TWI718225B - 研磨用組成物及矽基板之研磨方法 - Google Patents
研磨用組成物及矽基板之研磨方法 Download PDFInfo
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- TWI718225B TWI718225B TW105143929A TW105143929A TWI718225B TW I718225 B TWI718225 B TW I718225B TW 105143929 A TW105143929 A TW 105143929A TW 105143929 A TW105143929 A TW 105143929A TW I718225 B TWI718225 B TW I718225B
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- Prior art keywords
- water
- soluble polymer
- polishing
- polishing composition
- silica
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 201
- 239000000203 mixture Substances 0.000 title claims abstract description 100
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- 239000010703 silicon Substances 0.000 title claims description 41
- 229910052710 silicon Inorganic materials 0.000 title claims description 41
- 239000000758 substrate Substances 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 17
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 100
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 46
- 239000012086 standard solution Substances 0.000 claims abstract description 46
- 238000001179 sorption measurement Methods 0.000 claims abstract description 32
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- 239000000126 substance Substances 0.000 description 3
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- 239000001103 potassium chloride Substances 0.000 description 1
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- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 150000003377 silicon compounds Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
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- 230000003746 surface roughness Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- UJJLJRQIPMGXEZ-UHFFFAOYSA-N tetrahydro-2-furoic acid Chemical compound OC(=O)C1CCCO1 UJJLJRQIPMGXEZ-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L21/04—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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- H—ELECTRICITY
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Abstract
本發明提供可實現具有平滑性及低缺陷性之被研磨面之研磨用組成物。研磨用組成物含有滿足條件(A)及(B)之水溶性高分子。
條件(A):由平均一次粒徑35nm之氧化矽、水溶性高分子、氨及水所成之氧化矽濃度為0.48質量%,水溶性高分子之濃度為0.0125質量%,pH為10.0之第一標準液中,第一標準液中含有之吸附於氧化矽之水溶性高分子之量相對於水溶性高分子總量之比例的吸附率為10%以上。
條件(B):由平均一次粒徑35nm之氧化矽、水溶性高分子、氨及水所成之氧化矽濃度為0.48質量%,水溶性高分子之濃度為0.0125質量%,pH為10.4之第二標準液中,第二標準液中含有之吸附於氧化矽之水溶性高分子之量相對於水溶性高分子總量之比例的吸附率為65%以下。
Description
本發明係有關研磨用組成物及矽基板之研磨方法。
為了矽晶圓之表面平滑化或減低缺陷等之品質提高,而提案種種有關研磨用組成物或研磨方法之技術(例如參考專利文獻1)。然而,近幾年來,由於關於矽晶圓之表面品質之要求日益提高,故對該等技術要求進一步改良。
[專利文獻1]國際公開第2014/148399號
本發明未解決如上述之先前技術具有之問題點,而提供可實現具有高平滑性及低缺陷性之被研磨面之
研磨用組成物及矽基板之研磨方法。
為解決前述課題,本發明之一樣態之研磨用組成物其要旨係含有研磨粒及水溶性高分子之研磨用組成物,且水溶性高分子係滿足下述2個條件(A)及(B)者。
條件(A):由平均一次粒徑35nm之氧化矽、水溶性高分子、氨及水所成之氧化矽濃度為0.48質量%,水溶性高分子之濃度為0.0125質量%,pH為10.0之第一標準液中,第一標準液中含有之吸附於氧化矽之水溶性高分子之量相對於水溶性高分子總量之比例的吸附率為10%以上。
條件(B):由平均一次粒徑35nm之氧化矽、水溶性高分子、氨及水所成之氧化矽濃度為0.48質量%,水溶性高分子之濃度為0.0125質量%,pH為10.4之第二標準液中,第二標準液中含有之吸附於氧化矽之水溶性高分子之量相對於水溶性高分子總量之比例的吸附率為65%以下。
又,本發明之另一樣態之矽基板之研磨方法,其要旨係包含使用上述一樣態之研磨用組成物研磨矽基板。
依據本發明,可實現具有高平滑性及低缺陷
性之被研磨面。
針對本發明一實施形態詳細說明,本實施形態之研磨用組成物係含有研磨粒及水溶性高分子之研磨用組成物,且前述水溶性高分子係滿足下述2個條件(A)及(B)者。
條件(A):由平均一次粒徑35nm之氧化矽、水溶性高分子、氨及水所成之氧化矽濃度為0.48質量%,水溶性高分子之濃度為0.0125質量%,pH為10.0之第一標準液中,第一標準液中含有之吸附於氧化矽之水溶性高分子之量相對於水溶性高分子總量之比例的吸附率為10%以上。
條件(B):由平均一次粒徑35nm之氧化矽、水溶性高分子、氨及水所成之氧化矽濃度為0.48質量%,水溶性高分子之濃度為0.0125質量%,pH為10.4之第二標準液中,第二標準液中含有之吸附於氧化矽之水溶性高分子之量相對於水溶性高分子總量之比例的吸附率為65%以下。
換言之,調製含有水溶性高分子之第一標準液、第二標準液,並將該第一標準液、第二標準液中之水溶性高分子對氧化矽之吸附率設為上述條件(A)及條件(B)之數值範圍內時,其水溶性高分子可作為本實施形態之研磨用組成物所含有之水溶性高分子使用。
如此之本實施形態之研磨用組成物可較好地使用於對單體矽、矽化合物、金屬、陶瓷等之各種研磨對象物之研磨,可實現具有高平滑性(低濁度)之被研磨面。且可實現缺陷少之被研磨面。尤其,於矽基板之研磨中若使用本實施形態之研磨用組成物,則可製造具有高平滑性及低缺陷性之表面之矽單晶基板等之矽基板。
以下,針對本實施形態之研磨用組成物詳細說明。又以下說明之各種操作或物性測定,只要為特別限定,則為在室溫(20℃以上25℃以下)、相對溼度40%以上50%以下之條件下進行者。
本實施形態之吸附率係第一標準液或第二標準液中含有之吸附於氧化矽之水溶性高分子之量相對於水溶性高分子總量之百分率。詳言之,本實施形態之吸附率係第一標準液或第二標準液中含有之水溶性高分子總量中,吸附於氧化矽之水溶性高分子之量之比率(百分率)。
若為含有具有滿足條件(A)之性質之水溶性高分子之研磨用組成物,則使用於研磨對象物之研磨時,可實現具有高平滑性(低濁度)及低缺陷性之被研磨面。
使用本實施形態之研磨用組成物研磨研磨對象物之被研磨面時,吸附於研磨粒之水溶性高分子之量若較多,則研磨粒表面因水溶性高分子而受保護,使研磨對象物之被研磨面所受之加工負荷變小,故認為不易獲得高
平滑性性(低濁度)及低缺陷性之被研磨面。由於研磨時之研磨用組成物之pH通常為10.0左右,故以pH為10.0時之吸附率之數值作為指標。
pH為10.0時之吸附率為10%以上,但較好為20%以上,更好為50%以上。且pH為10.0時之吸附率較好為80%以下,更好為70%以下。若pH為10.0時之吸附率如上述,則可發揮獲得適當被研磨面之保護性之效果。
另一方面,若為含有具有如滿足條件(B)之性質之水溶性高分子之研磨用組成物,則附著研磨用組成物之研磨後之研磨對象物進行洗淨時,可實現缺陷少之被研磨面。
研磨結束後之研磨對象物之洗淨時,若水溶性高分子自研磨粒脫離而使吸附於研磨粒之水溶性高分子之量減少,則由於容易自研磨對象物洗淨研磨粒,故認為洗淨時不易於研磨對象物之被研磨面發生缺陷。洗淨時之研磨用組成物之pH(例如混合洗淨液之狀態下之pH)通常為10.4左右,故以pH為10.4時之吸附率之數值作為指標。
pH為10.4時之吸附率為65%以下或小於前述之pH為10.0時之吸附率且為65%以下,較好為50%以下或小於前述之pH為10.0時之吸附率且為50%以下,更好為40%以下或小於前述之pH為10.0時之吸附率且為40%以下,又更好為30%以下或小於前述之pH為10.0時之吸附率且為30%以下。
本實施形態之研磨用組成物中含有之研磨粒種類並未特別限定,可使用例如無機粒子、有機粒子、有機無機複合粒子等作為研磨粒。無機粒子之具體例舉例有由氧化矽、氧化鋁、氧化鈰、氧化鈦等之金屬氧化物所成之粒子、或氮化矽、碳化矽、氮化硼等之陶瓷所成之粒子。又,作為有機粒子之具體例舉例為聚甲基丙烯酸甲酯(PMMA)粒子。該等中較好為氧化矽。作為氧化矽之具體例舉例為膠體氧化矽、發煙氧化矽、沉降氧化矽等,特佳為膠體氧化矽。該等研磨粒可單獨使用1種,亦可組合併用2種以上。
再者,研磨粒之平均一次粒徑並未特別限定,但可為100nm以下,較好為50nm以下,更好為40nm以下,又更好為30nm以下。研磨粒之平均一次粒徑若為上述範圍內,則發揮提高被研磨面之平滑性效果。另一方面,研磨粒之一次平均粒徑可為5nm以上,較好為10nm以上,更好為20nm以上。研磨粒之平均一次粒徑若為上述範圍內,則發揮提高利用研磨用組成物之研磨對象物之研磨速度之效果。又,研磨粒之平均一次粒徑可藉由例如氮吸附法(BET法)測定由比表面積算出。
又,研磨粒之平均二次粒徑並未特別限定,但可為150nm以下,較好為100nm以下,更好為80nm以下,又更好為60nm以下。研磨粒之平均二次粒徑若為上
述範圍內,則發揮提高被研磨面之平滑性效果。另一方面,研磨粒之二次平均粒徑可為10nm以上,較好為20nm以上,更好為30nm以上,又更好為40nm以上。研磨粒之平均二次粒徑若為上述範圍內,則發揮可以更短時間進行研磨之效果。又,研磨粒之平均二次粒徑可藉由例如日機裝股份有限公司製之UPA-UT151藉由動態光散射法測定。
再者,本實施形態之研磨用組成物中之研磨粒含量可為0.01質量%以上,較好為0.05質量%以上,更好為0.10質量%以上,又更好為0.15質量%以上。研磨粒含量若為上述範圍內,則發揮提高利用研磨用組成物之研磨對象物之研磨速度之效果。另一方面,研磨粒之含量可為3.0質量%以下,更好為1.0質量%以下,又更好為0.50質量%以下,再更好為0.30質量%以下,又再更好為0.20質量%以下。研磨粒含量若為上述範圍內,則可提高研磨用組成物之分散安定性。
本實施形態之研磨用組成物中,添加滿足前述對研磨粒之吸附率條件之水溶性高分子(可為共聚物。且亦可為該等之鹽、衍生物等)。水溶性高分子可提高研磨粒之表面及被研磨面之保護性及被研磨面之濡濕性。
作為水溶性高分子,可使用於分子中含有選自陽離子基、陰離子基及非離子基之至少一種官能基者。具體而
言,可使用分子中包含羥基、羧基、醯氧基、磺基、醯胺基、脒基、亞胺基、醯亞胺基、四級氮構造、含前述官能基單位之雜環構造、乙烯基構造、聚氧伸烷基構造等者之任一者。
作為水溶性高分子之具體例舉例為纖維素衍生物、聚乙烯醇、聚(甲基)丙烯酸、聚(甲基)丙烯醯胺烷基磺酸、聚異戊二烯磺酸、聚乙烯磺酸、聚烯丙基磺酸、聚異戊烯磺酸、聚苯乙烯磺酸鹽、聚(甲基)丙烯醯胺、聚烷基胺基烷基(甲基)丙烯醯胺、聚乙烯吡咯啶酮、構造之一部分含有聚乙烯吡咯啶酮之共聚物、聚乙烯己內醯胺、構造之一部分含有聚乙烯己內醯胺之共聚物、聚烷氧基烷基(甲基)丙烯醯胺、聚羥基烷基(甲基)丙烯醯胺、聚(甲基)丙烯醯基嗎啉、聚脒、聚伸乙基亞胺、親水化聚醯亞胺、各種聚胺基酸、聚(N-醯基伸烷基亞胺)等之亞胺衍生物、聚乙烯醇之羥基部分之一部分取代為四級氮構造之聚乙烯醇衍生物、聚氧乙烯、具有聚氧伸烷基構造之聚合物、具有該等之二嵌段型或三嵌段型、無規型、交替型之複數種構造之聚合物等。又,聚(甲基)丙烯酸之(甲基)丙烯酸之記述意指丙烯酸及/或甲基丙烯酸,關於其他化合物亦同。
上述水溶性高分子中,基於提高矽晶圓等之基板之研磨面之濡濕性、抑制顆粒附著及減低表面粗糙度等之觀點,較好為纖維素衍生物、聚乙烯醇、聚(甲基)丙烯醯基嗎啉、具有聚氧伸烷基構造之聚合物。作為纖維
素衍生物之具體例舉例為羥乙基纖維素、羥丙基纖維素、羥乙基甲基纖維素、羥丙基甲基纖維素、甲基纖維素、乙基纖維素、乙基羥乙基纖維素、羧甲基纖維素等。該等纖維素衍生物中,基於提高對矽晶圓等之基板之研磨面賦予濡濕性之能力、具有良好洗淨性之觀點,特佳為羥乙基纖維素。且水溶性高分子可單獨使用一種,亦可組合使用兩種以上。
水溶性高分子之重量平均分子量並未特別限定。可為200萬以下,更好為100萬以下,又更好為50萬以下,再更好為30萬以下,又更好為20萬以下,特佳為10萬以下,最好為5萬以下。重量平均分子量若為上述範圍內,則發揮提高研磨用組成物之安定性並且減低研磨對象物之缺陷之效果。
另一方面,水溶性高分子之重量平均分子量可為1000以上,更好為5000以上,更好為1萬以上。重量平均分子量若為上述範圍內,則發揮提高研磨對象物之研磨速度之效果。
又,水溶性高分子之重量平均分子量可使用例如凝膠滲透層析儀(GPC),藉由聚環氧乙烷換算而算出。
又本實施形態之研磨用組成物中之水溶性高分子含量可為0.0001質量%以上,較好為0.001質量%以上,更好為0.005質量%以上。水溶性高分子之含量若為上述範圍內,則發揮提高研磨對象物之濡濕性之效果。另一方面,水溶性高分子之含量可為1.0質量%以下,較好
為0.1質量%以下,更好為0.02質量%以下,又更好為0.01質量%以下。水溶性高分子之含量若為上述範圍內,則提高研磨用組成物之分散安定性。
再者,水溶性高分子之聚合方法並未特別限定,可採用例如聚加成、聚縮合、加成縮合、離子聚合等之反應。水溶性高分子亦可為藉由該等反應等所得之連鎖聚合物、逐次聚合物或活性聚合物。且,亦可併用聚合方法不同之複數種水溶性高分子。
本實施形態之研磨用組成物亦可含有鹼性化合物。鹼性化合物係對矽基板等之研磨對象物表面賦予化學作用進行化學研磨(化學蝕刻)。藉此,容易提高研磨研磨對象物時之研磨速度。
鹼性化合物之種類並未特別限定,可為有機鹼性化合物,亦可為鹼金屬氫氧化物、鹼金屬碳酸氫鹽、鹼金屬碳酸鹽、氨等之無機鹼性化合物。該等鹼性化合物可單獨使用1種,亦可組合2種以上使用。
作為鹼性化合物之具體例舉例為鹼金屬或鹼土類金屬之氫氧化物或鹽、氫氧化四級銨或其鹽、氨、胺等。鹼金屬之具體例舉例為鉀、鈉等。鹼土類金屬之具體例舉例為鈣、鎂等。鹽之具體例舉例為碳酸鹽、碳酸氫鹽、硫酸鹽、乙酸鹽等。四級銨之具體例舉例為四甲銨、四乙銨、四丁銨等。
鹼金屬之氫氧化物之具體例舉例為氫氧化鉀、碳酸鉀、碳酸氫鉀、硫酸鉀、乙酸鉀、氯化鉀等。鹼土類金屬之氫氧化物或鹽之具體例舉例為氫氧化鈣等。氫氧化四級銨或其鹽之具體例舉例為氫氧化四鉀銨、氫氧化四乙銨、氫氧化四丁銨等。
胺之具體例舉例為甲胺、二甲胺、三乙胺、乙胺、二乙胺、三乙胺、乙二胺、單乙醇胺、N-(β-胺基乙基)乙醇胺、六亞甲基二胺、二伸乙基三胺、三伸乙基四胺、無水哌嗪、哌嗪六水合物、1-(2-胺基乙基)哌嗪、N-甲基哌嗪、胍、咪唑或三唑等之唑類等。
該等鹼性化合物可單獨使用一種,亦可組合兩種以上使用。
該等鹼性化合物中,較好為選自氨、銨鹽、鹼金屬氫氧化物、鹼金屬鹽、及四級銨氫氧化物之至少一種。因此進而更好為選自氨、氫氧化鉀、氫氧化鈉、氫氧化四甲銨、氫氧化四乙銨、碳酸氫銨、碳酸銨、碳酸氫鉀、碳酸鉀、碳酸氫鈉、及碳酸鈉之至少一種。再者,又更好為選自氨、氫氧化鉀、氫氧化鈉、氫氧化四甲胺及氫氧化四乙銨之至少一種,又更好為選自氨及氫氧化四甲銨之至少一種,最好為氨。
本實施形態之研磨用組成物中之鹼性化合物含量可為0.0001質量%以上,較好為0.001質量%以上,更好為0.005質量%以上。鹼性化合物含量若為上述範圍內,則提高利用研磨用組成物之研磨對象物之研磨速度。
另一方面,研磨用組成物中之鹼性化合物含量可為1.0質量%以下,較好為0.5質量%以下,更好為0.1質量%以下,又更好為0.05質量%以下,再更好為0.02質量%以下。鹼性化合物含量若為上述範圍內,則可抑制研磨對象物之過度研磨,提高被研磨面之平滑性。
本實施形態之研磨用組成物之pH並未特別限定,但可為9.0以上11.5以下,較好9.5以上11.0以下,更好為9.8以上10.5以下。pH若為上述範圍內,則易獲得適當之研磨速度。研磨用組成物之pH可藉由添加例如後述之pH調整劑而調整。
本實施形態之研磨用組成物中,為了提高其性能,亦可根據需要添加pH調整劑、界面活性劑、螯合劑、防黴劑等之各種添加劑。惟,較好實質上不含氧化劑。
本實施形態之研磨用組成物之pH值可藉由添加pH調整劑而調整。藉由調整研磨用組成物之pH,可控制研磨對象物之研磨速度或研磨粒之分散性等。pH調整劑之添加量並未特別限定,只要適當調整為研磨用組成物所期望之pH即可。
作為pH調整劑之具體例舉例為無機酸或羧酸、有機硫酸等之有機酸。作為無機酸之具體例舉例為鹽酸、硫酸、硝酸、氫氟酸、硼酸、碳酸、次磷酸、亞磷酸、磷酸等。且羧酸之具體例舉例為甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、正庚酸、2-甲基己酸、正辛酸、2-乙基己酸、苯甲酸、乙醇酸、水楊酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、鄰苯二甲酸、蘋果酸、酒石酸、檸檬酸、乳酸、二乙醇酸、2-呋喃羧酸、2,5-呋喃二羧酸、3-呋喃羧酸、2-四氫呋喃羧酸、甲氧基乙酸、甲氧基苯基乙酸、苯氧基乙酸等。再者,有機硫酸之具體例舉例為甲烷磺酸、乙烷磺酸、羥乙磺酸等。該等酸可單獨使用1種,亦可組合2種以上使用。
本實施形態之研磨用組成物中亦可添加界面活性劑。界面活性劑之例舉例為陰離子性或非離子性界面活性劑,其中較好為非離子性界面活性劑。
作為非離子性界面活性劑之具體例舉例為氧伸烷基之均聚物、複數種類之氧伸烷基之共聚物、聚氧伸烷基加成物。該等非離子性界面活性劑中,較好為複數種類之氧伸烷基之共聚物或聚氧伸烷基加成物。
本實施形態之研磨用組成物中亦可添加螯合劑。螯合劑藉由捕捉研磨系中之金屬雜質成分而形成錯合物,藉此抑制矽基板之金屬汙染(尤其是受到鎳、銅之汙染)。
螯合劑之具體例舉例為葡萄糖酸等之羧酸系螯合劑、乙二胺、二伸乙三胺、三甲基四胺等之胺系螯合劑、乙二胺四乙酸、氮基三乙酸、羥基乙基乙二胺三乙酸、三伸乙四胺六乙酸、二伸乙三胺五乙酸等之聚胺聚羧酸系螯合劑、2-胺基乙基磺酸、1-羥基亞乙基-1,1-二磺酸、胺基三(亞甲基磺酸)、乙二胺四(亞甲基磺酸)、二伸乙三胺五(亞甲基磺酸)、乙烷-1,1-二磺酸、乙烷-1,1,2-三磺酸、甲烷羥基磺酸、1-磺基丁烷-2,3,4-三碳酸等之有機磺酸系螯合劑、酚衍生物、1,3-二酮等。該等螯合劑中,較好為有機磺酸系螯合劑,尤其是乙二胺四(亞甲基磺酸)。該等螯合劑可單獨使用1種,亦可組合2種以上使用。
本實施形態之研磨用組成物中亦可添加防黴劑。防黴劑之具體例舉例為噁唑啶-2,5-二酮等之噁唑啉等。
本實施形態之研磨用組成物較好實質上不含氧化劑。其理由為若研磨用組成物中含氧化劑,則因將該研磨用組
成物供給於研磨對象物(例如矽晶圓)而使該研磨對象物表面氧化生成氧化膜,藉此使所需研磨時間變長。此處所稱之氧化劑具體例舉例為過氧化氫(H2O2)、過硫酸鈉、過硫酸銨、過錳酸鉀、二氯異氰尿酸鈉等。
又所謂研磨用組成物實質上不含氧化劑係指至少不刻意含有氧化劑。因此,不可避免地含有源自原料或製法等之微量(例如研磨用組成物中之氧化劑莫耳濃度為0.0005莫耳/L以下,較好0.0001莫耳/L以下,更好0.00001莫耳/L以下,特佳為0.000001莫耳/L以下)之氧化劑之研磨用組成物可包含於此處所謂之實質上不含氧化劑之研磨用組成物之概念。
本實施形態之研磨用組成物亦可含有水。水係作為用以分散或溶解研磨用組成物中之各成分(研磨粒、水溶性高分子、鹼性化合物、添加劑等)之分散介質或溶劑之功能。為了極力避免阻礙研磨用組成物中所含之各成分之作用,較好使用例如過渡金屬離子合計含量為100ppb以下之水。藉由例如使用離子交換樹脂去除雜質離子、藉由過濾器去除粒子、藉由蒸餾等操作,可提高水之純度。具體而言較好使用離子交換水、純水、超純水、蒸餾水等。
本實施形態之研磨用組成物之製造方法並未特別限
定,可藉由將研磨粒、水溶性高分子及依期望之鹼性化合物等之各種添加劑於水中攪拌、混合而製造。混合時之溫度並未特別限制,較好為10℃以上40℃以下,亦可加熱以提高溶解速度。且混合時間亦未特別限制。
本實施形態之研磨用組成物之用途並未特別限定,可使用於研磨對象物之預研磨(一次研磨、二次研磨)、或使預研磨後之研磨對象物表面進行鏡面精加工之精加工研磨等,但尤其較好使用於矽基板之精加工研磨。
又,使用本實施形態之研磨用組成物之研磨對象物之研磨可藉由通常之研磨所用之研磨裝置或研磨條件進行。例如可使用單面研磨裝置或雙面研磨裝置。
例如將研磨對象物設為矽基板,使用單面研磨裝置進行研磨時,可使用稱為載具之保持具保持矽基板,將矽基板單面壓抵於貼附研磨布之壓盤,邊供給研磨用組成物邊使壓盤旋轉,藉此研磨矽基板單面。
且使用雙面研磨裝置研磨矽基板時,可使用稱為載具之保持具保持矽基板,自矽基板兩側將貼附研磨布之壓盤分別壓抵於矽基板兩面,邊供給研磨用組成物邊使兩側壓盤旋轉,藉此研磨矽基板兩面。
使用任一研磨裝置時,亦可藉由摩擦(研磨布及研磨用組成物與矽基板之摩擦)之物理作用與研磨用組成物施加於矽基板之化學作用而研磨矽基板。
作為研磨布,可使用聚胺基甲酸酯、不織布、麂皮等之各種材料者。且可使用材料不同、以及硬度或厚度等之物性種種不同者。再者,可使用含研磨粒者、不含研磨粒者之任一者,但較好使用不含研磨粒者。再者可使用施以可積存液狀研磨用組成物之槽加工者。
再者,研磨條件中之研磨荷重(對研磨對象物負荷之壓力)並未特別限定,但可為5kPa以上50kPa以下,較好8kPa以上30kPa以下,更好10kPa以上20kPa以下。研磨荷重若為該範圍內,則可發揮充分之研磨速度,可抑制因荷重而使研磨對象物破損、於研磨對象物表面發生傷痕等缺陷。
且,研磨條件中,研磨所用之研磨布與矽基板等之研磨對象物之相對速度(線速度)並未特別限定,但可為10m/分以上300m/分以下,較好為30m/分以上200m/分以下。研磨布與研磨對象物之相對速度若在該範圍內,則獲得充分之研磨速度。且可抑制因研磨對象物之摩擦所致之研磨布破損,進而可對研磨對象物充分傳遞摩擦,抑制所謂之研磨對象物滑動狀態,可充分研磨。
再者,關於研磨條件中之研磨用組成物之供給量,係隨研磨對象物種類、研磨裝置種類、研磨條件而異,但只要於研磨對象物與研磨布之間可無不均而全面供給研磨用組成物之充分量即可。研磨用組成物之供給量少時,則有無法對研磨對象物全體供給研磨用組成物,或研磨用組成物乾燥凝固而於研磨對象物表面產生缺陷之情
況。相反地研磨用組成物供給量較多時,除了不經濟以外,亦有因過量研磨用組成物(尤其是水)而妨礙摩擦而阻礙研磨之虞。
再者,本實施形態之研磨用組成物可於研磨對象物之研磨中使用後回收並再使用於研磨對象物之研磨。作為再使用研磨用組成物之方法之一例,舉例為將自研磨裝置排出之研磨用組成物回收於槽中,朝再度研磨裝置內循環而使用於研磨之方法。若循環使用研磨用組成物,由於可減低作為廢液而排出之研磨用組成物之量,故可減低環境負荷。又,由於可減少使用之研磨用組成物之量,故可抑制研磨對象物之研磨所需之製造成本。
再使用本實施形態之研磨用組成物時,只要添加因使用於研磨而消耗、損失之研磨粒、水溶性高分子、鹼性化合物、添加劑等之一部分或全部作為組成物調整劑而再使用即可。作為組成調整劑,可使用以任意混合比例混合研磨粒、水溶性高分子、鹼性化合物、添加劑等而得者。藉由追加添加組成調整劑,於再使用研磨用組成物時可調整為較佳組成,可進行較佳研磨。組成調整劑中含有之研磨粒、水溶性高分子、鹼性化合物及其他添加劑之濃度為任意,並未特別限定,只要根據槽大小或研磨條件適當調整即可。
又,本實施形態係例示本發明之一例者,本發明不限定於本實施形態。且,可對本實施形態加以各種變更或改良,該種加以變更或改良之形態亦可包含於本發
明。例如本實施形態之研磨用組成物可為一液型,亦可為將研磨用組成物之成分之一部分或全部以任意比例混合之二液型等之多液型。且,研磨對象物之研磨中,本實施形態之研磨用組成物之原液可直接使用而進行研磨,但亦可以水等稀釋液將原液稀釋例如10倍以上並使用研磨用組成物之稀釋物進行研磨。
以下顯示實施例,邊參考表1、2更具體說明本發明。
將由平均一次粒徑為25nm或35nm之氧化矽所成之研磨粒、水溶性高分子、鹼性化合物之氨與超純水以成為表1、2中記載之濃度之方式混合,製造實施例1~10及比較例1~11之研磨用組成物(漿料)。
所使用之水溶性高分子種類及重量平均分子量如表1、2所示。又,表1、2中記載之「PVA-PVP」意指聚乙烯醇-聚乙烯吡咯啶酮無規共聚物。以下同樣分別為「HEC」意指羥乙基纖維素,「PVA-PEO」意指聚乙烯醇聚環氧乙烷接枝共聚物,「PACMO」意指聚丙烯醯基嗎啉,「PAA」意指聚丙烯酸,「PNVA」意指聚N-乙烯基乙醯胺,「PVI」意指聚乙烯咪唑,「PVP」意指聚乙烯吡咯啶酮,「PVA」意指聚乙烯醇。
又,實施例1~10及比較例1~11之研磨用組成物中使用之水溶性高分子之pH為10.0時之對氧化矽之
吸附率及pH為10.4時之對氧化矽之吸附率分別如表1、2所記載。
又,吸附率之測定方法係如下。首先,針對pH為10.0時之水溶性高分子對氧化矽之吸附率之測定方法加以說明。
(1)調製平均一次粒徑35nm之氧化矽濃度為9.6質量%、水溶性高分子濃度為0.25質量%、氨濃度為0.08質量%、其餘部分為離子交換水之第一標準液原液。接著以離子交換水將第一標準液原液稀釋至體積比20倍,藉此調製pH10.0之第一標準液。又,水溶性高分子之水溶液為酸性時(例如聚丙烯酸)於與氧化矽、氨混合作成第一標準液原液之前,將水溶性高分子之水溶液之pH以氨調整至7.0,隨後與氧化矽、氨混合作成第一標準液原液。
(2)測定第一標準液之總有機體碳濃度(TOC值),將所得第一標準液之TOC值設為第一標準液中所含之水溶性高分子之總碳濃度(I)。TOC值之測定可使用例如島津製作所股份有限公司製之總有機體碳計TOC-5000A。
(3)其次,對於第一標準液以旋轉速度20000rpm進行30分鐘離心分離處理,藉此分離為含氧化矽之沉降物與不含氧化矽之上澄液後,使用例如島津製作所股份有限公司製之總有機體碳計TOC-5000A,測定上澄液之TOC值。接著,自第一標準液之TOC值減去上澄液
之TOC值,而算出吸附於氧化矽之水溶性高分子之碳濃度(II)。進而,藉由(II)/(I)×100算出第一標準液中吸附於氧化矽之水溶性高分子之碳濃度(II)相對於所含之水溶性高分子之總碳濃度(I)之比率(百分率),所得數值設為pH為10.0時之水溶性高分子對於氧化矽之吸附率。
其次,針對pH為10.4時之水溶性高分子對於氧化矽之吸附率之測定方法加以說明。
(1)調製平均一次粒徑35nm之氧化矽濃度為9.6質量%、水溶性高分子濃度為0.25質量%、氨濃度為0.5質量%、其餘部分為離子交換水之第二標準液原液。接著以離子交換水將第二標準液原液稀釋至體積比20倍,藉此調製pH10.4之第二標準液。又,水溶性高分子之水溶液為酸性時(例如聚丙烯酸)於與氧化矽、氨混合作成第二標準液原液之前,將水溶性高分子之水溶液之pH以氨調整至7.0,隨後與氧化矽、氨混合作成第二標準液原液。
(2)測定第二標準液之總有機體碳濃度(TOC值),將所得第二標準液之TOC值設為第二標準液中所含之水溶性高分子之總碳濃度(III)。TOC值之測定可使用例如島津製作所股份有限公司製之總有機體碳計TOC-5000A。
(3)其次,對於第二標準液以旋轉速度20000rpm進行30分鐘離心分離處理,藉此分離為含氧化
矽之沉降物與不含氧化矽之上澄液後,使用例如島津製作所股份有限公司製之總有機體碳計TOC-5000A,測定上澄液之TOC值。接著,自第二標準液之TOC值減去上澄液之TOC值,而算出吸附於氧化矽之水溶性高分子之碳濃度(IV)。進而,藉由(IV)/(III)×100算出第二標準液中吸附於氧化矽之水溶性高分子之碳濃度(IV)相對於所含之水溶性高分子之總碳濃度(III)之比率(百分率),所得數值設為pH為10.4時之水溶性高分子對於氧化矽之吸附率。
其次,使用實施例1~10及比較例1~11之研磨用組成物,以下述研磨條件進行矽晶圓之研磨。該矽晶圓直徑為300mm。且傳導型為P型,結晶方位為<100>,電阻率為0.1Ω.cm以上且未達100Ω.cm。
研磨裝置:岡本工作機械製作所股份有限公司製之研磨裝置,型號「PNX332B」
研磨墊(研磨布):富士紡愛媛股份有限公司製「POLYPAS27NX」
研磨荷重:15kPa
壓盤旋轉速度:30min-1
壓頭(載具)旋轉速度:30min-1
研磨時間:120秒
研磨用組成物之供給速度:2L/min(源源流出使用)
研磨用組成物之溫度:20℃
接著,將研磨後之矽晶圓於洗淨液中浸漬6分鐘洗淨(SC-1洗淨)後,以浸漬於去離子水之狀態使用超音波振盪器進行超音坡處理。接著,使用2-丙醇去除水分予以乾燥。又,洗淨液係使濃度29質量%之氨水、濃度31質量%之過氧化氫水溶液、去離子水以體積比1:3:30混合而成之混合液。
針對完成研磨、洗淨及乾燥之矽晶圓,使用GLI TENCOL公司製之晶圓檢查裝置Surfscan SP2(商品
名),測定濁度及缺陷數。缺陷數係存在於矽晶圓表面之61nm以上大小之缺陷(LPD-N)之個數。測定結果分別示於表1、2。
又,表1、2中之濁度及缺陷數之數值係以將比較例2之濁度及缺陷數設為100時之相對值。又,表1、2中所謂「無法研磨」意指因研磨時矽晶圓與研磨墊之摩擦大而使研磨裝置振動,故無法研磨。且所謂「無法測定」意指LPD-N過大而使測定結果變為溢流。
如由表1、2所了解,實施例1~10之研磨用組成物由於使用pH10.0時對氧化矽之吸附率為10%以上且pH10.4時對氧化矽之吸附率為65%以下之水溶性高分子,故矽晶圓為低濁度且LPD-N少。
Claims (5)
- 一種研磨用組成物,其係含有研磨粒及水溶性高分子之研磨用組成物,且前述水溶性高分子係滿足下述2個條件(A)及(B)者,並且前述水溶性高分子係(1)重量平均分子量為325000以上200萬以下之具有含醯胺基之雜環構造的水溶性高分子、(2)纖維素衍生物、(3)構造之一部分含有聚乙烯吡咯啶酮之共聚物,且為具有選自二嵌段型、三嵌段型、無規型及交替型之至少一種構造之聚合物、(4)具有聚氧伸烷基構造之聚合物的任一者,條件(A):由平均一次粒徑35nm之氧化矽、前述水溶性高分子、氨及水所成之前述氧化矽濃度為0.48質量%,前述水溶性高分子之濃度為0.0125質量%,pH為10.0之第一標準液中,前述第一標準液中含有之吸附於前述氧化矽之前述水溶性高分子之量相對於前述水溶性高分子總量之比例的吸附率為10%以上;條件(B):由平均一次粒徑35nm之氧化矽、前述水溶性高分子、氨及水所成之前述氧化矽濃度為0.48質量%,前述水溶性高分子之濃度為0.0125質量%,pH為10.4之第二標準液中,前述第二標準液中含有之吸附於前述氧化矽之前述水溶性高分子之量相對於前述水溶性高分子總量之比例的吸附率為65%以下。
- 如請求項1之研磨用組成物,其中前述水溶性高分子係連鎖聚合物、逐次聚合物或活性聚合物。
- 如請求項1或2之研磨用組成物,其中進而含有鹼 性化合物。
- 如請求項1或2之研磨用組成物,其係矽之研磨用。
- 一種矽基板之研磨方法,包含使用如請求項1~4中任一項之研磨用組成物研磨矽基板。
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