TWI646396B - 包含含有羰基之聚羥芳香環酚醛樹脂之阻劑下層膜形成組成物 - Google Patents
包含含有羰基之聚羥芳香環酚醛樹脂之阻劑下層膜形成組成物 Download PDFInfo
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- TWI646396B TWI646396B TW102146076A TW102146076A TWI646396B TW I646396 B TWI646396 B TW I646396B TW 102146076 A TW102146076 A TW 102146076A TW 102146076 A TW102146076 A TW 102146076A TW I646396 B TWI646396 B TW I646396B
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
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- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 description 1
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 1
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- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000005389 semiconductor device fabrication Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 description 1
- 229950000329 thiouracil Drugs 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
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- 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
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- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
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- C—CHEMISTRY; METALLURGY
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- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/094—Multilayer resist systems, e.g. planarising layers
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0277—Electrolithographic processes
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31144—Etching the insulating layers by chemical or physical means using masks
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- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0332—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their composition, e.g. multilayer masks, materials
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- Y—GENERAL 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
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Abstract
本發明之課題在於提供一種具有高耐乾式蝕刻性、耐扭動性、耐熱性等之微影步驟中所使用之阻劑下層膜。
本發明之解決手段是一種微影用阻劑下層膜形成組成物,其係包含含有下列式(1)的單位結構之聚合物,
(式(1)中,A表示來自聚羥芳香族化合物之碳數6至40之經羥基取代的伸芳基,B表示碳數6至40的伸芳基或是含有氮原子、氧原子、硫原子或此等的組合之碳數4
至30的雜環基,X+表示H+、NH4 +、1級銨離子、2級銨離子、3級銨離子、或4級銨離子,T為氫原子、或是可經鹵素基、羥基、硝基、胺基、羧酸酯基、腈基、或此等的組合之取代基所取代之碳數1至10的烷基、碳數6至40的芳基或是含有氮原子、氧原子、硫原子或此等的組合之碳數4至30的雜環基,B與T,可與此等所鍵結之碳原子成為一體而形成碳數4至40的環)。
Description
本發明係關於在半導體基板加工時為有效之微影用阻劑下層膜形成組成物,以及使用該阻劑下層膜形成組成物之阻劑圖型形成法,以及半導體裝置之製造方法。
以往,在半導體裝置的製造中,係依據使用光阻組成物之微影來進行細微加工。前述細微加工,為將光阻組成物的薄膜形成於矽晶圓等之被加工基板上,並經由描繪有半導體裝置的圖型之遮罩圖型,將紫外線等之活化光線照射在其上方並進行顯影,並以所得之光阻圖型作為保護膜對矽晶圓等之被加工基板進行蝕刻處理之加工法。惟近年來隨著半導體裝置之高積體化的發展,所使用之活化光線亦有從KrF準分子雷射光(波長248nm)往ArF準分子雷射光(波長193nm)短波長化之傾向。伴隨
於此,從基板所產生之活化光線的漫射或駐波的影響會形成較大問題。因此,於光阻與被加工基板之間設置抗反射膜(Bottom Anti-Reflective Coating,BARC)之方法,已逐漸被廣泛地探討。
今後,隨著阻劑圖型之細微化的進展,會產
生解像度的問題或是阻劑圖型於顯影後倒塌之問題,故較佳可達成阻劑的薄膜化。因而下列製程乃逐漸變得必要,亦即於基板加工時不易得到充分的阻劑圖型膜厚,且不僅是阻劑圖型,對於在阻劑與被加工之半導體基板之間所形成之阻劑下層膜,亦須具有可作為於基板加工時之遮罩功能。該製程用的阻劑下層膜,與以往之高蝕刻速率性(蝕刻速度快)的阻劑下層膜不同,係逐漸要求具有接近於阻劑之乾式蝕刻速度的選擇比之微影用阻劑下層膜,並且具有較阻劑更小之乾式蝕刻速度的選擇比之微影用阻劑下層膜或具有較半導體基板更小之乾式蝕刻速度的選擇比之微影用阻劑下層膜。
上述阻劑下層膜形成組成物所使用之聚合
物,係揭示有:酚、間苯二酚、萘酚,與苯甲醛或呋喃醛之酚醛樹脂(參考專利文獻1)。
此外,上述阻劑下層膜形成組成物所使用之聚合物,係揭示有:具有羥基或醛基之芘或萘,與甲醛水之酚醛樹脂(參考專利文獻2)。
再者,係揭示有:使用咔唑酚醛樹脂之阻劑下層膜形成組成物,以及使用含有羥基之使用咔唑酚醛樹脂之阻劑
下層膜形成組成物(參考專利文獻3、專利文獻4)。
此外,係有人申請一種含有聚羥苯酚醛樹脂之阻劑下層膜形成組成物之專利(參考專利文獻5)。
專利文獻1:日本特開2005-114921
專利文獻2:日本特開2010-117629
專利文獻3:國際特許出願公開WO2010/147155手冊
專利文獻4:國際特許出願公開WO2012/077640手冊
專利文獻5:國際特許出願號碼PCT/JP2012/075625
本發明係提供一種用於半導體裝置製造的微影製程之阻劑下層膜形成組成物。此外,本發明係提供一種不會引起與阻劑層的互混,可得到優異的阻劑圖型且具有接近於阻劑之乾式蝕刻速度的選擇比之微影用阻劑下層膜,並且具有較阻劑更小之乾式蝕刻速度的選擇比之微影用阻劑下層膜或具有較半導體基板更小之乾式蝕刻速度的選擇比之微影用阻劑下層膜。此外,本發明亦可賦予在將248nm、193nm、157nm等之波長的照射光使用在細微加工時,可有效地吸收來自基板的反射光之性能。再者,本
發明係提供一種使用阻劑下層膜形成組成物之阻劑圖型之形成法。此外,係提供一種用以形成亦兼具耐熱性之阻劑下層膜之阻劑下層膜形成組成物。
本發明之第1觀點係一種微影用阻劑下層膜形成組成物,其係包含含有下列式(1)的單位結構之聚合物,
(式(1)中,A表示來自聚羥芳香族化合物之碳數6至40之經羥基取代的伸芳基,B表示碳數6至40的伸芳基、或是含有氮原子、氧原子、硫原子或此等的組合之碳數4至30的雜環基,X+表示H+、NH4 +、1級銨離子、2級銨離子、3級銨離子、或4級銨離子,T為氫原子、或是可經鹵素基、羥基、硝基、胺基、羧酸酯基、腈基、或此等的組合之取代基所取代之碳數1至10的烷基、碳數6至40的芳基、或是含有氮原子、氧原子、硫原子或此等的組合之碳數4至30的雜環基,B與T,可與此等所鍵結之碳原子成為一體而形成碳數4至40的環,n1表示
1至可與由B定義之基的氫原子或B與T鍵結所形成之環上的氫原子取代之數的整數);第2觀點,如第1觀點之阻劑下層膜形成組成物,其中由A定義之經羥基取代的伸芳基,為來自苯二醇、苯三醇、或萘二醇之經羥基取代的伸芳基;第3觀點,如第1觀點之阻劑下層膜形成組成物,其中由A定義之經羥基取代的伸芳基,為來自兒茶酚、間苯二酚、氫醌、苯三酚、偏苯三酚、或間苯三酚之經羥基取代的伸苯基;第4觀點,如第1觀點至第3觀點中任一觀點之阻劑下層膜形成組成物,其中由B定義之伸芳基,為依據苯環、萘環、或蒽環之有機基,或是與T鍵結而依據茀環之有機基;第5觀點,如第1觀點至第3觀點中任一觀點之阻劑下層膜形成組成物,其中由B定義之雜環基,為依據可經取代之呋喃環、噻吩環、吡咯環、咔唑環、或二苯并呋喃環之有機基;第6觀點,如第1觀點至第5觀點中任一觀點之阻劑下層膜形成組成物,其中由B定義之伸芳基或雜環基,為具有鹵素基、羥基、硝基、胺基、羧酸酯基、腈基、或此等的組合作為取代基;第7觀點,如第1觀點至第6觀點中任一觀點之阻劑下層膜形成組成物,其中進一步包含交聯劑;第8觀點係一種阻劑下層膜,其係將如第1觀點至第
7觀點中任一觀點之阻劑下層膜形成組成物塗佈於半導體基板上並燒結而得到;第9觀點係一種使用在半導體的製造之阻劑圖型之形成方法,其係包含:將如第1觀點至第7觀點中任一觀點之阻劑下層膜形成組成物塗佈於半導體基板上並燒結以形成下層膜之步驟;第10觀點係一種半導體裝置之製造方法,其係包含:藉由如第1觀點至第7觀點中任一觀點之阻劑下層膜形成組成物將下層膜形成於半導體基板上之步驟、於其上方形成阻劑膜之步驟、藉由光或電子束的照射及顯影來形成阻劑圖型之步驟、藉由阻劑圖型對該下層膜進行蝕刻之步驟、以及藉由經圖型化後之下層膜來加工半導體基板之步驟;第11觀點係一種半導體裝置之製造方法,其係包含:藉由如第1觀點至第7觀點中任一觀點之阻劑下層膜形成組成物將阻劑下層膜形成於半導體基板上之步驟、於其上方形成硬遮罩之步驟、再於其上方形成阻劑膜之步驟、藉由光或電子束的照射及顯影來形成阻劑圖型之步驟、藉由阻劑圖型對硬遮罩進行蝕刻之步驟、藉由經圖型化後之硬遮罩對該阻劑下層膜進行蝕刻之步驟、以及藉由經圖型化後之阻劑下層膜來加工半導體基板之步驟;以及第12觀點,如第11觀點之製造方法,其中硬遮罩藉由無機物的塗佈物或無機物的蒸鍍所形成。
藉由本發明之阻劑下層膜形成組成物,不會引起阻劑下層膜的上層部與被覆於其上方之層之互混,可形成良好的阻劑圖型形狀。
此外,本發明之阻劑下層膜形成組成物,可賦予有效率地抑制來自基板的反射光之性能,而兼具作為曝光光的抗反射膜之效果。
再者,藉由本發明之阻劑下層膜形成組成物,可提供一種具有接近於阻劑之乾式蝕刻速度的選擇比,並且具有較阻劑更小之乾式蝕刻速度的選擇比或是具有較半導體基板更小之乾式蝕刻速度的選擇比之優異的阻劑下層膜。
為了防止隨著阻劑圖型的細微化使阻劑圖型在顯影後倒塌之情形,係進行阻劑的薄膜化。如此的薄膜阻劑中,係有藉由蝕刻製程將阻劑圖型轉印至該下層膜,並以該下層膜作為遮罩來進行基板加工之製程;或是重複進行下列步驟,亦即藉由蝕刻製程將阻劑圖型轉印至該下層膜,並使用不同的氣體組成,將被轉印至下層膜之圖型轉印至該下層膜之步驟,來進行最終的基板加工之製程。本發明之阻劑下層膜及其形成組成物,對於該製程為有效,使用本發明之阻劑下層膜將基板加工時,相對於加工基板(例如基板上的熱氧化矽膜、氮化矽膜、多晶矽膜等),係具有充分的耐蝕刻性。
此外,本發明之阻劑下層膜,可作為平坦化
膜、阻劑下層膜、阻劑層的抗污染膜。具有乾式蝕刻選擇性之膜使用。藉此,可容易且精度佳地進行半導體製造之微影製程中的阻劑圖型形成。
具體可列舉出:將由本發明之阻劑下層膜形
成組成物所形成之阻劑下層膜形成於基板上,於其上方形成硬遮罩,再於其上方形成阻劑膜,並藉由曝光及顯影來形成阻劑圖型,藉由乾式蝕刻將阻劑圖型轉印至硬遮罩,並將藉由乾式蝕刻轉印至硬遮罩之阻劑圖型轉印至阻劑下層膜,並藉由該阻劑下層膜來進行半導體基板的加工之製程。此時,當藉由乾式蝕刻氣體來進行乾式蝕刻時,由本發明之阻劑下層膜所形成之圖型,乃成為圖型的耐扭動性(anti-wiggling)優異之圖型。
此外,於該製程中,係有藉由含有有機聚合
物或無機聚合物(矽聚合物)與溶劑之塗佈型的組成物來進行硬遮罩形成之情形,以及藉由無機物的真空蒸鍍來進行硬遮罩形成之情形。無機物(例如氮氧化矽)的真空蒸鍍中,蒸鍍物沉積於阻劑下層膜表面,但此時,阻劑下層膜表面的溫度上升至400℃左右。由於本發明中所使用之聚合物為含有多量的苯系單位結構之聚合物,所以耐熱性極高,不會因蒸鍍物的沉積而產生熱劣化。再者,由於本發明中所得之阻劑下層膜可藉由鹼水溶液來去除,故可期待於去除時能夠降低對基板所造成之破壞。
本發明為包含含有式(1)的單位結構之聚合
物之微影用阻劑下層膜形成組成物。本發明中,上述微影用阻劑下層膜形成組成物包含上述聚合物與溶劑。此外,可包含交聯劑與酸,且因應必要可包含酸產生劑、界面活性劑等之添加劑。該組成物的固體成分為0.1至70質量%,或0.1至60質量%。固體成分為從阻劑下層膜形成組成物扣除溶劑後之全部成分的含有比率。固體成分中,可以1至100質量%,或1至99.9質量%,或50至99.9質量%,或50至95質量%,或50至90質量%的比率含有上述聚合物。
本發明所使用之聚合物,該重量平均分子量為600至1000000,或600至200000。
式(1)中,A表示來自聚羥芳香族化合物之
碳數6至40之經羥基取代的伸芳基,B表示碳數6至40的伸芳基、或是含有氮原子、氧原子、硫原子或此等的組合之碳數4至30的雜環基,X+表示H+(氫離子)、NH4 +、1級銨離子、2級銨離子、3級銨離子、或4級銨離子,T為氫原子、或是可經鹵素基、羥基、硝基、胺基、羧酸酯基、腈基、或此等的組合之取代基所取代之碳數1至10的烷基、碳數6至40的芳基、或是含有氮原子、氧原子、硫原子或此等的組合之碳數4至30的雜環基,B與T,可與此等所鍵結之碳原子成為一體而形成碳數4至40的環,n1表示1至可與由B定義之基的氫原子或B與T鍵結所形成之環上的氫原子取代之數的整數。
1級銨離子、2級銨離子、3級銨離子、及4級銨離子的有機基,可列舉出烷基或芳基,可例示如下。1級銨離子、2級銨離子、及3級銨離子係來自1級胺、2級胺、3級胺,可列舉出甲胺、乙胺、苯胺、二甲胺、二乙胺、二苯胺、三甲胺、三乙胺、三苯胺等。4級銨離子可列舉出四甲基銨、四乙基銨等。
由A定義之經羥基取代的伸芳基,可構成為來自苯二醇、苯三醇、或萘二醇之經羥基取代的伸芳基。此外,由A定義之經羥基取代的伸芳基,可構成為來自兒茶酚、間苯二酚、氫醌、苯三酚、偏苯三酚、或間苯三酚之經羥基取代的伸芳基。
由B定義之伸芳基,可構成為依據苯環、萘環、或蒽環之有機基,或是與T鍵結而依據茀環之有機基。此外,由B定義之雜環基,可構成為依據可經取代之呋喃環、噻吩環、吡咯環、咔唑環、或二苯并呋喃環之有機基。再者,由B定義之伸芳基或雜環基,可構成為具有鹵素基、羥基、硝基、胺基、羧酸酯基、腈基、或此等的組合作為取代基。
鹵素基可列舉出氟基、氯基、溴基、及碘基。
羧酸酯基為-COOR基,R可列舉出碳數1至10的烷基、或碳數6至40的芳基。
碳數1至10的烷基,可列舉出甲基、乙基、正丙基、異丙基、環丙基、正丁基、異丁基、二級丁基、三級丁基、環丁基、1-甲基-環丙基、2-甲基-環丙基、正
戊基、1-甲基-正丁基、2-甲基-正丁基、3-甲基-正丁基、1,1-二甲基-正丙基、1,2-二甲基-正丙基、2,2-二甲基-正丙基、1-乙基-正丙基、環戊基、1-甲基-環丁基、2-甲基-環丁基、3-甲基-環丁基、1,2-二甲基-環丙基、2,3-二甲基-環丙基、1-乙基-環丙基、2-乙基-環丙基、正己基、1-甲基-正戊基、2-甲基-正戊基、3-甲基-正戊基、4-甲基-正戊基、1,1-二甲基-正丁基、1,2-二甲基-正丁基、1,3-二甲基-正丁基、2,2-二甲基-正丁基、2,3-二甲基-正丁基、3,3-二甲基-正丁基、1-乙基-正丁基、2-乙基-正丁基、1,1,2-三甲基-正丙基、1,2,2-三甲基-正丙基、1-乙基-1-甲基-正丙基、1-乙基-2-甲基-正丙基、環己基、1-甲基-環戊基、2-甲基-環戊基、3-甲基-環戊基、1-乙基-環丁基、2-乙基-環丁基、3-乙基-環丁基、1,2-二甲基-環丁基、1,3-二甲基-環丁基、2,2-二甲基-環丁基、2,3-二甲基-環丁基、2,4-二甲基-環丁基、3,3-二甲基-環丁基、1-正丙基-環丙基、2-正丙基-環丙基、1-異丙基-環丙基、2-異丙基-環丙基、1,2,2-三甲基-環丙基、1,2,3-三甲基-環丙基、2,2,3-三甲基-環丙基、1-乙基-2-甲基-環丙基、2-乙基-1-甲基-環丙基、2-乙基-2-甲基-環丙基及2-乙基-3-甲基-環丙基等。
碳數6至40的芳基,可列舉出苯基、鄰甲基
苯基、間甲基苯基、對甲基苯基、鄰氯苯基、間氯苯基、對氯苯基、鄰氟苯基、對氟苯基、鄰甲氧苯基、對甲氧苯基、對硝苯基、對氰苯基、α-萘基、β-萘基、鄰聯苯基、間聯苯基、對聯苯基、1-蒽基、2-蒽基、9-蒽基、1-
菲基、2-菲基、3-菲基、4-菲基、芘基、及9-菲基。
碳數6至40的伸芳基,可列舉出對應於碳數6至40的芳基之伸芳基。
上述式(1)的單位結構可例示如下。
上述式(1-29)至式(1-42),R為碳數1至10的烷基或碳數6至40的芳基,例如可列舉出上述基。
本發明中,可使用使聚羥芳香族化合物與醛或酮縮合之包含式(1)的重複單位結構之酚醛樹脂作為聚合物。該酚醛樹脂,可藉由酸,使聚羥芳香族化合物、以及具有醛基或酮基與羧酸基或羧酸鹽的基之芳基化合物
或雜環化合物縮合而得到。
聚羥芳香族化合物,可列舉出苯二醇、苯三醇、或萘二醇。具體而言,苯系中,可列舉出兒茶酚、間苯二酚、氫醌、苯三酚、偏苯三酚、或間苯三酚。此外,萘系中,可列舉出2,7-二羥萘、2,6-二羥萘、1,4-二羥萘、2,3-二羥萘、1,5-二羥萘等。
芳基化合物或雜環化合物,為具有醛基或酮基與羧酸基或羧酸鹽的基之化合物。例如,具有醛基與羧基之化合物,可列舉出對甲醯苯甲酸、間甲醯苯甲酸,具有醛基與羧基之雜環化合物,例如可使用甲醯呋喃羧酸、甲醯噻吩羧酸等。
此外,具有酮基與羧基之化合物,可列舉出茀酮羧酸等。
該反應中,相對於上述酚類1莫耳,可將醛類或酮類構成為0.1至10莫耳,較佳為0.8至2.2莫耳,更佳為1.0莫耳之比率進行反應。
上述縮合反應所使用之酸催化劑,例如可使用硫酸、磷酸、過氯酸等之礦酸類;對甲苯磺酸、對甲苯磺酸二水合物等之有機磺酸類;甲酸、草酸等之羧酸類。酸催化劑的用量,可因應所使用之酸類的種類來選擇。通常相對於上述聚羥芳香族化合物與醛或酮的合計100質量份,為0.001至10000質量份,較佳為0.01至1000質量份,尤佳為0.1至100質量份。
上述縮合反應亦可在無溶劑下進行,但通常
會使用溶劑來進行。溶劑只要是不會阻礙反應者,均可使用。例如可列舉出四氫呋喃、二噁烷等之環狀醚類。此外,若所使用之酸催化劑為例如甲酸般之液狀者,則亦可兼具溶劑之功用。
縮合時的反應溫度,通常為40℃至200℃。反應時間可因應反應溫度適當地選擇,通常約為30分鐘至50小時。
以上所得到之聚合物的重量平均分子量Mw,通常為600至1000000,或600至200000。
所得到之具有羧基之聚合物,可使用鹼性水溶液構成為羧酸鹽。鹼性物質可使用氨、1級胺、2級胺、3級胺、氫氧化4級銨。胺或4級銨所含有之有機基,可使用上述烷基或芳基。
上述聚合物,於全部聚合物中,可在30質量
%以內混合其他聚合物來使用。此等其他聚合物,可列舉出聚丙烯酸酯化合物、聚甲基丙烯酸酯化合物、聚丙烯醯胺化合物、聚甲基丙烯醯胺化合物、聚乙烯化合物、聚苯乙烯化合物、聚順丁烯二醯亞胺化合物、聚順丁烯二酸酐、及聚丙烯腈化合物。
聚丙烯酸酯化合物的原料單體,可列舉出丙
烯酸甲酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸苄酯、丙烯酸萘酯、丙烯酸蒽酯、丙烯酸蒽甲酯、丙烯酸苯酯、丙烯酸2-羥乙酯、丙烯酸2-羥丙酯、丙烯酸2,2,2-三氟乙酯、丙烯酸4-羥丁酯、丙烯異丁酯、丙烯酸三級丁酯、丙
烯環己酯、丙烯酸異莰酯、丙烯酸2-甲氧乙酯、丙烯酸甲氧三乙二醇酯、丙烯酸2-乙氧乙酯、丙烯酸四氫呋喃酯、丙烯酸3-甲氧丁酯、丙烯酸2-甲基-2-金剛烷酯、丙烯酸2-乙基-2-金剛烷酯、丙烯酸2-丙基-2-金剛烷酯、丙烯酸2-甲氧丁基-2-金剛烷酯、丙烯酸8-甲基-8-三環癸酯、丙烯酸8-乙基-8-三環癸酯、及5-丙烯醯氧基-6-羥基降莰烯-2-羧基-6-內酯等。
聚甲基丙烯酸酯化合物的原料單體,可列舉
出甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸正戊酯、甲基丙烯酸環己酯、甲基丙烯酸苄酯、甲基丙烯酸萘酯、甲基丙烯酸蒽酯、甲基丙烯酸蒽甲酯、甲基丙烯酸苯酯、甲基丙烯酸2-苯基乙酯、甲基丙烯酸2-羥乙酯、甲基丙烯酸2-羥丙酯、甲基丙烯酸2,2,2-三氟乙酯、甲基丙烯酸2,2,2-三氯乙酯、丙烯酸甲酯、甲基丙烯酸異丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸異癸酯、甲基丙烯酸正十二烷酯、甲基丙烯酸正十八烷酯、甲基丙烯酸甲氧二乙二醇酯、甲基丙烯酸甲氧聚乙二醇酯、甲基丙烯酸四氫呋喃酯、甲基丙烯酸異莰酯、甲基丙烯酸三級丁酯、甲基丙烯酸異十八烷酯、甲基丙烯酸正丁氧乙酯、甲基丙烯酸3-氯-2-羥丙酯、甲基丙烯酸2-甲基-2-金剛烷酯、甲基丙烯酸2-乙基-2-金剛烷酯、甲基丙烯酸2-丙基-2-金剛烷酯、甲基丙烯酸2-甲氧丁基-2-金剛烷酯、甲基丙烯酸8-甲基-8-三環癸酯、甲基丙烯酸8-乙基-8-三環癸酯、5-甲基丙烯醯氧基-6-羥基降莰烯-2-羧基-6-內酯、及甲基丙烯
酸2,2,3,3,4,4,4-七氟丁酯等。
聚丙烯醯胺化合物的原料單體,可列舉出丙
烯醯胺、N-甲基丙烯醯胺、N-乙基丙烯醯胺、N-苄基丙烯醯胺、N-苯基丙烯醯胺、及N,N-二甲基丙烯醯胺等。
聚甲基丙烯醯胺化合物的原料單體,可列舉出甲基丙烯醯胺、N-甲基甲基丙烯醯胺、N-乙基甲基丙烯醯胺、N-苄基甲基丙烯醯胺、N-苯基甲基丙烯醯胺、及N,N-二甲基甲基丙烯醯胺等。
聚乙烯化合物的原料單體,可列舉出乙烯
醚、甲基乙烯醚、苄基乙烯醚、2-羥乙基乙烯醚、苯基乙烯醚、及丙基乙烯醚等。聚苯乙烯化合物的原料單體,可列舉出,苯乙烯、甲基苯乙烯、氯苯乙烯、溴苯乙烯、及羥基苯乙烯等。
聚順丁烯二醯亞胺化合物的原料單體,可列舉出順丁烯二醯亞胺、N-甲基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、及N-環己基順丁烯二醯亞胺等。
此等聚合物的製造,可在將加成聚合性單體
以及因應必要所添加之連鎖轉移劑(相對於單體的質量為10%以下)溶解於有機溶劑後,加入聚合起始劑以進行聚合反應,然後添加聚合停止劑而製造出。聚合起始劑的添加量,相對於單體的質量為1至10%,聚合停止劑的添加量為0.01至0.2質量%。所使用之有機溶劑,可列舉出丙二醇單甲醚、丙二醇單丙醚、乳酸乙酯、環己酮、丁酮、及二甲基甲醯胺等,連鎖轉移劑可列舉出十二烷硫醇及十
二基硫醇等,聚合起始劑可列舉出偶氮雙異丁腈及偶氮雙環己烷羰腈等,聚合停止劑可列舉出4-甲氧基酚等。反應溫度可從30℃至100℃,反應時間可從1小時至48小時適當地選擇。
本發明之阻劑下層膜形成組成物可包含交聯
劑成分。該交聯劑可列舉出三聚氰胺系、經取代的脲系、或此等之聚合物系等。較佳為具有至少2個交聯形成取代基之交聯劑,有甲氧甲基化二醇脲、丁氧甲基化二醇脲、甲氧甲基化三聚氰胺、丁氧甲基化三聚氰胺、甲氧甲基化苯并胍胺、丁氧甲基化苯并胍胺、甲氧甲基化脲、丁氧甲基化脲、甲氧甲基化硫脲、或甲氧甲基化硫脲等之化合物。此外,亦可使用此等化合物之縮合物。
此外,上述交聯劑可使用耐熱性高之交聯劑。耐熱性高之交聯劑,較佳可使用含有於分子內具有芳香族環(例如苯環、萘環)之交聯形成取代基之化合物。
此等化合物,可列舉出具有下列式(2)的部分結構之化合物,或是具有下列式(3)的重複單位之聚合物或低聚物。
式(2)中,R10及R11分別為氫原子、碳數1至10的烷基、或碳數6至20的芳基,n10為1至4的整數,n11為1至(5-n10)的整數,(n10+n11)表示2至5的整數。
式(3)中,R12為氫原子或碳數1至10的烷基,R13為碳數1至10的烷基,n12為1至4的整數,n13為0至(4-n12)的整數,(n12+n13)表示1至4的整數。低聚物及聚合物,可使用重複單位結構的數目為2至100或2至50的範圍者。
此等之烷基及芳基,可例示上述烷基及芳基。
式(2)、式(3)的化合物、聚合物、低聚物可例示如下。
上述化合物可從旭有機材工業股份有限公司、本州化學工業股份有限公司的製品中取得。例如在上述交聯劑中,可從旭有機材工業股份有限公司中,取得商品名稱TM-BIP-A者作為式(2-21)的化合物。
交聯劑的添加量,因所使用之塗佈溶劑、所使用之底層基板、所要求之溶液黏度、所要求之膜形狀等的不同而改變,但相對於全體固體成分,可於0.001至80質量%,較佳於0.01至50質量%,更佳於0.05至40質量%中使用。此等交聯劑雖有藉由自我縮合而引發交聯反應者,但當本發明之上述聚合物中存在有交聯性取代基時,可與此
等交聯性取代基引發交聯反應。
本發明中,用以促進上述交聯反應之催化劑,可調配對甲苯磺酸、三氟甲烷磺酸、對甲苯磺酸吡啶鹽、柳酸、磺柳酸、檸檬酸、苯甲酸、羥基苯甲酸、萘羧酸等之酸性化合物或/及2,4,4,6-四溴環己二烯酮、甲苯磺酸安息香酯、甲苯磺酸2-硝苄酯、其他有機磺酸烷酯等之熱酸產生劑。調配量相對於全體固體成分,可設為0.0001至20質量%,較佳為0.0005至10質量%,更佳為0.001至3質量%。
本發明之微影用塗佈型下層膜形成組成物,
為了使與微影步驟中被覆於上層之光阻的酸性度一致,可添加光酸產生劑。較佳的光酸產生劑,例如可列舉出雙(4-三級丁基苯基)錪鹽三氟甲烷磺酸酯、三苯基鋶鹽三氟甲烷磺酸酯等之鎓鹽系光酸產生劑類;苯基-雙(三氯甲基)-s-三嗪等之含有鹵素之化合物系光酸產生劑類;甲苯磺酸安息香酯、N-羥基琥珀醯亞胺三氟甲烷磺酸酯等之磺酸系光酸產生劑等。上述光酸產生劑相對於全體固體成分,可為0.2至10質量%,較佳為0.4至5質量%。
本發明之微影用阻劑下層膜材料,除了上述
以外,可因應必要進一步添加吸光劑、流變調整劑、黏著輔助劑、界面活性劑等。
更具體的吸光劑,例如可較佳地使用「工業
用色素的技術與市場」(CMC出版)或「染料便覽」(有機合成化學協會編)所記載之市售的吸光劑,例如C.I.
Disperse Yellow 1,3,4,5,7,8,13,23,31,49,50,51,54,60,64,66,68,79,82,88,90,93,102,114及124;C.I.Disperse Orange 1,5,13,25,29,30,31,44,57,72及73;C.I.Disperse Red 1,5,7,13,17,19,43,50,54,58,65,72,73,88,117,137,143,199及210;C.I.Disperse Violet43;C.I.Disperse Blue 96;C.I.Fluorescent Brightening Agent 112,135及163;C.I.Solvent Orange 2及45;C.I.Solvent Red 1,3,8,23,24,25,27及49;C.I.Pigment Green 10;C.I.Pigment Brown 2等。上述吸光劑,通常相對於微影用阻劑下層膜材料的全體固體成分,以10質量%以下,較佳以5質量%以下的比率來調配。
流變調整劑,主要係提升阻劑下層膜形成組
成物的流動性,尤其在烘烤步驟中,係以提升阻劑下層膜的膜厚均一性,或是提高阻劑下層膜形成組成物往孔內部的充填性之目的而添加。具體例可列舉出鄰苯二甲酸二甲酯、鄰苯二甲酸二乙酯、鄰苯二甲酸二異丁酯、鄰苯二甲酸二己酯、鄰苯二甲酸丁基異癸酯等之鄰苯二甲酸衍生物;己二酸二正丁酯、己二酸二異丁酯、己二酸二異辛酯、己二酸辛基癸酯等之己二酸衍生物;順丁烯二酸二正丁酯、順丁烯二酸二乙酯、順丁烯二酸二壬酯等之順丁烯二酸衍生物;油酸甲酯、油酸丁酯、油酸四氫呋喃酯等之油酸衍生物;或是硬脂酸正丁酯、硬脂酸甘油酯等之硬脂酸衍生物。此等流變調整劑,相對於微影用阻劑下層膜材料的全體固體成分,通常以未達30質量%的比率來調
配。
黏著輔助劑,主要係提升基板或阻劑與阻劑
下層膜形成組成物之緊密性,尤其以在顯影時不會使阻劑剝離之目的而添加。具體例可列舉出三甲基氯矽烷、二甲基乙烯基氯矽烷、甲基二苯基氯矽烷、氯甲基二甲基氯矽烷等之氯矽烷類;三甲基甲氧矽烷、二甲基二乙氧矽烷、甲基二甲氧矽烷、二甲基乙烯基乙氧矽烷、二苯基二甲氧矽烷、苯基三乙氧矽烷等之烷氧矽烷類;六甲基二矽氮烷、N,N’-雙(三甲基矽烷)脲、二甲基三甲基矽烷胺、三甲基矽烷咪唑等之矽氮烷類;乙烯基三氯矽烷、γ-氯丙基三甲氧矽烷、γ-胺丙基三乙氧矽烷、γ-環氧丙氧基丙基三甲氧矽烷等之矽烷類;苯并***、苯并咪唑、吲唑、咪唑、2-巰基苯并咪唑、2-巰基苯并噻唑、2-巰基苯并噁唑、脲唑、硫脲嘧啶、巰基咪唑、巰基嘧啶等之雜環型化合物、1,1-二甲基脲、1,3-二甲基脲等之脲、或是硫脲化合物。此等黏著輔助劑,相對於微影用阻劑下層膜材料的全體固體成分,通常以未達5質量%,較佳以未達2質量%的比率來調配。
本發明之微影用阻劑下層膜材料,為了防止
針孔或擦痕的產生等,且更進一步提升相對於表面不均之塗佈性,可調配界面活性劑。界面活性劑,例如可列舉出聚氧乙烯月桂醚、聚氧乙烯硬脂醚、聚氧乙烯鯨蠟醚、聚氧乙烯油醚等之聚氧乙烯烷醚類,聚氧乙烯辛酚醚、聚氧乙烯壬酚醚等之聚氧乙烯烷基烯丙醚類,聚氧乙烯-聚氧
丙烯嵌段共聚物類,山梨醇單月桂酸酯、山梨醇單棕櫚酸酯、山梨醇單硬脂酸酯、山梨醇單油酸酯、山梨醇三油酸酯、山梨醇三硬脂酸酯等之山梨醇脂肪酸酯類,聚氧乙烯山梨醇單月桂酸酯、聚氧乙烯山梨醇單棕櫚酸酯、聚氧乙烯山梨醇單硬脂酸酯、聚氧乙烯山梨醇三油酸酯、聚氧乙烯山梨醇三硬脂酸酯等之聚氧乙烯山梨醇脂肪酸酯類等之非離子系界面活性劑;F-TOP EF301、EF303、EF352(Tohkem Products股份有限公司製,商品名稱)、Megafac F171、F173、R-30(Dainippon Ink股份有限公司製,商品名稱)、Fluorad FC430、FC431(Sumitomo 3M股份有限公司製,商品名稱)、AsahiGuard AG710、Surflon S-382、SC101、SC102、SC103、SC104、SC105、SC106(Asahi Glass股份有限公司製,商品名稱)等之氟系界面活性劑;有機矽氧烷聚合物KP341(信越化學工業股份有限公司製)等。此等界面活性劑的調配量,相對於本發明之微影用阻劑下層膜材料的全體固體成分,通常為2.0質量%以下,較佳為1.0質量%以下。此等界面活性劑可單獨添加或組合2種以上添加。
本發明中,溶解上述聚合物及交聯劑成分、
交聯催化劑等之溶劑,可使用乙二醇單甲醚、乙二醇單***、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單***、丙二醇、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單***、丙二醇單***乙酸酯、丙二醇丙醚乙酸酯、甲苯、二甲苯、丁酮、環戊酮、環己
酮、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧丙酸甲酯、3-甲氧丙酸乙酯、3-乙氧丙酸乙酯、3-乙氧丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯等。此等有機溶劑可單獨使用或組合2種以上使用。
再者,亦可混合丙二醇單丁醚、丙二醇單丁醚乙酸酯等之高沸點溶劑來使用。此等溶劑中,丙二醇單甲醚、丙二醇單甲醚乙酸酯、乳酸乙酯、乳酸丁酯、及環己酮等,相對於平坦性的提升為較佳。
本發明所使用之阻劑,為光阻或電子束阻劑。
於本發明之微影用阻劑下層膜的上部所塗佈之光阻,負型、正型均可使用,係有由酚醛樹脂與1,2-萘醌二疊氮磺酸酯所構成之正型光阻、由具有可藉由酸所分解以提升鹼溶解速度之基之黏合劑與光酸產生劑所構成之化學增幅型光阻、由鹼可溶性黏合劑與可藉由酸所分解以提升光阻的鹼溶解速度之低分子化合物與光酸產生劑所構成之化學增幅型光阻、由具有可藉由酸所分解以提升鹼溶解速度之基之黏合劑與可藉由酸所分解以提升光阻的鹼溶解速度之低分子化合物與光酸產生劑所構成之化學增幅型光阻、以及於骨架具有Si原子之光阻等,例如可列舉出Rohm and Haas公司製,商品名稱APEX-E者。
此外,於本發明之微影用阻劑下層膜的上部
所塗佈之電子束阻劑,例如可列舉出由主鏈中含有Si-Si鍵且於末端含有芳香族環之樹脂與可藉由電子束的照射而產生酸之酸產生劑所構成之組成物,或是由羥基由含有N-羧胺之有機基所取代之聚(對羥基苯乙烯)與可藉由電子束的照射而產生酸之酸產生劑所構成之組成物等。於後者的電子束阻劑組成物中,藉由電子束照射從酸產生劑所產生之酸與聚合物側鏈的N-羧基氨氧基反應,使聚合物側鏈分解為羥基,顯示出鹼可溶性並溶解於鹼顯影液,而形成阻劑圖型。藉由該電子束的照射而產生酸之酸產生劑,可列舉出1,1-雙[對氯苯基]-2,2,2-三氯乙烷、1,1-雙[對甲氧苯基]-2,2,2-三氯乙烷、1,1-雙[對氯苯基]-2,2-二氯乙烷、2-氯-6-(三氯甲基)吡啶等之鹵化有機化合物;三苯基鋶鹽、二苯基錪鹽等之鎓鹽;甲苯磺酸硝苄酯、甲苯磺酸二硝苄酯等之磺酸酯。
具有使用本發明之微影用阻劑下層膜材料所
形成之阻劑下層膜之阻劑的顯影液,可使用氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨水等之無機鹼類;乙胺、正丙胺等之一級胺類;二乙胺、二正丁胺等之二級胺類;三乙胺、甲基二乙胺等之三級胺類;二甲基乙醇胺、三乙醇胺等之醇胺類;氫氧化四甲基銨、氫氧化四乙基銨、膽鹼等之四級銨鹽;吡咯、哌啶等之環狀胺類等之鹼類的水溶液。此外,可於上述鹼類的水溶液添加適當量的異丙醇等之醇類、非離子系等的界面活性劑。此等當中,較佳的顯影液為四級銨鹽,更佳為氫氧化四甲基銨及
膽鹼。
接著說明本發明之阻劑圖型形成法,於精密
積體電路元件的製造時所使用之基板(例如矽/二氧化矽被覆、玻璃基板、ITO基板等之透明基板)上,藉由旋轉塗佈機、塗佈機等之適當的塗佈方法塗佈阻劑下層膜形成組成物後,進行烘烤使其硬化而製作塗佈型下層膜。在此,阻劑下層膜的膜厚較佳約為0.01至3.0μm。此外,塗佈後烘烤的條件,為於80至350℃進行0.5至120分鐘。然後於阻劑下層膜上直接塗佈阻劑,或是因應必要使1層至數層的塗膜材料成膜於阻劑下層膜上後再塗佈阻劑,並通過既定的遮罩進行光或電子束的照射,然後藉由顯影、淋洗、乾燥而可得到良好的阻劑圖型。亦可因應必要,於光或電子束的照射進行加熱(PEB:Post Exposure Bake)。此外,可藉由乾式蝕刻,去除阻劑經由前述步驟被顯影去除之部分的阻劑下層膜,而在基板上形成期望的圖型。
上述光阻中的曝光光,為近紫外線、遠紫外
線、或超紫外線(例如EUV,波長13.5nm)等之化學射線,例如可使用248nm(KrF雷射光)、193nm(ArF雷射光)、157nm(F2雷射光)等之波長光。光照射,只要是可從光酸產生劑產生酸之方法,則可無特別限制地使用,曝光量為1至2000mJ/cm2,或10至1500mJ/cm2,或50至1000mJ/cm2。此外,電子束阻劑的電子束照射,例如可使用電子束照射裝置來照射。
本發明中,可經由下列步驟來製造半導體裝
置,亦即藉由阻劑下層膜形成組成物將該阻劑下層膜形成於半導體基板之步驟、於其上方形成阻劑膜之步驟、藉由光或電子束的照射及顯影來形成阻劑圖型之步驟、藉由阻劑圖型對該阻劑下層膜進行蝕刻之步驟、以及藉由經圖型化後之阻劑下層膜來加工半導體基板之步驟。
今後,隨著阻劑圖型之細微化的進展,會產
生解像度的問題或是阻劑圖型於顯影後倒塌之問題,故希望達成阻劑的薄膜化。因而下列製程乃逐漸變得必要,亦即於基板加工時不易得到充分的阻劑圖型膜厚,且不僅是阻劑圖型,對於在阻劑與被加工之半導體基板之間所形成之阻劑下層膜,亦須具有可作為於基板加工時之遮罩功能。本發明,與以往之高蝕刻速率性的阻劑下層膜不同,可提供具有接近於阻劑之乾式蝕刻速度的選擇比之微影用阻劑下層膜,並且具有較阻劑更小之乾式蝕刻速度的選擇比之微影用阻劑下層膜或具有較半導體基板更小之乾式蝕刻速度的選擇比之微影用阻劑下層膜,作為如此之製程用的阻劑下層膜。此外,亦可對如此的阻劑下層膜賦予抗反射能,而兼具以往之抗反射膜的功能。
再者,為了得到細微的阻劑圖型,亦開始採
用下列製程,亦即於阻劑下層膜的乾式蝕刻時,將阻劑圖型與阻劑下層膜形成較阻劑顯影時的圖型寬度更細。本發明,與以往之高蝕刻速率性的抗反射膜不同,亦可提供具有接近於阻劑之乾式蝕刻速度的選擇比之阻劑下層膜作為
如此之製程用的阻劑下層膜。此外,亦可對如此的阻劑下層膜賦予抗反射能,而兼具以往之抗反射膜的功能。
本發明中,在將本發明之阻劑下層膜成膜於
基板上後,可於阻劑下層膜上直接塗佈阻劑,或是因應必要使1層至數層的塗膜材料成膜於阻劑下層膜上後再塗佈阻劑。藉此,即使在窄化阻劑的圖型寬度,且為了防止圖型倒塌而較薄地被覆阻劑時,亦可藉由選擇適當的蝕刻氣體來加工基板。
具體而言,可經由下列步驟來製造半導體裝
置,亦即藉由阻劑下層膜形成組成物將該阻劑下層膜形成於半導體基板之步驟、於其上方形成由含有矽成分等之塗膜材料所構成之硬遮罩或是由蒸鍍所形成之硬遮罩(例如氮氧化矽)之步驟、再於其上方形成阻劑膜之步驟、藉由光或電子束的照射及顯影來形成阻劑圖型之步驟、藉由阻劑圖型並以鹵素系氣體對硬遮罩進行蝕刻之步驟、藉由經圖型化後之硬遮罩並以氧系氣體或氫系氣體對該阻劑下層膜進行蝕刻之步驟、以及藉由經圖型化後之阻劑下層膜並以鹵素系氣體來加工半導體基板之步驟。
如此,本發明之微影用阻劑下層膜形成組成
物,在考量到作為抗反射膜的效果時,由於光吸收部位被擷取至骨架中,所以在加熱乾燥時不會有擴散於光阻中的擴散物,此外,由於光吸收部位具有充分大的吸光性能,所以抗反射光的效果高。
此外,本發明之微影用阻劑下層膜形成組成
物中,熱穩定性高,可防止燒結時的分解物對上層膜造成污染,並且可使燒結步驟的溫度臨限具有更大的寬容度。
再者,本發明之微影用阻劑下層膜材料,可
因應製程條件的不同而使用作為具有下列功能之膜,亦即防止光的反射之功能,以及防止基板與光阻之相互作用,或是防止光阻所使用之材料或於光阻的曝光時所生成之物質對基板造成不良作用之功能。
將間苯三酚(東京化成工業股份有限公司製)20.0g、對甲醯苯甲酸(東京化成工業股份有限公司製)20.3g、丙二醇單甲醚120.8g放入於300ml燒瓶中。然後在加熱迴流下迴流攪拌約5小時。反應結束後進行離子交換處理,得到茶褐色的間苯三酚樹脂溶液。所得之聚合物相當於式(1-1)。藉由GPC並經聚苯乙烯換算所測得之重量平均分子量Mw為2,450,多分散度Mw/Mn為1.6。
將間苯三酚(東京化成工業股份有限公司製)5.1g、1,5-二羥基萘(東京化成工業股份有限公司製)6.5g、對甲醯苯甲酸(東京化成工業股份有限公司製)9.2g、丙二醇單甲醚62.3g放入於100ml燒瓶中。然後在加熱迴流下
迴流攪拌約3小時。反應結束後進行離子交換處理,得到茶褐色的樹脂溶液。所得之聚合物,相當於包含式(1-1)與式(1-8)的單位結構之共聚物。藉由GPC並經聚苯乙烯換算所測得之重量平均分子量Mw為4,430,多分散度Mw/Mn為6.4。
將間苯三酚(東京化成工業股份有限公司製)5.5g、間苯二酚(東京化成工業股份有限公司製)4.8g、對甲醯苯甲酸(東京化成工業股份有限公司製)10.7g、丙二醇單甲醚63.1g放入於100ml燒瓶中。然後在加熱迴流下迴流攪拌約3小時。反應結束後進行離子交換處理,得到茶褐色的間苯三酚樹脂溶液。所得之聚合物,相當於包含式(1-1)與式(1-5)的單位結構之共聚物。藉由GPC並經聚苯乙烯換算所測得之重量平均分子量Mw為3,000,多分散度Mw/Mn為1.9。
將間苯三酚(東京化成工業股份有限公司製)12.0g、苯甲醛(東京化成工業股份有限公司製)10.1g、丙二醇單甲醚53.7g、甲烷磺酸(東京化成工業股份有限公司製)0.92g放入於100ml茄形燒瓶中。然後在加熱迴流下迴流攪拌約4小時。反應結束後進行離子交換處理,得到茶褐色的間苯三酚樹脂溶液。所得之聚合物相當於式
(3-1)。藉由GPC並經聚苯乙烯換算所測得之重量平均分子量Mw為1,870,多分散度Mw/Mn為1.6。
將間苯三酚(東京化成工業股份有限公司製)45.0g、4-羥基苯甲醛(東京化成工業股份有限公司製)43.6g、丙二醇單甲醚170.9g、甲烷磺酸(東京化成工業股份有限公司製)3.46g放入於300ml茄形燒瓶中。然後在加熱迴流下迴流攪拌約3小時。反應結束後進行離子交換處理,得到茶褐色的間苯三酚樹脂溶液。所得之聚合物相當於式(3-2)。藉由GPC並經聚苯乙烯換算所測得之重量平均分子量Mw為1,260,多分散度Mw/Mn為1.5。
將合成例1中所得之樹脂2g(固體成分)與四甲氧甲基甘脲0.3g,溶解於丙二醇單甲醚16.1g與丙二醇單甲醚乙酸酯6.9g,調製出由多層膜所構成之使用在微影製程之阻劑下層膜形成組成物的溶液。
將合成例2中所得之樹脂2g(固體成分)與四甲氧甲基雙酚0.3g,溶解於丙二醇單甲醚16.1g與丙二醇單甲醚乙酸酯6.9g,調製出由多層膜所構成之使用在微影製程之阻劑下層膜形成組成物的溶液。
將合成例3中所得之樹脂2g(固體成分)與四甲氧甲基甘脲0.3g,溶解於丙二醇單甲醚16.1g與丙二醇單甲醚乙酸酯6.9g,調製出由多層膜所構成之使用在微影製程之阻劑下層膜形成組成物的溶液。
將甲酚酚醛樹脂(市售品,重量平均分子量為4000)1g(固體成分),溶解於丙二醇單甲醚10.34g與環己酮2.59g,調製出由多層膜所構成之使用在微影製程之阻劑下層膜形成組成物的溶液。
將比較合成例1中所得之樹脂2g(固體成分),溶解於四甲氧甲基甘脲0.3g、丙二醇單甲醚16.1g與丙二醇單甲醚乙酸酯6.9g,調製出由多層膜所構成之使用在微影製程之阻劑下層膜形成組成物的溶液。
將比較合成例2中所得之樹脂2g(固體成分),溶解於四甲氧甲基甘脲0.3g、丙二醇單甲醚16.1g與丙二醇單甲醚乙酸酯6.9g,調製出由多層膜所構成之使用在微影製程之阻劑下層膜形成組成物的溶液。
使用旋轉塗佈機,將實施例1至3、比較例1至3中所調製之各阻劑下層膜形成組成物的溶液分別塗佈於矽晶圓上。在加熱板上,於240℃進行1分鐘的燒結而形成阻劑下層膜(膜厚0.05μm)。使用分光橢圓測厚儀,對此等阻劑下層膜測定於波長193nm時的折射率(n值)及光學吸光係數(k值,亦稱為衰減係數)。結果如第1表所示。
乾式蝕刻速度的測定中所使用之蝕刻機及蝕刻氣體,係使用下列所示者。
RIE-10NR(SAMCO公司製):CF4
使用旋轉塗佈機,將實施例1至3、比較例2至3中所調製之各阻劑下層膜形成組成物的溶液分別塗佈於矽晶圓上。在加熱板上,於240℃進行1分鐘的燒結後,於400℃進行2分鐘(比較例1係於240℃進行1分鐘)的燒結,而形成阻劑下層膜(膜厚0.20μm)。使用CF4氣體作為蝕刻氣體來測定乾式蝕刻速度。此外,使用旋轉塗佈機,將比較例1的溶液塗佈於矽晶圓上而形成塗膜。使用CF4氣體作為蝕刻氣體來測定乾式蝕刻速度,並分別進行實施例1至3及比較例2至3之阻劑下層膜的乾式蝕刻速度,與比較例1之阻劑下層膜的乾式蝕刻速度之比較。結果如第2表所示。速度比為(各實施例1至3及比較例2至3中所得之阻劑下層膜)/(比較例1中所得之阻劑下層膜)之乾式蝕刻速度比。
使用旋轉塗佈機,將實施例1至3、比較例1至3中所調製之阻劑下層膜形成組成物的溶液塗佈於矽晶圓上。在加熱板上,於240℃進行1分鐘的燒結而形成阻劑下層膜層(膜厚0.20μm)。對此等阻劑下層膜層,進行相對於阻劑所使用之溶劑,例如丙二醇單甲醚、丙二醇單甲醚乙酸酯之浸漬試驗。結果如第3表所示。殘膜率,為分別浸漬在各溶劑60秒,測定浸漬前後的膜厚,並以(浸漬後的膜厚)/(浸漬前的膜厚)×100所算出之結果。
使用旋轉塗佈機,將實施例1至3中所調製之阻劑下層膜形成組成物的溶液塗佈於矽晶圓上。在加熱板上,於240℃進行1分鐘的燒結而形成阻劑下層膜(膜厚0.20μm)。對此等阻劑下層膜,進行相對於2.38質量%氫氧化四甲基銨水溶液之浸漬試驗。結果如第4表所示。浸漬於2.38質量%氫氧化四甲基銨水溶液60秒,並觀察浸漬後之膜的概況,未殘存膜時為可去除,殘存膜時為不可去除。
由本發明之多層膜所形成之使用在微影製程之阻劑下層膜材料,與以往之高蝕刻速率性抗反射膜不同,係具有高耐乾式蝕刻性,所以具有作為硬遮罩之特性。此外,相對於以往在去除阻劑下層膜時採用灰化(灰化去除)方式,本發明所得到之阻劑下層膜可藉由鹼水溶液去除,所以可期待於去除時能夠降低對基板所造成之破壞。
Claims (11)
- 一種微影用阻劑下層膜形成組成物,其係包含含有下列式(1)的單位結構之聚合物,及交聯劑,
- 如申請專利範圍第1項之阻劑下層膜形成組成物,其中由A定義之經羥基取代的伸芳基,為來自苯二醇、苯三醇、或萘二醇之經羥基取代的伸芳基。
- 如申請專利範圍第1項之阻劑下層膜形成組成物,其中由A定義之經羥基取代的伸芳基,為來自兒茶酚、間苯二酚、氫醌、苯三酚、偏苯三酚、或間苯三酚之經羥基取代的伸苯基。
- 如申請專利範圍第1至3項中任一項之阻劑下層膜形成組成物,其中由B定義之伸芳基,為依據苯環、萘環、或蒽環之有機基,或是與T鍵結而依據茀環之有機基。
- 如申請專利範圍第1至3項中任一項之阻劑下層膜形成組成物,其中由B定義之雜環基,為依據可經取代之呋喃環、噻吩環、吡咯環、咔唑環、或二苯并呋喃環之有機基。
- 如申請專利範圍第1至3項中任一項之阻劑下層膜形成組成物,其中由B定義之伸芳基或雜環基,為具有鹵素基、羥基、硝基、胺基、羧酸酯基、腈基、或此等的組合作為取代基。
- 一種阻劑下層膜,其係將如申請專利範圍第1至6項中任一項之阻劑下層膜形成組成物塗佈於半導體基板上並燒結而得到。
- 一種使用在半導體的製造之阻劑圖型之形成方法,其係包含:將如申請專利範圍第1至6項中任一項之阻劑下層膜形成組成物塗佈於半導體基板上並燒結以形成下層膜之步驟。
- 一種半導體裝置之製造方法,其係包含:藉由如申 請專利範圍第1至6項中任一項之阻劑下層膜形成組成物將下層膜形成於半導體基板上之步驟、於其上方形成阻劑膜之步驟、藉由光或電子束的照射及顯影來形成阻劑圖型之步驟、藉由阻劑圖型對該下層膜進行蝕刻之步驟、以及藉由經圖型化後之下層膜來加工半導體基板之步驟。
- 一種半導體裝置之製造方法,其係包含:藉由如申請專利範圍第1至6項中任一項之阻劑下層膜形成組成物將下層膜形成於半導體基板上之步驟、於其上方形成硬遮罩之步驟、再於其上方形成阻劑膜之步驟、藉由光或電子束的照射及顯影來形成阻劑圖型之步驟、藉由阻劑圖型對硬遮罩進行蝕刻之步驟、藉由經圖型化後之硬遮罩對該阻劑下層膜進行蝕刻之步驟、以及藉由經圖型化後之阻劑下層膜來加工半導體基板之步驟。
- 如申請專利範圍第10項之製造方法,其中硬遮罩藉由無機物的塗佈物或無機物的蒸鍍所形成。
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