甲基也可取代為醚鍵或羰基;
Rb 為氫原子或酸不安定基;
X為鹵素原子;
n及m為符合1≦n≦4、0≦m≦3及1≦n+m≦4之整數。
2.如1.之聚合性單體,其中,X1 為單鍵。
3.如1.或2.之聚合性單體,其中,X為碘原子。
4.一種聚合物,含有於側鏈具下式(B)表示之次結構之重複單元;
[化2]
式中,X1 為單鍵、醚鍵、酯鍵或醯胺鍵;
Ra 為碳數1~20之1價烴基,存在2個以上之Ra 時,相鄰的2個Ra 也可互相鍵結並和它們所鍵結之碳原子一起形成脂環結構;又,構成該1價烴基之亞甲基也可取代為醚鍵或羰基;
Rb 為氫原子或酸不安定基;
X為鹵素原子;
n及m為符合1≦n≦4、0≦m≦3及1≦n+m≦4之整數;
虛線係指和聚合物之主鏈之原子鍵結。
5.如4.之聚合物,其中,該重複單元以下式(a)表示;
[化3]
式中,Ra 、Rb 、X1 、X、n及m同前所述;RA 為氫原子、甲基或三氟甲基。
6.如4.或5.之聚合物,其中,X1 為單鍵。
7.如4.至6.中任一項之聚合物,其中,X為碘原子。
8.如4.至7.中任一項之聚合物,更含有具因酸而改變極性之基之重複單元。
9.如8.之聚合物,其中,具有因酸而改變極性之基之重複單元以下式(b1)或(b2)表示;
[化4]
式中,RA 各自獨立地為氫原子、甲基或三氟甲基;
Y1 為單鍵、伸苯基或伸萘基、或含有醚鍵、酯鍵或內酯環之碳數1~12之連結基;
Y2 為單鍵、酯鍵或醯胺鍵;
R1 及R2 各自獨立地為酸不安定基;
R3 為氟原子、三氟甲基、氰基、碳數1~6之烷基、碳數1~6之烷氧基、碳數2~7之醯基、碳數2~7之醯氧基、或碳數2~7之烷氧基羰基;
R4 為單鍵、或碳數1~6之伸烷基,且其碳原子之一部分也可以取代為醚鍵或酯鍵;
p為1或2;
q為0~4之整數。
10.如4.至9.中任一項之聚合物,更含有至少1種含選自羥基、羧基、內酯環、碳酸酯基、硫碳酸酯基、羰基、環狀縮醛基、醚鍵、酯鍵、磺酸酯鍵、氰基、醯胺基、-O-C(=O)-S-及-O-C(=O)-NH-中之密合性基之重複單元。
11.如4.至10.中任一項之聚合物,更含有選自下式(d1)~(d3)表示之重複單元中之至少1種;
[化5]
式中,RA 各自獨立地為氫原子、甲基或三氟甲基;
R11 及R12 各自獨立地為也可以含有雜原子之碳數1~20之1價烴基;R11 與R12 也可互相鍵結並和它們所鍵結之硫原子一起形成環;
L1 為單鍵、伸苯基、-C(=O)- L11 - L12 -或-O- L12 -,L11 為-O-或-NH-,L12 為碳數1~6之2價脂肪族烴基、或伸苯基,該2價脂肪族烴基也可以含有羰基、酯鍵、醚鍵或羥基;
L2 為單鍵、或-L21 -C(=O)-O-,L21 為也可以含有雜原子之碳數1~20之2價烴基;
L3 為單鍵、亞甲基、伸乙基、伸苯基、氟化伸苯基、-C(=O)- L31 - L32 -或-O- L32 -,L31 為-O-或-NH-,L32 為碳數1~6之2價脂肪族烴基、或伸苯基,該2價脂肪族烴基也可以含有羰基、酯鍵、醚鍵或羥基;
M- 為非親核性相對離子;
Q+ 為下式(d4)表示之鋶陽離子、或下式(d5)表示之錪陽離子;
[化6]
式中,R13 ~R17 各自獨立地為也可以含有雜原子之碳數1~20之1價烴基;R13 、R14 及R15 中之任二者也可互相鍵結並和它們所鍵結之硫原子一起形成環。
12.一種光阻材料,包含:含有如4.至10.中任一項之聚合物之基礎樹脂、有機溶劑、及酸產生劑。
13.一種光阻材料,包含:含有如11.之聚合物之基礎樹脂、及有機溶劑。
14.如12.或13.之光阻材料,更含有淬滅劑。
15.如12.至14.中任一項之光阻材料,更含有界面活性劑。
16.一種圖案形成方法,包括下列步驟:
將如12.至15.中任一項之光阻材料塗佈在基板上,進行加熱處理而形成光阻膜;將該光阻膜以高能射線進行曝光;及使用顯影液將已曝光之光阻膜進行顯影。
17.如16.之圖案形成方法,其中,該高能射線係i射線、KrF準分子雷射、ArF準分子雷射、電子束、或波長3~15nm之極紫外線。
[發明之效果]
使用本發明之聚合物作為基礎樹脂之光阻材料,在高能射線尤其波長13.5nm之EUV曝光中,由於鹵素原子所為之吸收非常大,故曝光中會從碘有效地產生2次電子。此2次電子傳遞到酸產生劑會因而有效率地產生酸,故感度提高。又,本發明之聚合物因主鏈之鄰位具有苯酚性羥基,所以對於鹼顯影液有適度的溶解速度。因此能建構低CDU之光阻材料。
以下對於本發明詳細説明。又,以下之説明中,取決於化學式表示之結構,可能存在不對稱碳並且存在鏡像異構物、非鏡像異構物,但於此情形,以一個式子來代表表示此等異構物。此等異構物可單獨使用,也可以混合物的形式使用。
[聚合性單體]
本發明之聚合性單體以下式(A)表示。
[化7]
本發明之聚合性單體以下式(A)表示。
[化7]
式(A)中,RA
為氫原子、甲基或三氟甲基。X1
為單鍵、醚鍵、酯鍵或醯胺鍵,但考量使聚合物之主鏈為剛直之觀點,X1
宜為單鍵。又,X1
為酯鍵或醯胺鍵時,該等鍵結中之氧原子或氮原子與芳香環上之碳原子宜鍵結較佳。
式(A)中,Ra
為碳數1~20之1價烴基,有2個以上之Ra
存在時,相鄰的2個Ra
也可互相鍵結並和它們所鍵結之碳原子一起形成脂環結構。又,構成前述1價烴基之亞甲基也可取代為醚鍵或羰基。
前述碳數1~20之1價烴基可為直鏈狀、分支狀、環狀之任一者。前述1價烴基可列舉甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、2-乙基己基、正辛基等直鏈狀或分支狀之烷基、環戊基、環己基、降莰基、三環癸基、金剛烷基等1價脂環族飽和烴基。
作為相鄰的2個Ra
互相鍵結並和它們所鍵結之碳原子一起形成之脂環結構,具體而言可列舉環丙烷環、環丁烷環、環戊烷環、環己烷環等。
式(A)中,Rb
為氫原子或酸不安定基。Rb
為酸不安定基時,宜和相鄰的氧原子一起形成縮醛結構、3級醚結構,但不限定於此等。
式(A)中,X為鹵素原子。前述鹵素原子可列舉氟原子、氯原子、溴原子、碘原子。該等之中,EUV之吸收效率高之溴原子或碘原子較理想,碘原子更理想。
式(A)中,n及m為符合1≦n≦4、0≦m≦3及1≦n+m≦4之整數,但n為2~4之整數較佳,m宜為0較佳。
式(A)表示之聚合性單體可列舉如下但不限於此等。又,下式中,RA
及Rb
同前述。
[化8]
[化8]
[化9]
[化10]
[化11]
[化12]
[化13]
[化14]
[化15]
[化16]
[化17]
[化18]
[化19]
本發明之聚合性單體,特徵為:在聚合性基所鍵結之芳香環上之碳原子之鄰位具有苯酚性羥基或該苯酚性羥基經酸不安定基保護之結構,且該芳香環上之碳原子上有鹵素原子鍵結。本發明之聚合性單體納入到聚合物時,於曝光中會從鹵素原子有效地產生2次電子。其藉由傳遞到酸產生劑,會有效率地產生酸,據認為感度提高。鹵素原子之中,碘原子在高能射線尤其波長13.5nm之EUV曝光之吸收非常大,故尤其前述鹵素原子為碘原子時,此效果大。又,聚合物主鏈之鄰位有苯酚性羥基,所以在針對鹼顯影液進行顯影時有適當的溶解速度。經酸不安定基保護時,因酸作用會進行脱保護反應並生成苯酚性羥基,因此曝光部與未曝光部之對比度提高。因這些相乘效果,能建構CDU小的光阻材料。
式(A)表示之聚合性單體,例如可依下列所示之反應合成,但不限於此。以下舉例針對式(A)中之RA
為氫原子且X1
為單鍵之單體(A')之合成説明。
[化20]
式中,Ra 、Rb 、X、n及m同前述。
[化20]
式中,Ra 、Rb 、X、n及m同前述。
單體(A'),可藉由將成為原料之芳香族化合物之甲醯基利用Wittig反應變換為乙烯基而獲得。
反應可依常法進行。例如:將甲基三苯基溴化鏻等Wittig試藥前驅體溶於四氫呋喃、或二乙醚等醚系溶劑,邊適當冷卻邊添加鹼而製備Wittig試藥。使用之鹼宜為強鹼,具體而言可列舉正丁基鋰等烷基鋰試藥、第三丁氧基鉀等鹼金屬鹽。於系中製備Wittig試藥後,將原料溶於四氫呋喃、或二乙醚等醚系溶劑並進行滴加、熟成,可獲得單體(A')。
針對Wittig試藥之使用量,考量原料之羥基所致之失活,相對於芳香族化合物1莫耳宜為2.0~5.0莫耳較理想,2.0~3.0莫耳更理想。若超過5.0莫耳,由於原料費增加有時在成本方面會變得不利,而且有時去除為副產物之三苯基氧化膦會變得困難。也可使用羥基經酸不安定基保護之原料。反應可因應必要進行冷卻或加熱等而實施,但通常在0℃~溶劑之沸點左右之範圍進行。就產率觀點,反應時間宜利用氣體層析(GC)、矽膠薄層層析(TLC)來追蹤反應並使反應完成,通常0.5~2小時左右。可從反應混合物利用通常之水系處理(aqueous work-up)獲得單體(A'),若有必要,可依蒸餾、層析、再結晶等常法進行精製。
又,就其他方法,單體(A')可藉由對於成為原料之芳香族化合物之甲醯基利用甲基鋰等有機鋰試藥、或甲基氯化鎂等有機鎂試藥實施加成反應,並將生成之化合物(A'')脱水而變換為乙烯基以獲得。
[化21]
式中,Ra 、Rb 、X、n及m同前述。
[化21]
式中,Ra 、Rb 、X、n及m同前述。
第一階段,係對於成為原料之芳香族化合物之甲醯基,實施利用甲基鋰等有機鋰試藥、或甲基氯化鎂等有機鎂試藥所為之加成反應,獲得化合物(A'')之反應。
反應可依常法進行。使用之甲基鋰等有機鋰試藥、或甲基氯化鎂等有機鎂試藥,可依公知之配方於使用前製備,也可使用市售且買入者。使用市售品時,宜取決於買入時之濃度以四氫呋喃、二乙醚等溶劑適當稀釋後使用。可藉由在有機金屬試藥中滴加成為原料之芳香族化合物之溶液而獲得化合物(A'')。
針對有機金屬試藥之使用量,考量成為原料之芳香族化合物之羥基所致之失活,相對於芳香族化合物1莫耳為2.0~4.0莫耳較理想,2.0~3.0莫耳更理想。若超過4.0莫耳,有時會因原料費增加造成於成本方面不利。反應可因應必要而進行冷卻或加熱等而實施,通常於0~50℃之範圍內進行。考量產率的觀點,宜利用氣體層析(GC)、矽膠薄層層析(TLC)追蹤反應而使反應完結,反應時間通常為約0.5~12小時。可從反應混合物利用通常之水系處理(aqueous work-up)獲得化合物(A''),若有必要,可利用蒸餾、層析、再結晶等常法進行精製。
第2階段,係將化合物(A'')之2級羥基使用酸觸媒脱水並獲得單體(A')之步驟。
反應可依常法進行。藉由將化合物(A'')溶解於正庚烷、甲苯、二甲苯等烴系溶劑並加入酸觸媒,進行加熱,脱水反應進行,並獲得單體(A')。使用之酸觸媒宜為強酸較理想,其中硫酸、硝酸、對甲苯磺酸、三氟甲磺酸尤佳。反應溫度通常在60℃~溶劑之沸點之範圍內進行。為了使反應加快,宜將產生之水餾出到系外較佳。從產率的觀點,宜利用氣體層析(GC)、矽膠薄層層析(TLC)追蹤反應並使反應完結較理想,反應時間通常為1~24小時左右。可從反應混合物利用通常的水系處理(aqueous work-up)獲得單體(A'),若有必要可依蒸餾、層析、再結晶等常法進行精製。
[聚合物]
本發明之聚合物,含有在側鏈具下式(B)表示之次結構之重複單元。
[化22]
式中,X1 、Ra 、Rb 、X、n及m同前述。虛線係指和聚合物之主鏈間之原子鍵結。
本發明之聚合物,含有在側鏈具下式(B)表示之次結構之重複單元。
[化22]
式中,X1 、Ra 、Rb 、X、n及m同前述。虛線係指和聚合物之主鏈間之原子鍵結。
式(B)中,X1
宜為單鍵。又,X宜為碘原子較佳。
專利文獻2針對含有來自含碘原子之對羥基苯乙烯、間羥基苯乙烯之重複單元之聚合物記載,但當使用係苯乙烯結構且主鏈的對位或間位有苯酚性羥基之結構單元時,會形成苯酚性羥基突向主鏈外側之結構。因而和鹼顯影液之親和性高,預料高分子化合物之鹼顯影液溶解速度會變得非常快。溶解速度過快因而正型光阻的情形連未曝光部也有一部分溶解,據認為LWR、CDU劣化。
作為有式(B)表示之次結構之重複單元,宜為來自式(A)表示之聚合性單體者,亦即下式(a)表示之重複單元(以下也稱為重複單元a)較佳。
[化23]
式中,RA 、X1 、Ra 、Rb 、X、n及m同前述。
[化23]
式中,RA 、X1 、Ra 、Rb 、X、n及m同前述。
又,本發明之聚合物中也可以含有具因酸而改變極性之基之重複單元(以下也稱為重複單元b)。本發明之聚合物含有重複單元b時,含該聚合物之本發明之光阻材料可作為利用鹼顯影而獲得正型圖案之正型光阻材料、或利用有機溶劑顯影而獲得負型圖案之負型光阻材料使用。
作為重複單元b宜為下式(b1)表示之重複單元(以下也稱為重複單元b1)或下式(b2)表示之重複單元(以下也稱為重複單元b2)較佳。
[化24]
[化24]
式中,RA
同前述。Y1
為單鍵、伸苯基或伸萘基、或含醚鍵、酯鍵或內酯環之碳數1~12之連結基。Y2
為單鍵、酯鍵或醯胺鍵。R1
及R2
各自獨立地為酸不安定基。R3
為氟原子、三氟甲基、氰基、碳數1~6之烷基、碳數1~6之烷氧基、碳數2~7之醯基、碳數2~7之醯氧基、或碳數2~7之烷氧基羰基。R4
為單鍵、或碳數1~6之伸烷基,且其碳原子之一部分也可取代為醚鍵或酯鍵。p為1或2。q為0~4之整數。
重複單元b1可列舉如下但不限於此等。又,下式中,RA
及R1
同前述。
[化25]
[化25]
重複單元b2可列舉如下但不限於此等。又,下式中,RA
及R2
同前述。
[化26]
[化26]
式(b1)及(b2)中之、R1
及R2
表示之酸不安定基,例如:日本特開2013-80033號公報、日本特開2013-83821號公報記載者。
一般而言,前述酸不安定基可列舉下式(AL-1)~(AL-3)表示者。
[化27]
[化27]
式(AL-1)及(AL-2)中,RL1
及RL2
為1價烴基,也可以含有氧原子、硫原子、氮原子、氟原子等。前述1價烴基可為直鏈狀、分支狀、環狀之任一者,宜為碳數1~40之烷基較理想,碳數1~20之烷基更理想。式(AL-1)中,a為0~10之整數,1~5之整數較佳。
式(AL-2)中,RL3
及RL4
各自獨立地為氫原子、或1價烴基,也可以含有氧原子、硫原子、氮原子、氟原子等。前述1價烴基可為直鏈狀、分支狀、環狀之任一者,宜為碳數1~20之烷基較佳。又,RL2
、RL3
及RL4
中任二者也可互相鍵結並和它們所鍵結之碳原子或碳原子以及氧原子一起形成碳數3~20之環。前述環宜為碳數4~16之環較理想,尤其脂環為較佳。
式(AL-3)中,RL5
、RL6
及RL7
各自獨立地為1價烴基,也可以含有氧原子、硫原子、氮原子、氟原子等。前述1價烴基可為直鏈狀、分支狀、環狀之任一者,宜為碳數1~20之烷基較佳。又,RL5
、RL6
及RL7
中任二者也可互相鍵結並和它們所鍵結之碳原子一起形成碳數3~20之環。前述環宜為碳數4~16之環較理想,尤其脂環為較佳。
本發明之聚合物中,就重複單元b而言也可含有因酸所致之脱水反應而從親水性變化為疏水性之重複單元(以下也稱為重複單元b3。)。使用重複單元b3時,後述本發明之光阻材料可作為利用鹼顯影獲得負型圖案之負型光阻材料使用。
作為給予重複單元b3之單體可列舉如下但不限於此等。又,下式中,RA
同前述。
[化28]
[化28]
本發明之聚合物也可更含有含選自羥基、羧基、內酯環、碳酸酯基、硫碳酸酯基、羰基、環狀縮醛基、醚鍵、酯鍵、磺酸酯鍵、氰基、醯胺基、-O-C(=O)-S-、及-O-C(=O)-NH-中之密合性基之重複單元(以下也稱為重複單元c。)。作為給予重複單元c之單體可列舉如下但不限於此等。又,下式中,RA
同前述。
[化29]
[化30]
[化31]
[化32]
[化33]
[化34]
[化35]
[化36]
重複單元c宜為有羥基或內酯環者較理想,尤其有苯酚性羥基或內酯環者更理想。
本發明之聚合物也可以更含有選自下式(d1)~(d3)表示之重複單元(以下也分別稱為重複單元d1~d3)中之至少1種。
[化37]
[化37]
式(d1)~(d3)中,RA
同前述。L1
為單鍵、伸苯基、-C(=O)- L11
- L12
-或-O- L12
-,L11
為-O-或-NH-,L12
為碳數1~6之2價脂肪族烴基、或伸苯基,前述2價脂肪族烴基也可以含有羰基、酯鍵、醚鍵或羥基。L2
為單鍵、或-L21
-C(=O)-O-,L21
為也可以含有雜原子之碳數1~20之2價烴基。L3
為單鍵、亞甲基、伸乙基、伸苯基、氟化伸苯基、-C(=O)- L31
- L32
-或-O- L32
-,L31
為-O-或-NH-,L32
為碳數1~6之2價脂肪族烴基、或伸苯基,前述2價脂肪族烴基也可以含有羰基、酯鍵、醚鍵或羥基。M-
為非親核性相對離子。
L12
或L32
表示之2價脂肪族烴基可為直鏈狀、分支狀、環狀任一者。其具體例可列舉亞甲基、乙烷-1,1-二基、乙烷-1,2-二基、丙烷-1,2-二基、丙烷-2,2-二基、丙烷-1,3-二基、2-甲基丙烷-1,3-二基、丁烷-1,3-二基、丁烷-2,3-二基、丁烷-1,4-二基、戊烷-1,3-二基、戊烷-1,4-二基、2,2-二甲基丙烷-1,3-二基、戊烷-1,5-二基、己烷-1,6-二基、環戊烷-1,2-二基、環戊烷-1,3-二基、環己烷-1,6-二基等直鏈狀、分支狀或環狀之2價飽和脂肪族烴基、乙烯-1,2-二基、1-丙烯-1,3-二基、2-丁烯-1,4-二基、1-甲基-1-丁烯-1,4-二基、2-環己烯-1,4-二基等直鏈狀、分支狀或環狀之2價不飽和脂肪族烴基。
L21
表示之也可以含有雜原子之2價烴基可為直鏈狀、分支狀、環狀中任一者。其具體例可列舉如下但不限於此等。
[化38]
式中,虛線為原子鍵結。
[化38]
式中,虛線為原子鍵結。
式(d2)及(d3)中,Q+
為下式(d4)表示之鋶陽離子、或下式(d5)表示之錪陽離子。
[化39]
[化39]
式(d1)、(d4)及(d5)中,R11
~R17
各自獨立地為也可以含有雜原子之碳數1~20之1價烴基。R11
與R12
也可互相鍵結並和它們所鍵結之硫原子一起形成環,R13
、R14
及R15
中之任二者也可互相鍵結並和它們所鍵結之硫原子一起形成環。
R11
~R17
表示之1價烴基可為直鏈狀、分支狀、環狀中之任一者,其具體例可列舉甲基、乙基、正丙基、異丙基、正丁基、第三丁基等直鏈狀或分支狀之烷基、環丙基、環戊基、環己基、環丙基甲基、4-甲基環己基、環己基甲基、降莰基、金剛烷基等環狀飽和1價烴基;乙烯基、1-丙烯基、2-丙烯基、丁烯基、己烯基等直鏈狀或分支狀之烯基、環己烯基等環狀不飽和1價烴基;苯基、萘基、噻吩基等芳基;苄基、1-苯基乙基、2-苯基乙基等芳烷基等,但芳基較佳。又,該等基之氫原子之一部分也可取代為含有氧原子、硫原子、氮原子、鹵素原子等雜原子之基,該等基之碳原子之一部分也可取代為含有氧原子、硫原子、氮原子等雜原子之基,其結果也可以含有羥基、氰基、硝基、羰基、磺醯基、醚鍵、酯鍵、磺酸酯鍵、碳酸酯基、內酯環、磺內酯環、羧酸酐、鹵烷基等。
藉由使酸產生劑鍵結於聚合物主鏈可減小酸擴散,防止由於酸擴散之模糊導致解像性下降。又,酸產生劑藉由均勻分散,可改善邊緣粗糙度(LER、LWR)。
R11
與R12
互相鍵結並和它們所鍵結之硫原子一起形成環時、或R13
、R14
及R15
中之任二者互相鍵結並和它們所鍵結之硫原子一起形成環時之具體例可列舉如下但不限於此等。
[化40]
式中,R18
為也可以含有雜原子之碳數1~20之1價烴基。前述1價烴基可列舉和在R11
~R17
之説明敘述者為同樣者。
式(d4)表示之鋶陽離子可列舉如下但不限於此等。
[化41]
[化42]
[化43]
[化44]
[化45]
[化46]
[化47]
[化48]
[化49]
[化50]
式(d5)表示之錪陽離子可列舉如下但不限於此等。又,下式中,Me為甲基。
[化51]
[化51]
作為M-
表示之非親核性相對離子可列舉氯化物離子、溴化物離子等鹵化物離子;三氟甲磺酸根、1,1,1-三氟乙磺酸根、九氟丁磺酸根等氟烷基磺酸根;甲苯磺酸根、苯磺酸根、4-氟苯磺酸根、1,2,3,4,5-五氟苯磺酸根等芳基磺酸根;甲磺酸根、丁磺酸根等烷基磺酸根;雙(三氟甲基磺醯基)醯亞胺離子、雙(全氟乙基磺醯基)醯亞胺離子、雙(全氟丁基磺醯基)醯亞胺等醯亞胺酸離子;參(三氟甲基磺醯基)甲基化物離子、參(全氟乙基磺醯基)甲基化物等甲基化物酸離子等。
又,前述非親核性相對離子也可列舉下式(F-1)表示之α位取代為氟原子而得之磺酸根離子、及下式(F-2)表示之α及β位取代為氟原子之磺酸根離子。
[化52]
[化52]
式(F-1)中,R19
為氫原子、碳數1~20之烷基、碳數2~20之烯基、或碳數6~20之芳基,也可以含有醚鍵、酯鍵、羰基、內酯環或氟原子。前述烷基及烯基可為直鏈狀、分支狀、環狀中任一者。
式(F-2)中,R20
為氫原子、碳數1~30之烷基、碳數2~30之醯基、碳數2~20之烯基、碳數6~20之芳基、或碳數6~20之芳氧基,也可以含有醚鍵、酯鍵、羰基或內酯環。前述烷基、醯基及烯基可為直鏈狀、分支狀、環狀中任一者。
重複單元d1之具體例可列舉如下但不限於此等。又,下式中,RA
同前述。
[化53]
[化53]
重複單元d2之具體例可列舉如下但不限於此等。又,下式中,RA
同前述。
[化54]
[化54]
[化55]
[化56]
[化57]
重複單元d3之具體例可列舉如下但不限於此等。又,下式中,RA
同前述。
[化58]
[化58]
本發明之聚合物除了含有重複單元d1~d3以外,也可含有日本專利第5548473號公報之段落[0129]~[0151]記載之在主鏈鍵結有磺酸、醯亞胺酸或甲基化酸陰離子之重複單元、在主鏈鍵結有鋶陽離子之重複單元,也可以含有國際公開第2011/070947號之段落[0034]~[0038]記載之來自含磺酸陰離子之單體之重複單元。
重複單元d1~d3作為酸產生劑之作用。藉由使酸產生劑鍵結於聚合物主鏈可減小酸擴散,防止由於酸擴散之模糊導致解像性下降。又,酸產生劑藉由均勻分散,可改善邊緣粗糙度。
本發明之聚合物也可更含有下式(e1)~(e5)表示之來自茚、乙烯合萘、色酮、香豆素或降莰二烯之重複單元e1~e5。
[化59]
式中,R31
各自獨立地為碳數1~30之烷基、碳數1~30之鹵化烷基、羥基、碳數1~30之烷氧基、碳數1~30之醯基、碳數2~30之烷氧基羰基、碳數6~10之芳基、鹵素原子、或1,1,1,3,3,3-六氟-2-丙醇基。h為0或1。R32
原子、碳數1~30之烷基、碳數1~30之鹵化烷基、羥基、碳數1~30之烷氧基、碳數1~30之醯基、碳數2~30之烷氧基羰基、碳數6~10之芳基、鹵素原子、或1,1,1,3,3,3-六氟-2-丙醇基。X0
為亞甲基、氧原子或硫原子。前述烷基、鹵化烷基、烷氧基、醯基及烷氧基羰基可為直鏈狀、分支狀、環狀之任一者。
本發明之聚合物也可更含有來自苯乙烯、乙烯基萘、乙烯基蒽、乙烯基芘或亞甲基二氫茚之重複單元f。
本發明之聚合物中之重複單元a~f之比例為0<a<1.0、0≦b1<1.0、0≦b2<1.0、0<b1+b2<1.0、0≦c≦0.9、0≦d1≦0.5、0≦d2≦0.5、0≦d3≦0.5、0≦d1+d2+d3≦0.5、0≦e1≦0.5、0≦e2≦0.5、0≦e3≦0.5、0≦e4≦0.5、0≦e5≦0.5、0≦e1+e2+e3+e4+e5≦0.5、及0≦f≦0.5較理想,0.02≦a≦0.8、0≦b1≦0.7、0≦b2≦0.7、0.1≦b1+b2≦0.7、0<c≦0.8、0≦d1≦0.4、0≦d2≦0.4、0≦d3≦0.4、0≦d1+d2+d3≦0.4、0≦e1≦0.4、0≦e2≦0.4、0≦e3≦0.4、0≦e4≦0.4、0≦e5≦0.4、0≦e1+e2+e3+e4+e5≦0.4、及0≦f≦0.4更佳,0.05≦a≦0.7、0≦b1≦0.6、0≦b2≦0.6、0.1≦b1+b2≦0.6、0<c≦0.7、0≦d1≦0.3、0≦d2≦0.3、0≦d3≦0.3、0≦d1+d2+d3≦0.3、0≦e1≦0.3、0≦e2≦0.3、0≦e3≦0.3、0≦e4≦0.3、0≦e5≦0.3、0≦e1+e2+e3+e4+e5≦0.3、及0≦f≦0.3更理想。又,a+b1+b2+c+d1+d2+d3+e1+e2+e3+e4+e5+f=1較佳。
本發明之聚合物的重量平均分子量(Mw)較佳為1,000~500,000,更佳為2,000~30,000。Mw若為前述範圍,則光阻材料之耐熱性、鹼溶解性良好。又,Mw係使用四氫呋喃(THF)作為溶劑之凝膠滲透層析(GPC)獲得之聚苯乙烯換算測定値。
又,本發明之聚合物於分子量分布(Mw/Mn)廣時,因存在低分子量、高分子量之聚合物,曝光後會在圖案上出現異物、或圖案之形狀惡化。故隨著圖案規則的微細化,如此的分子量、分子量分布之影響易增大,故為了獲得適合微細的圖案尺寸使用的光阻材料,前述聚合物之分子量分布宜為1.0~2.0,尤其1.0~1.5之窄分散較佳。
本發明之聚合物之合成方法,例如:將給予重複單元a~f之單體中之所望之單體於有機溶劑中,添加自由基聚合起始劑並進行加熱聚合之方法。
聚合時使用之有機溶劑可列舉甲苯、苯、THF、二乙醚、二烷、環己烷、環戊烷、甲乙酮、γ-丁內酯等。聚合起始劑可列舉2,2'-偶氮雙異丁腈(AIBN)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2-偶氮雙(2-甲基丙酸)二甲酯、過氧化苯甲醯、過氧化月桂醯等。反應溫度較佳為50~80℃,反應時間較佳為2~100小時,更佳為5~20小時。
將含有羥基之單體進行共聚合時,聚合時可先將羥基以乙氧基乙氧基等易以酸脱保護之縮醛基取代,於聚合後以弱酸與水進行脱保護,也可以先以乙醯基、甲醯基、三甲基乙醯基等取代,於聚合後進行鹼水解。
尤其將羥基苯乙烯、羥基乙烯基萘進行共聚合時,亦有將羥基苯乙烯、羥基乙烯基萘改為使用乙醯氧基苯乙烯、乙醯氧基乙烯基萘,於聚合後利用前述鹼水解將乙醯氧基進行脱保護而成為聚羥基苯乙烯、羥基聚乙烯基萘之方法。
鹼水解時之鹼可以使用氨水、三乙胺等。又,反應溫度較佳為-20~100℃,更佳為0~60℃,反應時間較佳為0.2~100小時,更佳為0.5~20小時。
[光阻材料]
本發明之光阻材料中,含有含前述聚合物之基礎樹脂、及有機溶劑。前述基礎樹脂可為將組成比率、Mw、分子量分布相異之2個以上之前述聚合物摻混而得者。
本發明之光阻材料中,含有含前述聚合物之基礎樹脂、及有機溶劑。前述基礎樹脂可為將組成比率、Mw、分子量分布相異之2個以上之前述聚合物摻混而得者。
[有機溶劑]
前述有機溶劑可列舉日本特開2008-111103號公報之段落[0144]~[0145]記載之環己酮、甲基正戊酮等酮類;3-甲氧基丁醇、3-甲基-3-甲氧基丁醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇等醇類;丙二醇單甲醚、乙二醇單甲醚、丙二醇單乙醚、乙二醇單乙醚、丙二醇二甲醚、二乙二醇二甲醚等醚類;丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、乳酸乙酯、丙酮酸乙酯、乙酸丁酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸第三丁酯、丙酸第三丁酯、丙二醇單第三丁醚乙酸酯等酯類;γ-丁內酯等內酯類等。該等溶劑可單獨使用1種或混用2種以上。
前述有機溶劑可列舉日本特開2008-111103號公報之段落[0144]~[0145]記載之環己酮、甲基正戊酮等酮類;3-甲氧基丁醇、3-甲基-3-甲氧基丁醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇等醇類;丙二醇單甲醚、乙二醇單甲醚、丙二醇單乙醚、乙二醇單乙醚、丙二醇二甲醚、二乙二醇二甲醚等醚類;丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、乳酸乙酯、丙酮酸乙酯、乙酸丁酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸第三丁酯、丙酸第三丁酯、丙二醇單第三丁醚乙酸酯等酯類;γ-丁內酯等內酯類等。該等溶劑可單獨使用1種或混用2種以上。
有機溶劑之摻合量相對於基礎樹脂100質量份為50~10,000質量份較理想,100~5,000質量份更理想。
[酸產生劑]
本發明之光阻材料中,為了使其作為化學增幅光阻材料,也可以含有酸產生劑(以下也稱為添加型酸產生劑。)。前述添加型酸產生劑,例如:感應活性光線或放射線而產生酸之化合物(光酸產生劑)。又,基礎樹脂含有重複單元d1~d3時,亦即酸產生劑係含在基礎樹脂中時,也可不含有添加型酸產生劑。
本發明之光阻材料中,為了使其作為化學增幅光阻材料,也可以含有酸產生劑(以下也稱為添加型酸產生劑。)。前述添加型酸產生劑,例如:感應活性光線或放射線而產生酸之化合物(光酸產生劑)。又,基礎樹脂含有重複單元d1~d3時,亦即酸產生劑係含在基礎樹脂中時,也可不含有添加型酸產生劑。
前述光酸產生劑只要是因高能射線照射而產酸之化合物即無特殊限制。理想的光酸產生劑可列舉鋶鹽、錪鹽、磺醯基重氮甲烷、N-磺醯氧基醯亞胺、肟-O-磺酸酯型酸產生劑等。如此的光酸產生劑之具體例可列舉日本特開2008-111103號公報之段落[0122]~[0142]記載者。
又,光酸產生劑也可理想地使用下式(1-1)表示之鋶鹽、下式(1-2)表示之錪鹽。
[化60]
[化60]
式(1-1)及(1-2)中,R101
、R102
、R103
、R104
及R105
各自獨立地為也可以含有雜原子之碳數1~20之1價烴基。又,R101
、R102
及R103
中之任二者也可互相鍵結並和它們所鍵結之硫原子一起形成環。前述1價烴基可為直鏈狀、分支狀、環狀中任一者,其具體例可列舉和在式(d1)、(d4)及(d5)之R11
~R17
之説明於前述者為同樣者。
作為式(1-1)表示之鋶鹽之陽離子部分可列舉和就式(d4)表示之陽離子於前述者為同樣者。又,作為式(1-2)表示之錪鹽之陽離子部分,可列舉和就式(d5)表示之陽離子部分於前述者為同樣者。
式(1-1)及(1-2)中,X-
係選自下式(1A)~(1D)之陰離子。
[化61]
[化61]
式(1A)中,Rfa
為氟原子、或也可以含有雜原子之碳數1~40之1價烴基。前述1價烴基可為直鏈狀、分支狀、環狀中之任一者,其具體例可列舉和就後述R105
之説明記述者為同樣者。
式(1A)表示之陰離子宜為下式(1A')表示者較佳。
[化62]
[化62]
式(1A')中,R104
為氫原子或三氟甲基,較佳為三氟甲基。R105
為也可以含有雜原子之碳數1~38之1價烴基。前述雜原子宜為氧原子、氮原子、硫原子、鹵素原子等較理想,氧原子更理想。考量在微細圖案形成獲得高解像性之觀點,前述1價烴基尤其宜為碳數6~30者較佳。前述1價烴基可為直鏈狀、分支狀或環狀中之任一者,其具體例可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、新戊基、環戊基、己基、庚基、2-乙基己基、壬基、十一基、十三基、十五基、十七基、二十基等直鏈狀或分支狀之烷基;環己基、1-金剛烷基、2-金剛烷基、1-金剛烷基甲基、降莰基、降莰基甲基、三環癸基、四環十二基、四環十二基甲基、二環己基甲基等1價飽和環狀脂肪族烴基;烯丙基、3-環己烯基等1價不飽和脂肪族烴基;苄基、二苯基甲基等芳烷基等。又,作為含有雜原子之1價烴基,可列舉四氫呋喃基、甲氧基甲基、乙氧基甲基、甲硫基甲基、乙醯胺甲基、三氟乙基、(2-甲氧基乙氧基)甲基、乙醯氧基甲基、2-羧基-1-環己基、2-側氧基丙基、4-側氧基-1-金剛烷基、3-側氧基環己基等。又,該等基之氫原子之一部分也可以取代為含有氧原子、硫原子、氮原子、鹵素原子等雜原子之基,或該等基之碳原子之一部分也可取代為含有氧原子、硫原子、氮原子等雜原子之基,其結果也可以含有羥基、氰基、羰基、醚鍵、酯鍵、磺酸酯鍵、碳酸酯基、內酯環、磺內酯環、羧酸酐、鹵烷基等。
針對含有式(1A')表示之陰離子之鋶鹽之合成,詳見日本特開2007-145797號公報、日本特開2008-106045號公報、日本特開2009-7327號公報、日本特開2009-258695號公報等。又,日本特開2010-215608號公報、日本特開2012-41320號公報、日本特開2012-106986號公報、日本特開2012-153644號公報等記載之鋶鹽也宜使用。
式(1A)表示之陰離子可列舉如下但不限於此等。又,下式中,Ac為乙醯基。
[化63]
[化63]
[化64]
[化65]
[化66]
式(1B)中,Rfb1
及Rfb2
各自獨立地為氟原子、或也可以含有雜原子之碳數1~40之1價烴基。前述1價烴基可為直鏈狀、分支狀或環狀中之任一者,其具體例可列舉和在前述R105
之説明列舉者為同樣者。Rfb1
及Rfb2
宜較佳為氟原子或碳數1~4之直鏈狀氟化烷基。又,Rfb1
與Rfb2
也可互相鍵結並和它們所鍵結之基(-CF2
-SO2
-N-
-SO2
-CF2
-)一起形成環,於此情形,Rfb1
與Rfb2
互相鍵結而獲得之基宜為氟化伸乙基或氟化伸丙基較佳。
式(1C)中,Rfc1
、Rfc2
及Rfc3
各自獨立地為氟原子、或也可以含有雜原子之碳數1~40之1價烴基。前述1價烴基可為直鏈狀、分支狀或環狀中之任一者,其具體例可列舉和在前述R105
之説明列舉者為同樣者。Rfc1
、Rfc2
及Rfc3
較佳為氟原子或碳數1~4之直鏈狀氟化烷基。又,Rfc1
與Rfc2
也可以互相鍵結並和它們所鍵結之基(-CF2
-SO2
-C-
-SO2
-CF2
-)一起形成環,於此情形,Rfc1
與Rfc2
互相鍵結而獲得之基宜為氟化伸乙基或氟化伸丙基較佳。
式(1D)中,Rfd
為也可以含有雜原子之碳數1~40之1價烴基。前述1價烴基可為直鏈狀、分支狀或環狀中任一者,其具體例可列舉和在前述R105
之説明列舉者為同樣者。
針對含有式(1D)表示之陰離子之鋶鹽之合成詳見日本特開2010-215608號公報及特開2014-133723號公報。
式(1D)表示之陰離子可列舉如下但不限於此等。
[化67]
[化67]
又,含有式(1D)表示之陰離子之光酸產生劑在磺基之α位沒有氟,但因為在β位有2個三氟甲基,具有為了將光阻聚合物中之酸不安定基予以切斷的充分的酸性度。所以,可以作為光酸產生劑使用。
又,也可使用下式(2)表示者作為光酸產生劑。
[化68]
[化68]
式(2)中,R201
及R202
各自獨立地為也可以含有雜原子之碳數1~30之1價烴基。R203
為也可以含有雜原子之碳數1~30之2價烴基。又,R201
、R202
及R203
中之任二者也可互相鍵結並和它們所鍵結之硫原子一起形成環。LA
為單鍵、醚鍵、或也可以含有雜原子之碳數1~20之2價烴基。XA
、XB
、XC
及XD
各自獨立地氫原子、氟原子或三氟甲基。惟XA
、XB
、XC
及XD
中之至少一者為氟原子或三氟甲基。k為0~3之整數。
前述1價烴基可以為直鏈狀、分支狀或環狀中之任一者,其具體例可以列舉甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、第三戊基、正己基、正辛基、正壬基、正癸基、2-乙基己基等直鏈狀或分支狀之烷基;環戊基、環己基、環戊基甲基、環戊基乙基、環戊基丁基、環己基甲基、環己基乙基、環己基丁基、降莰基、氧雜降莰基、三環[5.2.1.02,6
]癸基、金剛烷基等1價飽和環狀烴基;苯基、萘基、蒽基等芳基等。又,該等基之氫原子之一部分也可以取代為氧原子、硫原子、氮原子、鹵素原子等雜原子,該等基之碳原子之一部分也可以取代為含有氧原子、硫原子、氮原子等雜原子之基,其結果也可以含有羥基、氰基、羰基、醚鍵、酯鍵、磺酸酯鍵、碳酸酯基、內酯環、磺內酯環、羧酸酐、鹵烷基等。
前述2價烴基可為直鏈狀、分支狀或環狀中之任一者,其具體例可列舉亞甲基、伸乙基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、辛烷-1,8-二基、壬烷-1,9-二基、癸烷-1,10-二基、十一烷-1,11-二基、十二烷-1,12-二基、十三烷-1,13-二基、十四烷-1,14-二基、十五烷-1,15-二基、十六烷-1,16-二基、十七烷-1,17-二基等直鏈狀或分支狀之烷二基;環戊烷二基、環己烷二基、降莰烷二基、金剛烷二基等2價飽和環狀烴基;伸苯基、伸萘基等不飽和環狀2價烴基等。又,該等基之氫原子之一部分也可取代為甲基、乙基、丙基、正丁基、第三丁基等烷基,該等基之氫原子之一部分也可以取代為含有氧原子、硫原子、氮原子、鹵素原子等雜原子之基,或該等基之碳原子之一部分也可以取代為含有氧原子、硫原子、氮原子等雜原子之基,其結果也可以含有羥基、氰基、羰基、醚鍵、酯鍵、磺酸酯鍵、碳酸酯基、內酯環、磺內酯環、羧酸酐、鹵烷基等。前述雜原子宜為氧原子較佳。
式(2)表示之光酸產生劑宜為下式(2')表示者較佳。
[化69]
[化69]
式(2')中,LA
同前述。R為氫原子或三氟甲基,較佳為三氟甲基。R301
、R302
及R303
各自獨立地為氫原子、或也可以含有雜原子之碳數1~20之1價烴基。前述1價烴基可為直鏈狀、分支狀或環狀中之任一者,其具體例可列舉和在前述R105
之説明列舉者為同樣者。x及y各自獨立地為0~5之整數,z為0~4之整數。
式(2)表示之光酸產生劑可列舉如下但不限於此等。又,下式中,R同前述,Me為甲基。
[化70]
[化70]
[化71]
[化72]
前述光酸產生劑之中,含有式(1A')或(1D)表示之陰離子者,酸擴散小且對於光阻溶劑之溶解性優良,特別理想。又,含有式(2')表示之陰離子者,酸擴散極小,特別理想。
就前述光酸產生劑而言,也可使用下式(3-1)或(3-2)表示之含有碘化苯甲醯氧基之氟化磺酸之鋶鹽及錪鹽。
[化73]
[化73]
式(3-1)及(3-2)中,R401
為氫原子、羥基、羧基、硝基、氰基、氟原子、氯原子、溴原子、胺基、或也可以含有氟原子、氯原子、溴原子、羥基、胺基或烷氧基之碳數1~20之烷基、碳數1~20之烷氧基、碳數2~20之烷氧基羰基、碳數2~20之醯氧基或碳數1~4之烷基磺醯氧基,或-NR407
-C(=O)-R408
或-N R407
-C(=O)-O- R408
,R407
為氫原子、或也可以含有鹵素原子、羥基、烷氧基、醯基或醯氧基之碳數1~6之烷基,R408
為碳數1~16之烷基、碳數2~16之烯基、或碳數6~12之芳基,也可以含有鹵素原子、羥基、烷氧基、醯基或醯氧基。
X11
於r為1時係單鍵或碳數1~20之2價之連結基,於r為2或3時係碳數1~20之3價或4價之連結基,該連結基也可以含有氧原子、硫原子或氮原子。
Rf11 ~Rf14 各自獨立地為氫原子、氟原子或三氟甲基,但該等中之至少一者為氟原子或三氟甲基。又,Rf11 與Rf12 也可合併而形成羰基。
Rf11 ~Rf14 各自獨立地為氫原子、氟原子或三氟甲基,但該等中之至少一者為氟原子或三氟甲基。又,Rf11 與Rf12 也可合併而形成羰基。
R402
、R403
、R404
、R405
及R406
各自獨立地為碳數1~12之烷基、碳數2~12之烯基、碳數2~12之炔基、碳數6~20之芳基、或碳數7~12之芳烷基或芳氧基烷基,該等基之氫原子之一部分或全部也可取代為羥基、羧基、鹵素原子、氰基、側氧基、醯胺基、硝基、磺內酯基、碸基(sulfone group)或含鋶鹽之基,該等基之碳原子之一部分也可以取代為醚鍵、酯鍵、羰基、碳酸酯基或磺酸酯鍵。又,R402
與R403
也可以互相鍵結並和它們所鍵結之硫原子一起形成環。
r為1~3之整數。s為1~5之整數。t為0~3之整數。
又,前述烷基、烷氧基、烷氧基羰基、醯氧基、烷基磺醯氧基、烯基及炔基可為直鏈狀、分支狀、環狀中之任一者。
又,也可使用下式(3-3)或(3-4)表示之含碘化苯環之氟化磺酸之鋶鹽或錪鹽作為前述光酸產生劑。
[化74]
[化74]
式(3-3)及(3-4)中,R411
各自獨立地為羥基、碳數1~20之烷基或烷氧基、碳數2~20之醯基或醯氧基、氟原子、氯原子、溴原子、胺基、或烷氧基羰基取代胺基。
R412
各自獨立地為單鍵、或碳數1~4之伸烷基。R413
於u為1時係單鍵或碳數1~20之2價之連結基,於u為2或3時係碳數1~20之3價或4價之連結基,該連結基也可以含有氧原子、硫原子或氮原子。
Rf21
~Rf24
各自獨立地為氫原子、氟原子或三氟甲基,但至少一者為氟原子或三氟甲基。又,Rf21
與Rf22
也可以合併而形成羰基。
R414
、R415
、R416
、R417
及R418
各自獨立地為碳數1~12之烷基、碳數2~12之烯基、碳數6~20之芳基、或碳數7~12之芳烷基或芳氧基烷基,該等基之氫原子之一部分或全部也可以取代為羥基、羧基、鹵素原子、氰基、側氧基、醯胺基、硝基、磺內酯基、碸基或含鋶鹽之基,該等基之碳原子之一部分也可取代為醚鍵、酯鍵、羰基、碳酸酯基或磺酸酯鍵。又,R414
與R415
也可以互相鍵結並和它們所鍵結之硫原子一起形成環。
u為1~3之整數。v為1~5之整數。w為0~3之整數。
又,前述烷基、烷氧基、醯基、醯氧基及烯基可為直鏈狀、分支狀、環狀中之任一者。
作為式(3-1)及(3-3)表示之鋶鹽之陽離子部分,可列舉和就式(d4)表示之陽離子於前述者為同樣者。又,就式(3-2)及(3-4)表示之錪鹽之陽離子部分而言,可列舉和就式(d5)表示之陽離子於前述者為同樣者。
式(3-1)~(3-4)表示之鎓鹽之陰離子部分可列舉如下但不限於此等。
[化75]
[化75]
[化76]
[化77]
[化78]
[化79]
[化80]
[化81]
[化82]
[化83]
[化84]
[化85]
[化86]
[化87]
[化88]
[化89]
[化90]
[化91]
[化92]
[化93]
[化94]
[化95]
[化96]
本發明之光阻材料含有添加型酸產生劑時,其含量相對於基礎樹脂100質量份為0.1~50質量份較理想,1~40質量份更理想。
[其他成分]
本發明之光阻材料中,也可以更含有淬滅劑、溶解控制劑、界面活性劑、乙炔醇類等。
本發明之光阻材料中,也可以更含有淬滅劑、溶解控制劑、界面活性劑、乙炔醇類等。
藉由於光阻材料摻合淬滅劑,例如能抑制酸在光阻膜中之擴散速度,使解像度更好。前述淬滅劑可列舉鹼性化合物,具體而言,可列舉日本特開2008-111103號公報之段落[0146]~[0164]記載者。該等之中,1級、2級或3級之胺化合物,尤其含有羥基、醚鍵、酯鍵、內酯環、氰基、磺酸酯鍵等之胺化合物為較佳。含有鹼性化合物作為淬滅劑時,其含量相對於基礎樹脂100質量份為0~100質量份較理想,0.001~50質量份更理想。
本發明之光阻材料中,也可以摻合日本特開2008-239918號公報記載之聚合物型淬滅劑。其藉由配向在塗佈後之光阻表面,能夠提高圖案後之光阻之矩形性。聚合物型淬滅劑也可防止在光阻上施用保護膜時之圖案之膜損失、圖案頂部圓化之效果。含有前述聚合物型淬滅劑時,其含量在無損本發明之效果之範圍內可以為任意。
又,本發明之光阻材料中,也可以摻合下式(4)表示之α位未氟化之磺酸之鎓鹽、或下式(5)表示之羧酸之鎓鹽作為淬滅劑。
[化97]
[化97]
式中,R501
、R502
及R503
各自獨立地為氫原子、除氟原子以外的鹵素原子、或也可以含有雜原子之碳數1~40之1價烴基。又,R501
、R502
及R503
中之任二者也可以互相鍵結並和它們所鍵結之碳原子一起形成環。R504
為也可以含有雜原子之碳數1~40之1價烴基。M+
為鎓陽離子。前述1價烴基可為直鏈狀、分支狀或環狀中之任一者。
針對α位未氟化之磺酸之鎓鹽,詳見日本特開2008-158339號公報。產生α位未氟化之磺酸之光酸產生劑例如日本特開2010-155824號公報之段落[0019]~[0036]記載之化合物、日本特開2010-215608號公報之段落[0047]~[0082]記載之化合物。針對羧酸之鎓鹽詳見日本專利第3991462號公報。
式(4)或(5)中之陰離子為弱酸之共軛鹼。在此所指之弱酸,係指無法使基礎樹脂使用之含酸不安定基之單元之酸不安定基脱保護之酸性度。式(4)或(5)表示之鎓鹽,當和具有如α位氟化之磺酸之強酸之共軛鹼作為相對陰離子之鎓鹽型光酸產生劑併用時,作為淬滅劑之作用。
亦即,若將產生如α位氟化之磺酸之強酸之鎓鹽、和產生如未經氟取代之磺酸、羧酸之弱酸之鎓鹽混用時,當因高能射線照射而從光酸產生劑產生之強酸與未反應之具弱酸陰離子之鎓鹽碰撞,會因鹽交換而釋出弱酸,產生有強酸陰離子之鎓鹽。在此過程中,強酸被交換成觸媒能力較低之弱酸,因此巨觀上酸失活而可進行酸擴散之控制。
尤其α位未氟化之磺酸及羧酸之鋶鹽及錪鹽有光分解性,所以光強度強之部分之淬滅能力降低,且同時α位氟化之磺酸、醯亞胺酸或甲基化酸之濃度增加。藉此,曝光部分之對比度提高,可形成焦點深度(DOF)更改善之尺寸控制良好的圖案。
在此,產生強酸之光酸產生劑為鎓鹽時,如前述,可將因高能射線照射產生之強酸交換成弱酸,但據認為因高能射線照射產生之弱酸不能和未反應之產生強酸之鎓鹽碰撞而進行鹽交換。原因在於鎓陽離子較容易和較強酸之陰離子形成相對離子的現象。
於酸不安定基是對酸特別敏感的縮醛時,為了使保護基脱離之酸不一定需為α位經氟化之磺酸、醯亞胺酸、甲基化酸,有時α位未經氟化之磺酸也會進行脱保護反應。此時之淬滅劑無法使用磺酸之鎓鹽,故如此的情形,宜單獨使用羧酸之鎓鹽較佳。
作為α位未氟化之磺酸之鎓鹽、及羧酸之鎓鹽,宜各為下式(4')表示之磺酸之鋶鹽、及下式(5')表示之羧酸之鋶鹽較佳。
[化98]
[化98]
式中,R551
、R552
及R553
各自獨立地為也可以含有雜原子之碳數1~20之1價烴基。又,R551
、R552
及R553
中之任二者也可以互相鍵結並和它們所鍵結之原子及其間之原子一起形成環。R554
為也可以含有雜原子之碳數1~40之1價烴基。R555
及R556
各自獨立地為氫原子或三氟甲基。R557
及R558
各自獨立地為氫原子、氟原子或三氟甲基。R559
為氫原子、羥基、也可以含有雜原子之碳數1~35之1價烴基、或取代或非取代之碳數6~30之芳基。j為1~3之整數。z1
、z2
及z3
各自獨立地為0~5之整數。前述1價烴基可為直鏈狀、分支狀、環狀中之任一者。
使用如此的鎓鹽作為淬滅劑時,可單獨使用1種或組合使用2種以上。其含量相對於基礎樹脂100質量份為0~50質量份較理想,0.001~50質量份更佳,0.01~20質量份更理想。藉由在前述範圍內摻合如此的淬滅劑,容易調整光阻感度,此外酸在光阻膜中之擴散速度受抑制,解像度提高,可抑制曝光後之感度變化、或減小基板、環境依存性並使曝光余裕度、圖案輪廓等更好。又,藉由添加如此的淬滅劑,也能夠使基板密合性更好。
藉由在光阻材料中摻合界面活性劑,能夠使光阻材料之塗佈性更好或進行控制。界面活性劑可列舉在日本特開2008-111103號公報之段落[0165]~[0166]記載者。界面活性劑之含量相對於基礎樹脂100質量份為0~10質量份較理想,0.0001~5質量份更理想。
藉由在光阻材料中摻合溶解控制劑,能夠使曝光部與未曝光部間之溶解速度之差距更大,使解像度更好。溶解控制劑可列舉在日本特開2008-122932號公報之段落[0155]~[0178]記載者。溶解控制劑之含量相對於基礎樹脂100質量份為0~50質量份較理想,0~40質量份更理想。
乙炔醇類可列舉在日本特開2008-122932號公報之段落[0179]~[0182]記載者。乙炔醇類之含量宜為光阻材料中之0~2質量%較理想,0.02~1質量%更理想。
本發明之光阻材料中,也可以摻合為了使旋塗後之光阻表面之撥水性更好的撥水性增進劑。撥水性增進劑可使用在不採用面塗之浸潤微影。撥水性增進劑宜為含有氟化烷基之高分子化合物、含特定結構之1,1,1,3,3,3-六氟-2-丙醇殘基之高分子化合物等較理想,於日本特開2007-297590號公報、日本特開2008-111103號公報等有例示。前述撥水性增進劑需溶於有機溶劑顯影液。前述具1,1,1,3,3,3-六氟-2-丙醇殘基之撥水性增進劑對於顯影液之溶解性良好。就撥水性增進劑而言,在重複單元含有胺基、胺鹽之高分子化合物,防止曝光後烘烤(PEB)中之酸蒸發而防止顯影後之孔圖案之開口不良之效果高。含有撥水性增進劑時,其含量相對於光阻材料之基礎樹脂100質量份宜為0.1~20質量份較理想,0.5~10質量份更理想。
藉由在含有本發明之聚合物之基礎樹脂因應目的而將前述各成分適當組合並摻合而構成光阻材料,於曝光部,本發明之聚合物因觸媒反應而加快對於顯影液之溶解速度,所以可成為極高感度之光阻材料。本發明之光阻材料,由此獲得之光阻膜之溶解對比度及解像性高、有曝光余裕度,處理適應性優異、曝光後之圖案形狀良好且呈現更優良的蝕刻耐性,尤其可抑制酸擴散,因此疏密尺寸差小,因而實用性高,作為超LSI用光阻材料非常有效。尤其摻合酸產生劑並製成利用了酸觸媒反應之化學增幅光阻材料的話,可成為更高感度者,各特性更優良,極為有用。
[圖案形成方法]
本發明之光阻材料,例如含有基礎樹脂、酸產生劑、有機溶劑及鹼性化合物之化學增幅光阻材料,當使用在各種積體電路製造時,可採用公知之微影技術。
本發明之光阻材料,例如含有基礎樹脂、酸產生劑、有機溶劑及鹼性化合物之化學增幅光阻材料,當使用在各種積體電路製造時,可採用公知之微影技術。
例如將本發明之光阻材料利用適當的塗佈方法以旋塗、輥塗、流塗、浸塗、噴塗、刮刀塗佈等,塗佈在積體電路製造用之基板(Si、SiO2
、SiN、SiON、TiN、WSi、BPSG、SOG、有機抗反射膜等)或遮罩電路製造用之基板(Cr、CrO、CrON、MoSi2
、SiO2
等)上,使塗佈膜厚成為0.1~2.0μm。將其於熱板上,較佳為於60~150℃進行10秒~30分鐘,更佳為於80~120℃進行30秒~20分鐘預烘。也可以在光阻膜上形成保護膜。保護膜宜可溶於鹼顯影液較佳。顯影時,形成光阻圖案並同時進行保護膜之剝離。保護膜具有下列功能:減少來自光阻膜之散逸氣體之功能、作為阻斷從EUV雷射產生之13.5nm以外之波長140~300nm之頻外光(OOB)之濾器之功能、防止因環境影響而使光阻之形狀變成頂部廣或膜損失之功能。其次,以選自紫外線、遠紫外線、EUV、EB、X射線、軟X射線、準分子雷射、γ射線、同步加速器放射線等高能射線之光源,通過預定之遮罩或直接將目的圖案進行曝光。曝光宜以曝光量成為1~200mJ/cm2
左右,尤其10~100mJ/cm2
、或0.1~100μC/cm2
左右,尤其0.5~50μC/cm2
進行曝光較佳。然後在熱板上,較佳為於60~150℃進行10秒~30分鐘,更佳為於80~120℃進行30秒~20分鐘PEB。
進一步藉由使用0.1~10質量%,較佳為2~5質量%之氫氧化四甲基銨(TMAH)、四乙基氫氧化銨(TEAH)、四丙基氫氧化銨(TPAH)、四丁基氫氧化銨(TBAH)等鹼水溶液之顯影液,依浸漬(dip)法、浸置(puddle)法、噴灑(spray)法等常法進行3秒~3分鐘,較佳為5秒~2分鐘顯影,於本發明之聚合物含有重複單元b1及/或b2時,已照光之部分溶於顯影液,未照射到之部分不溶解,在基板上形成正型圖案,於本發明之聚合物含有重複單元b3時,在基板上形成負型圖案。又,本發明之光阻材料特別適合利用高能射線中之EB、EUV、X射線、軟X射線、γ射線、同步加速器放射線所為之微細圖案化。
一般而言,相較於廣泛使用之TMAH,烷基鏈加長之TEAH、TPAH、TBAH等,有使顯影中之膨潤減小而防止圖案崩塌之效果。日本專利第3429592號公報,揭示為了含有如甲基丙烯酸金剛烷酯之脂環結構之重複單元及含有如甲基丙烯酸第三丁酯之酸不安定基之重複單元且無親水性基而撥水性高之聚合物之顯影,使用了TBAH水溶液之例。
TMAH顯影液最常使用2.38質量%TMAH水溶液。其相當於0.26N,且TEAH、TPAH、TBAH等水溶液也宜為相同當量濃度較佳。成為0.26N之TEAH、TPAH及TBAH之質量各為3.84質量%、5.31質量%及6.78質量%。
在以EB或EUV解像之32nm以下之圖案中,會發生線扭轉、或線彼此纏結或纏結的線崩塌的現象。據認為原因是在顯影液中膨潤而膨大的線彼此纏結的原故。膨潤的線因為含有顯影液,像海綿般柔軟,所以易因淋洗之應力而崩塌。烷基鏈加長之顯影液,有防止膨潤且防止圖案崩塌之效果。
本發明之聚合物含有重複單元b1及/或b2時,可利用有機溶劑顯影而獲得負型圖案。顯影液可列舉2-辛酮、2-壬酮、2-庚酮、3-庚酮、4-庚酮、2-己酮、3-己酮、二異丁酮、甲基環己酮、苯乙酮、甲基苯乙酮、乙酸丙酯、乙酸丁酯、乙酸異丁酯、乙酸戊酯、乙酸丁烯酯、乙酸異戊酯、甲酸丙酯、甲酸丁酯、甲酸異丁酯、甲酸戊酯、甲酸異戊酯、戊酸甲酯、戊烯酸甲酯、巴豆酸甲酯、巴豆酸乙酯、丙酸甲酯、丙酸乙酯、3-乙氧基丙酸乙酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、乳酸異丁酯、乳酸戊酯、乳酸異戊酯、2-羥基異丁酸甲酯、2-羥基異丁酸乙酯、苯甲酸甲酯、苯甲酸乙酯、乙酸苯酯、乙酸苄酯、苯基乙酸甲酯、甲酸苄酯、甲酸苯基乙酯、3-苯基丙酸甲酯、丙酸苄酯、苯基乙酸乙酯、乙酸2-苯基乙酯等。該等溶劑可以單獨使用1種或混用2種以上。
顯影之結束時進行淋洗。淋洗液宜和顯影液混溶且不會使光阻膜溶解之溶劑較佳。如此的溶劑宜使用碳數3~10之醇、碳數8~12之醚化合物、碳數6~12之烷、烯、炔、芳香族系之溶劑較理想。
具體而言,碳數3~10之醇可以列舉正丙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、第三丁醇、1-戊醇、2-戊醇、3-戊醇、第三戊醇、新戊醇、2-甲基-1-丁醇、3-甲基-1-丁醇、3-甲基-3-戊醇、環戊醇、1-己醇、2-己醇、3-己醇、2,3-二甲基-2-丁醇、3,3-二甲基-1-丁醇、3,3-二甲基-2-丁醇、2-乙基-1-丁醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-甲基-3-戊醇、3-甲基-1-戊醇、3-甲基-2-戊醇、3-甲基-3-戊醇、4-甲基-1-戊醇、4-甲基-2-戊醇、4-甲基-3-戊醇、環己醇、1-辛醇等。
碳數8~12之醚化合物可列舉二正丁醚、二異丁醚、二第二丁醚、二正戊醚、二異戊醚、二第二戊醚、二第三戊醚、二正己醚等。
碳數6~12之烷可列舉己烷、庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、甲基環戊烷、二甲基環戊烷、環己烷、甲基環己烷、二甲基環己烷、環庚烷、環辛烷、環壬烷等。碳數6~12之烯可列舉己烯、庚烯、辛烯、環己烯、甲基環己烯、二甲基環己烯、環庚烯、環辛烯等。碳數6~12之炔可列舉己炔、庚炔、辛炔等。
芳香族系之溶劑可列舉甲苯、二甲苯、乙基苯、異丙苯、第三丁苯、均三甲苯等。
[實施例]
[實施例]
以下舉實施例及比較例對於本發明具體説明,但本發明不限於下列實施例等。
[1]
聚合性單體之合成
[實施例1-1]
單體1之合成
[化99]
聚合性單體之合成
[實施例1-1]
單體1之合成
[化99]
於氮氣環境下將甲基三苯基溴化鏻(89.3g)溶於THF(400mL),邊於冰浴冷卻邊以粉體形式添加第三丁氧基鉀(28.1g)。於冰浴中進行30分鐘熟成後,滴加由原料1(37.4g)及THF(100mL)構成之溶液。30分鐘熟成後,冷卻反應液,滴加水(200mL),使反應停止。之後以乙酸乙酯400mL萃取,進行通常之水系處理(aqueous work-up),將溶劑餾去後,將殘渣以矽膠管柱層析精製,獲得單體1之白色結晶(產量31.4g、產率84%)。
獲得之目的物之IR光譜數據、及核磁共振光譜(1
H-NMR)之結果如下。
IR(D-ATR):ν= 3403, 3084, 3057, 3023, 1834, 1750, 1717, 1658, 1623, 1569, 1543, 1442, 1414, 1394, 1370, 1323, 1303, 1258, 1235, 1202, 1126, 1100, 1038, 1023, 994, 915, 863, 804, 757, 734, 697, 664, 584, 542, 530 cm-1 .
1 H-NMR(600MHz,於DMSO-d6):δ= 9.64(1H, s), 7.89(1H, s), 7.73(1H, s), 6.90(1H, dd), 5.89(1H, d), 5.28(1H, d) ppm.
IR(D-ATR):ν= 3403, 3084, 3057, 3023, 1834, 1750, 1717, 1658, 1623, 1569, 1543, 1442, 1414, 1394, 1370, 1323, 1303, 1258, 1235, 1202, 1126, 1100, 1038, 1023, 994, 915, 863, 804, 757, 734, 697, 664, 584, 542, 530 cm-1 .
1 H-NMR(600MHz,於DMSO-d6):δ= 9.64(1H, s), 7.89(1H, s), 7.73(1H, s), 6.90(1H, dd), 5.89(1H, d), 5.28(1H, d) ppm.
[實施例1-2~1-7]
單體2~7之合成
將原料1替換為使用對應之原料,除此以外以和實施例1-1同樣的方法合成單體2~7。
[化100]
單體2~7之合成
將原料1替換為使用對應之原料,除此以外以和實施例1-1同樣的方法合成單體2~7。
[化100]
[2]
聚合物之合成
就光阻材料使用之聚合物而言,將各單體組合並於環戊酮溶劑下進行共聚合反應,析出於己烷,再以己烷重複洗淨後,單離、乾燥,獲得以下所示之聚合物(聚合物1~19、比較聚合物1~7)。獲得之聚合物之組成以1 H-NMR及13 C-NMR確認。又,Mw及Mn,係使用四氫呋喃(THF)作為溶劑,利用GPC獲得之聚苯乙烯換算値。
聚合物之合成
就光阻材料使用之聚合物而言,將各單體組合並於環戊酮溶劑下進行共聚合反應,析出於己烷,再以己烷重複洗淨後,單離、乾燥,獲得以下所示之聚合物(聚合物1~19、比較聚合物1~7)。獲得之聚合物之組成以1 H-NMR及13 C-NMR確認。又,Mw及Mn,係使用四氫呋喃(THF)作為溶劑,利用GPC獲得之聚苯乙烯換算値。
[實施例2-1]
聚合物1
[化101]
聚合物1
[化101]
[實施例2-2]
聚合物2
[化102]
聚合物2
[化102]
[實施例2-3]
聚合物3
[化103]
聚合物3
[化103]
[實施例2-4]
聚合物4
[化104]
聚合物4
[化104]
[實施例2-5]
聚合物5
[化105]
聚合物5
[化105]
[實施例2-6]
聚合物6
[化106]
聚合物6
[化106]
[實施例2-7]
聚合物7
[化107]
聚合物7
[化107]
[實施例2-8]
聚合物8
[化108]
聚合物8
[化108]
[實施例2-9]
聚合物9
[化109]
聚合物9
[化109]
[實施例2-10]
聚合物10
[化110]
聚合物10
[化110]
[實施例2-11]
聚合物11
[化111]
聚合物11
[化111]
[實施例2-12]
聚合物12
[化112]
聚合物12
[化112]
[實施例2-13]
聚合物13
[化113]
聚合物13
[化113]
[實施例2-14]
聚合物14
[化114]
聚合物14
[化114]
[實施例2-15]
聚合物15
[化115]
聚合物15
[化115]
[實施例2-16]
聚合物16
[化116]
聚合物16
[化116]
[實施例2-17]
聚合物17
[化117]
聚合物17
[化117]
[實施例2-18]
聚合物18
[化118]
聚合物18
[化118]
[實施例2-19]
聚合物19
[化119]
聚合物19
[化119]
[比較例1-1]
比較聚合物1
[化120]
比較聚合物1
[化120]
[比較例1-2]
比較聚合物2
[化121]
比較聚合物2
[化121]
[比較例1-3]
比較聚合物3
[化122]
比較聚合物3
[化122]
[比較例1-4]
比較聚合物4
[化123]
比較聚合物4
[化123]
[比較例1-5]
比較聚合物5
[化124]
比較聚合物5
[化124]
[比較例1-6]
比較聚合物6
[化125]
比較聚合物6
[化125]
[比較例1-7]
比較聚合物7
[化126]
比較聚合物7
[化126]
[3]
光阻材料之製備
在以表1及2所示之組成使各成分溶於已溶解作為界面活性劑之100ppm之3M公司製FC-4430之溶劑而成的溶液,以0.2μm尺寸之濾器過濾,製備光阻材料。
光阻材料之製備
在以表1及2所示之組成使各成分溶於已溶解作為界面活性劑之100ppm之3M公司製FC-4430之溶劑而成的溶液,以0.2μm尺寸之濾器過濾,製備光阻材料。
表1及2中,各成分如下。
・有機溶劑:PGMEA(丙二醇單甲醚乙酸酯)
CyH(環己酮)
PGME(丙二醇單甲醚)
DAA(二丙酮醇)
・有機溶劑:PGMEA(丙二醇單甲醚乙酸酯)
CyH(環己酮)
PGME(丙二醇單甲醚)
DAA(二丙酮醇)
・酸產生劑:PAG-1~PAG-3(參照下列結構式)
[化127]
[化127]
・淬滅劑:淬滅劑1~3(參照下列結構式)
[化128]
[化128]
[EUV曝光評價]
[實施例3-1~3-19、比較例2-1~2-7]
將表1及2所示之各光阻材料旋塗於已形成膜厚20nm之信越化學工業(股)製含矽旋塗式硬遮罩SHB-A940(矽之含量為43質量%)的Si基板上,使用熱板於105℃進行60秒預烘,製得膜厚60nm之光阻膜。對其使用ASML公司製EUV掃描曝光機NXE3300(NA0.33、σ0.9/0.6、四極照明、晶圓上尺寸為節距46nm、+20%偏差之孔圖案之遮罩)曝光,在熱板上以表1及2記載之溫度進行60秒PEB,並以2.38質量%TMAH水溶液進行30秒顯影,形成尺寸23nm之孔圖案。
使用日立先端科技(股)製之測長SEM(CG5000),測定孔於23nm形成時之曝光量,定義為感度,又,測定此時之50個孔之尺寸,求尺寸變異(CDU、3σ)。結果一併於表1及2。
[實施例3-1~3-19、比較例2-1~2-7]
將表1及2所示之各光阻材料旋塗於已形成膜厚20nm之信越化學工業(股)製含矽旋塗式硬遮罩SHB-A940(矽之含量為43質量%)的Si基板上,使用熱板於105℃進行60秒預烘,製得膜厚60nm之光阻膜。對其使用ASML公司製EUV掃描曝光機NXE3300(NA0.33、σ0.9/0.6、四極照明、晶圓上尺寸為節距46nm、+20%偏差之孔圖案之遮罩)曝光,在熱板上以表1及2記載之溫度進行60秒PEB,並以2.38質量%TMAH水溶液進行30秒顯影,形成尺寸23nm之孔圖案。
使用日立先端科技(股)製之測長SEM(CG5000),測定孔於23nm形成時之曝光量,定義為感度,又,測定此時之50個孔之尺寸,求尺寸變異(CDU、3σ)。結果一併於表1及2。
[表1]
[表2]
由表1及2所示之結果,啟示本發明之光阻材料,感度、CDU優異,在利用微影所為之微細加工極有效。
Claims (15)
- 如申請專利範圍第1項之聚合性單體,其中,X1為單鍵。
- 如申請專利範圍第3或4項之聚合物,其中,X1為單鍵。
- 如申請專利範圍第3或4項之聚合物,更含有具因酸而改變極性之基之重複單元。
- 如申請專利範圍第3或4項之聚合物,更含有至少1種含選自羥基、羧基、內酯環、碳酸酯基、硫碳酸酯基、羰基、環狀縮醛基、醚鍵、酯鍵、磺酸酯鍵、氰基、醯胺基、-O-C(=O)-S-及-O-C(=O)-NH-中之密合性基之重複單元。
- 如申請專利範圍第3或4項之聚合物,更含有選自下式(d1)~(d3)表示之重複單元中之至少1種;式中,RA各自獨立地為氫原子、甲基或三氟甲基;R11及R12各自獨立地為也可以含有雜原子之碳數1~20之1價烴基;R11與R12也可互相鍵結並和它們所鍵結之硫原子一起形成環;L1為單鍵、伸苯基、-C(=O)-L11-L12-或-O-L12-,L11為-O-或-NH-,L12為碳數1~6之2價脂肪族烴基、或伸苯基,該2價脂肪族烴基也可以含有羰基、酯鍵、醚鍵或羥基;L2為單鍵、或-L21-C(=O)-O-,L21為也可以含有雜原子之碳數1~20之2價烴基;L3為單鍵、亞甲基、伸乙基、伸苯基、氟化伸苯基、-C(=O)-L31-L32-或-O-L32-,L31為-O-或-NH-,L32為碳數1~6之2價脂肪族烴基、或伸苯基,該2價脂肪族烴基也可以含有羰基、酯鍵、醚鍵或羥基;M-為非親核性相對離子;Q+為下式(d4)表示之鋶陽離子、或下式(d5)表示之錪陽離子;式中,R13~R17各自獨立地為也可以含有雜原子之碳數1~20之1價烴基;R13、R14及R15中之任二者也可互相鍵結並和它們所鍵結之硫原子一起形成環。
- 一種光阻材料,包含:含有如申請專利範圍第3至8項中任一項之聚合物之基礎樹脂、有機溶劑、及酸產生劑。
- 一種光阻材料,包含:含有如申請專利範圍第9項之聚合物之基礎樹脂、及有機溶劑。
- 如申請專利範圍第10或11項之光阻材料,更含有淬滅劑。
- 如申請專利範圍第10或11項之光阻材料,更含有界面活性劑。
- 一種圖案形成方法,包括下列步驟:將如申請專利範圍第10至13項中任一項之光阻材料塗佈在基板上,進行加熱處理而形成光阻膜;將該光阻膜以高能射線進行曝光;及使用顯影液將已曝光之光阻膜進行顯影。
- 如申請專利範圍第14項之圖案形成方法,其中,該高能射線係i射線、KrF準分子雷射、ArF準分子雷射、電子束、或波長3~15nm之極紫外線。
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