TWI525164B - 用於包含氧化矽介電質及多矽膜之化學機械研磨基材之水性研磨組成物及方法 - Google Patents
用於包含氧化矽介電質及多矽膜之化學機械研磨基材之水性研磨組成物及方法 Download PDFInfo
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- TWI525164B TWI525164B TW100132009A TW100132009A TWI525164B TW I525164 B TWI525164 B TW I525164B TW 100132009 A TW100132009 A TW 100132009A TW 100132009 A TW100132009 A TW 100132009A TW I525164 B TWI525164 B TW I525164B
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- acid
- oxide
- aqueous
- optical
- abrasive composition
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- GECHUMIMRBOMGK-UHFFFAOYSA-N sulfapyridine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=CC=CC=N1 GECHUMIMRBOMGK-UHFFFAOYSA-N 0.000 description 1
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- 150000003536 tetrazoles Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229960004319 trichloroacetic acid 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
- 238000009966 trimming Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
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- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
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Classifications
-
- 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
- C09K13/00—Etching, surface-brightening or pickling compositions
-
- 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
- C09G1/06—Other polishing compositions
- C09G1/14—Other polishing compositions based on non-waxy substances
- C09G1/18—Other polishing compositions based on non-waxy substances on other substances
-
- 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
- H01L21/31—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
-
- 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
- H01L21/31—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
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本發明係針對新穎的水性研磨組成物,其尤其適用於研磨含有氧化矽介電質及多晶矽膜(可視情況含有氮化矽膜)之半導體基材。
此外,本發明係針對用於研磨用於製造電子、機械及光學裝置之基材之新穎方法,該基材材料包含氧化矽及多晶矽膜,視情況包含氮化矽膜。
引用文獻
本發明所引用之文件以整體引用方式併入。
化學機械平坦化或研磨(CMP)為達成積體電路(IC)裝置局部及全面平坦度之主要方法。該技術典型地應用含有磨料及其他添加劑之CMP組成物或漿料作為旋轉之基材表面與所施加負載下之研磨墊之間的活性化學劑。因此,CMP方法聯合諸如磨耗之物理方法及諸如氧化或螯合之化學方法。僅包含物理作用或僅包含化學作用對移除或研磨基材材料而言並非所欲,而為達成快速均勻的移除,兩者之協同組合較為理想。
以此種方式移除基材材料直至獲得所需平坦度,或直至障壁子層(barrier sublayer)或停止層(stopping layer)暴露。最終,獲得平坦的無缺陷表面,其使得能夠由後續光刻、圖案化、蝕刻及薄膜加工進行適合之多層IC裝置製造。
淺溝槽隔離(Shallow trench isolation,STI)為特定CMP應用,其一般需要在圖案化晶圓基材上對氮化矽選擇性移除二氧化矽。在此情況下,用例如二氧化矽之介電質材料過量裝填經蝕刻之溝槽,研磨該介電質材料並以氮化矽障壁膜作為停止層。在自障壁膜清除二氧化矽同時使暴露之氮化矽及溝槽氧化矽之移除減至最少的情況下結束CMP方法。
此舉需要CMP漿料能夠達到二氧化矽材料移除率MRR對氮化矽移除率MRR之高相對比率,該比率在該項技藝中亦稱為氧化物對氮化物之選擇性(oxide-to-nitride selectivity)。
近來,多晶矽薄膜亦用作為障壁膜或電極材料(參考美國專利US 6,626,968 B2)。因此,讓包含氧化矽介電質材料及多晶膜之基材的全面平坦化之CMP漿料及方法成為高度所需者。此需要展現高氧化物對氮化物之選擇性之CMP漿料。
甚至更需要的是可使另外含有氮化矽薄膜之基材全面平坦化之CMP漿料及方法。
在此情況下,為避免含有氧化矽、氮化矽及多晶矽區域之經全面平坦化、異質、經圖案化之表面中之碟型凹陷(dishing)及其他破壞及缺陷,其氧化物對氮化物之選擇性不應太高。然而,其氮化矽對多晶矽之選擇性亦應該是高的。
在STI應用中,基於氧化鈰之CMP漿料已因其能夠獲得較高的氧化物對氮化物之選擇性而頗受關注,而該高氧化物對氮化物之選擇性係歸因於氧化鈰對二氧化矽之高化學親和力,此在該項技藝中亦稱為氧化鈰之化學牙齒作用(tooth action)。
儘管如此,必須藉由「修改」該選擇性之添加劑以改良基於氧化鈰之CMP漿料的氧化物對多晶矽之選擇性。
已多次嘗試修改基於氧化鈰之CMP漿料的選擇性。
因此,Jae-Don Lee等人在Journal of the Electrochemical Society,149(8),G477-G481,2002中揭示:具有不同親水-親脂平衡(HLB)值之非離子界面活性劑,諸如聚氧化乙烯、氧化乙烯-氧化丙烯共聚物及氧化乙烯-氧化丙烯-氧化乙烯三嵌段共聚物對CMP期間氧化物對多晶矽之選擇性之影響。然而,使用煙霧狀二氧化矽作為磨料。
P.W.Carter等人在Electrochemical and Solid-State Letters,8(8) G218-G221(2005)之氧化鈰與二氧化矽與氮化矽表面之介面反應性,有機添加反應(Interfacial Reactivity between Ceria and Silicon Dioxide and Silicon Nitride Surfaces,Organic Additive Effects)中揭示麩胺酸、吡啶羧酸、4-烴苯甲酸、咪唑、乙酸、甲酸、3-烴基吡啶羧酸、鄰胺苯甲酸、吡咯羧酸、環己烷羧酸、哌、吡啶、2-苯乙酸、苯甲酸、3-胺苯酚、琥珀酸、甜菜鹼、甘胺酸、脯胺酸、苯磺酸、嗎啉、柳酸、對苯二甲酸、蘋果酸、異丙醇、檸檬酸及草酸對於氧化物對氮化物之選擇性之影響。
Y. N. Prasad等人在Electrochemical and Solid-State Letters,9(12) G337-G339(2006)中之在STI CMP過程中二氧化矽及氮化矽表面之胺-酸吸收的角色(Role of Amino-Acid Absorption on Silica and Silicon Nitride Surfaces during STI CMP)中揭示脯胺酸及精胺酸之影響。
Hyun-Goo Kang等人在Journal of Material Research,卷22,No. 3,2007,第777至787頁揭示在淺溝槽隔離化學機械平坦化中,氧化鈰漿料中之聚丙烯酸之磨料粒度及分子量對SiO2/Si3N4膜移除選擇性之影響。
S. Kim等人在Journal of Colloid and Interface Science,319(2008)第48至52頁中揭示用於化學機械研磨(CMP)之陰離子高分子電解質(polyelectrolyte)之吸收作用。
S. V. Babu等人在Electrochemical and Solid-State Letters,7(12) G327-G330(2004)之在CMP過程中漿料添加劑對於抑制氮化矽移除之影響(Slurry Additive Effects on the Suppression of Silicon Nitride Removal during CMP)中探討精胺酸、離胺酸、脯胺酸、N-甲基甘胺酸、丙胺酸、甘胺酸、吡啶羧酸、N,N-二甲基甘胺酸、3-丁胺酸及異菸鹼酸之影響。
Jae-Dong Lee等人在Journal of the Electrochemical Society,149(8),G477-G481,2002中之化學機械研磨期間,非離子界面活性劑對氧化物對多晶矽之選擇性的影響(Effects of Nonionic Surfactants on Oxide-To-Polysilicon Selectivity during Chemical Mechanical Polishing)揭示:諸如聚氧化乙烯(PEO)及氧化乙烯-氧化丙烯-氧化乙烯三嵌段共聚物之界面活性劑對選擇性的影響。然而,氧化物對氮化物之選擇性並未解決。
美國專利US 5,738,800、US 6,042,741、US 6,132,637及US 6,218,305B揭示一種基於氧化鈰之CMP漿料,其含有諸如蘋果酸、酒石酸、葡萄糖酸、檸檬酸、對二烴苯甲酸及聚烴苯甲酸、鄰苯二甲酸、兒茶酚、焦五倍子酚、五倍子酸、單寧酸及其鹽類之錯合劑。此外,基於氧化鈰之CMP漿料含有陰離子、陽離子、兩性或非離子性界面活性劑。其主張該基於氧化鈰之CMP漿料具有高氧化物對氮化物之選擇性。
美國專利US 5,759,917、US 6,689,692 B1及US 6,984,588 B2揭示一種基於氧化鈰之CMP漿料,其包含羧酸(諸如乙酸、己二酸、丁酸、癸酸、己酸、辛酸、檸檬酸、戊二酸、乙醇酸、甲酸、反丁烯二酸、乳酸、月桂酸、蘋果酸、順丁烯二酸、丙二酸、肉豆蔻酸、草酸、棕櫚酸、鄰苯二甲酸、丙酸、丙酮酸、硬脂酸、琥珀酸、酒石酸、戊酸、2-(2-甲氧乙氧)乙酸、2-[2-(2-甲氧乙氧)乙氧]乙酸、聚(乙二醇)二(羧甲基)醚及其衍生物及鹽類)。此外,該基於氧化鈰之CMP漿料包含水溶性有機及無機鹽類,諸如硝酸鹽、磷酸鹽及硫酸鹽。其主張該基於氧化鈰之CMP漿料優於氮化矽層地研磨氧化矽過填物。
美國專利US 6,299,659B1揭示一種基於氧化鈰之CMP漿料,其中以矽烷、鈦酸鹽、鋯酸鹽、鋁及磷酸鹽耦合劑處理磨料顆粒以改善氧化物對氮化物之選擇性。
美國專利申請案US 2002/0034875 A1及美國專利US 6,626,968 B2揭示一種基於氧化鈰之CMP漿料,其含有界面活性劑;pH調節劑,諸如氫氧化鉀、硫酸、硝酸、鹽酸或磷酸;及含有親水性官能基及疏水性官能基之聚合物,諸如聚乙烯甲醚(PVME)、聚乙二醇(PEG)、聚氧化乙烯23月桂醚(POLE)、聚丙酸(PPA)、聚丙烯酸(PM)及聚乙二醇二甲醚(PEGBE)。該基於氧化鈰之CMP漿料增加氧化物對多晶矽之選擇性。
美國專利US6,436,835B1揭示一種用於淺溝槽隔離製程之基於氧化鈰之CMP漿料,其包含具有羧酸或羧酸鹽或磺酸或磺氨基團之水溶性有機化合物,諸如聚丙烯酸、聚甲基丙烯酸、萘磺酸-福馬林縮合物、蘋果酸、乳酸、酒石酸、葡萄糖酸、檸檬酸、琥珀酸、己二酸、反丁烯二酸、天門冬胺酸,麩胺酸、甘胺酸4-丁胺酸、6-胺己酸、12-胺月桂酸、精胺酸、甘胺醯基甘胺酸、月桂苯磺酸及其鹽類。其主張該基於氧化鈰之CMP漿料具有高氧化物對氮化物之選擇性。
美國專利US 6,491,843 B1、US 6,544,892 B2以及US 6,627,107 B2揭示一種改善氧化物對氮化物之選擇性之基於氧化鈰之CMP漿料,其含有諸如離胺酸、丙胺酸及脯胺酸之α-胺酸。
美國專利US 6,616,514 B1揭示一種改善氧化物對氮化物之選擇性之基於氧化鈰之CMP漿料,其含有具有至少3個在水性介質中不易解離的羥基之有機多元醇;或由至少一種具有至少3個在水性介質中不易解離的羥基之單體所形成之聚合物,諸如甘露醇、山梨糖醇、甘露糖、木糖醇、山梨糖、蔗糖及糊精。
美國專利US 7,071,105 B2及美國申請案US 2006/0144824A1揭示一種含有研磨添加物之基於氧化鈰之CMP漿料,該研磨添加物包含具有pKa為4至9之官能基。該研磨添加物係選自由下列組合之群組:芳基胺、胺醇、脂族胺、雜環胺、羥胺酸、胺羧酸、環單羧酸、不飽和單羧酸、經取代之苯酚、磺醯胺、硫醇及其鹽類,尤其是氯化物、溴化物、硫酸鹽、磺酸鹽、三氟甲基磺酸鹽、乙酸鹽、三氟乙酸鹽、苦味酸鹽、全氟丁酸鹽以及鈉、鉀、銨鹽類。
特別提及,該芳基胺為苯胺、4-氯苯胺、3-甲氧苯胺、N-甲基苯胺、4-甲氧苯胺、對甲苯胺、鄰胺苯甲酸、3-胺-4-羥基苯磺酸、胺苯甲基醇、胺苯甲基胺、1-(-胺苯)吡咯、1-(3-胺苯)乙醇、2-胺苯醚、2,5-雙-(4-胺苯)-1,3,4-二唑、2-(2-胺苯)-1H-1,3,4-三唑、2-胺苯、3-胺苯、4-胺苯、二甲基胺苯酚、2-胺苯硫醇(2-aminothiolphenol)、3-胺苯硫醇、4-胺苯甲硫醚(4-aminophenyl methyl sulfide)、2-胺苯磺醯胺、鄰胺苯磺酸、3-胺苯硼酸、5-胺異鄰苯二甲酸、乙醯磺胺、磺胺酸、鄰胺苯胂酸或對胺苯胂酸及(3R)-3-(4-三氟甲基苯胺)戊酸。
特別提及,該胺醇為三乙醇胺、苯甲基二乙醇胺、三(羥甲基)胺甲烷、羥胺及四環素。
特別提及,該脂族胺為甲氧基胺、羥胺、N-甲基羥胺、N,O-二甲基羥胺、β-二氟乙基胺、乙二胺、三伸乙二胺(triethylenediamine)、((丁基胺)(2-羥基苯)甲基)磷酸二乙酯、亞胺乙烷、亞胺丁烷、三烯丙胺、諸如胺乙腈之氰胺、二甲基胺乙腈、2-胺基-2-氰丙烷、異丙基胺丙腈、二乙基胺丙腈、胺丙腈、二氰二乙基胺、肼、甲基肼、四甲基肼、N,N-二甲基肼、苯肼、N,N-二乙基肼、三甲基肼、乙基肼及其鹽類。
特別提及,該雜環胺為咪唑、1-甲基咪唑、2-甲基咪唑、2-乙基咪唑、2-羥甲基咪唑、1-甲基-2-羥甲基咪唑、苯并咪唑、喹啉、異喹啉、羥基喹啉、三聚氰胺、吡啶、二吡啶、2-甲基吡啶、4-甲基吡啶、2-胺吡啶、3-胺吡啶、2,3-吡啶二羧酸、2,5-吡啶二羧酸、2,6-吡啶二羧酸、5-丁基-2-吡啶羧酸、2-吡啶羧酸、3-羥基-2-吡啶羧酸、4-羥基-2-吡啶羧酸、3-苯甲醯基-2-吡啶羧酸、6-甲基-2-吡啶羧酸、3-甲基-2-吡啶羧酸、6-溴基-2-吡啶羧酸、6-氯基-2-吡啶羧酸、3,6-二氯基-2-吡啶羧酸、4-肼基-3,5,6-三氯基-2-吡啶羧酸、2-喹啉羧酸、4-甲氧基-2-喹啉羧酸、8-羥基-2-喹啉羧酸、4,8-羥基-2-喹啉羧酸、7-氯基-4-羥基-2-喹啉羧酸、5,7-二氯基-4-羥基-2-喹啉羧酸、5-硝基-2-喹啉羧酸、1-異喹啉羧酸、3-異喹啉羧酸、吖啶、苯并喹啉、苯并吖啶、可尼丁、毒藜鹼、降菸鹼、三唑吡啶、吡哆醇、腦激胺、組織胺、苯二氮平、吖環丙烷、嗎啉、1,8-二吖雙環(5,4,0)十一烯-7DABCO、六亞甲四胺、哌、N-苯甲醯基哌、1-磺醯基哌、N-羧乙基哌、1,2,3-三唑、1,2,4-三唑、2-胺噻唑、吡咯、吡咯-2-羧酸、3-二氫吡咯-2-羧酸、乙基二氫吡咯、環己基二氫吡咯、二氫吡咯(tolylpyrroline)、四唑、5-環丙基四唑、5-羥基四唑、5-苯氧基四唑、5-苯四唑、氟尿嘧啶、甲基硫尿嘧啶、5,5-二苯尿囊素、5,5-二甲基-2,4-唑啶二酮、酞醯亞胺、琥珀醯亞胺、3,3-甲基苯戊二醯亞胺(3,3-methylphenylglutarimide)、3,3-二甲基琥珀醯亞胺、咪唑[2,3-b]噻唑(thioxazole)、羥基咪唑[2,3-a]異吲哚(hydroxyemidazo[2,3-a]isoindole)、5,5-甲基苯巴比妥酸、1,5,5-三甲基巴比妥酸、六巴比妥鹽、5,5-二甲基巴比妥酸、1,5-二甲基-5-苯巴比妥酸及其鹽類。
特別提及,該異羥肟酸(hydroxamic acids)為甲異羥肟酸、乙異羥肟酸、苯異羥肟酸、柳異羥肟酸、2-胺苯異羥肟酸、2-氯苯異羥肟酸、2-氟異羥肟酸、2-硝苯異羥肟酸、3-硝苯異羥肟酸、4-胺苯異羥肟酸、4-氯苯異羥肟酸、4-氟苯異羥肟酸、4-硝苯異羥肟酸及其鹽類。
特別提及,該胺羧酸為麩胺酸、β-羥基麩胺酸、天門冬胺酸、天門冬醯胺酸、氮絲胺酸、半胱胺酸、組胺酸、3-甲基組胺酸、胞嘧啶、7-胺頭孢烷酸(7-aminocephalosporanic acid)及肌肽。
特別提及,該環單羧酸為萘-2-羧酸、環己烷羧酸、環己乙酸、2-苯乳酸、4-烴苯甲酸、3-烴苯甲酸、2-吡啶羧酸、順-環己烷羧酸及反-環己烷羧酸、苯甲酸及其鹽類。
特別提及,該不飽和單羧酸為桂皮酸、丙烯酸、3-氯丙基-2-烯羧酸、巴豆酸、4-丁-2-烯羧酸、順-2-戊酸或反-2-戊酸、2-甲基-2-戊酸、2-己烯酸及3-乙基-2-己烯酸及其鹽類。
特別提及,該苯酚為硝苯酚、2,6-二鹵基-4-硝苯酚、2,6-二-C1-12-烷基-4-硝苯酚、2,4-二硝苯酚、3,4-二硝苯酚、2-C1-12-烷基-4,6-二硝苯酚、2-鹵基-4,6-二硝苯酚、二硝基-鄰-甲酚、苦味酸及其鹽類。
特別提及,該磺醯胺為N-氯磺醯胺、二氯苯醯胺磺胺米隆(dichlorophenamide mafenide)、尼美舒利(nimesulide)、磺胺甲噻唑、磺胺普羅林(sulfaperin)、乙醯磺胺、磺胺嘧啶、磺胺二甲(sulfadimethoxine)、磺胺二甲嘧啶、磺胺吡啶、磺胺喹啉(sulfaquinoxaline)及其鹽類。
特別提及,該硫醇為二硫化二氫、半胱胺、半胱胺醯基半胱胺酸、甲基半胱胺酸、硫酚、對-氯硫酚、鄰-胺苯硫醇、鄰-硫醇苯乙酸對-硝基苯硫酚、2-硫醇乙基磺酸鹽、N-二甲基半胱胺、二丙基半胱胺、二乙基半胱胺、硫醇乙基嗎啉、甲基硫乙醇酸鹽、硫醇乙基胺、N-三甲基半胱胺酸、麩胱甘肽、硫醇乙基哌啶、二乙基胺丙烷硫醇及其鹽類。
咸信該等研磨添加劑提高氧化物對氮化物之選擇性。
美國專利申請案US 2006/0124594 A1揭示一種基於氧化鈰之CMP漿料,其具有至少1.5 cP之黏度且包含增黏劑,該增黏劑包括諸如聚乙二醇(PEG)之非離子聚合物。據稱該基於氧化鈰之CMP漿料具有高氧化物對氮化物之選擇性及低晶圓內非均勻性WIWNU。
美國專利申請案US 2006/0207188 A1揭示一種基於氧化鈰之CMP漿料,其含有諸如聚丙烯酸或聚(甲基丙烯酸烷基酯)之聚合物與諸如丙烯醯胺、甲基丙烯醯胺、乙基-甲基丙烯醯胺、乙烯基吡啶或乙烯吡咯啶酮之單體的反應產物。咸信該等反應產物亦增加氧化物對氮化物之選擇性。
美國專利申請案US 2006/0216935 A1揭示一種基於氧化鈰之CMP漿料,其包含蛋白質、離胺酸及/或精胺酸,及吡咯啶酮化合物,諸如聚乙烯吡咯啶酮(PVP)、N-辛基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-羥乙基-2-吡咯啶酮、N-環己基-2-吡咯啶酮、N-丁基-2-吡咯啶酮、N-己基-2-吡咯啶酮、N-癸基-2-吡咯啶酮、N-十八烷基-2-吡咯啶酮及N-十六烷基-2-吡咯啶酮。基於氧化鈰之CMP漿料可另外含有分散劑,如聚丙烯酸、乙二醇及聚乙二醇。特定實例使用脯胺酸、聚乙烯吡咯啶酮或N-辛基-2-吡咯啶酮、PPO/PEO嵌段共聚物及戊二醛。咸信該基於氧化鈰之CMP漿料未侵略性地移除溝槽二氧化矽,因而允許超出端點之延伸性研磨而未實質上增加最小的梯級高度。
美國專利申請案US 2007/0077865 A1揭示一種基於氧化鈰之CMP漿料,其含有較佳來自由BASF銷售之PluronicTM家族的聚氧化乙烯/聚氧化丙烯共聚物。基於氧化鈰之CMP漿料可另外含有胺基醇,諸如2-二甲基胺基-2-甲基-1-丙醇(DMAMP)、2-胺基-2-乙基-1-丙醇(AMP)、2-(2-胺基乙基胺基)乙醇、2-(異丙基胺基)乙醇、2-(甲基胺基)乙醇、2-(二乙基胺基)乙醇、2-(2-二甲基胺基)乙氧基)乙醇、1,1'-[[3-(二甲基胺基)丙基]亞胺基]-雙-2-丙醇、2-(2-丁基胺基)乙醇、2-(第三丁基胺基)乙醇、2-(二異丙基胺基)乙醇及N-(3-胺基丙基)嗎啉。該基於氧化鈰之CMP漿料可另外含有四級銨化合物,如四甲基銨氫氧化物;成膜劑,諸如烷基胺、烷醇胺、羥胺、磷酸酯、月桂基硫酸鈉、脂肪酸、聚丙烯酸酯、聚甲基丙烯酸酯、聚乙烯基膦酸酯、聚蘋果酸酯、聚苯乙烯磺酸酯、聚乙烯硫酸酯、苯并三唑、三唑及苯并咪唑;及錯合劑,諸如乙醯丙酮、乙酸鹽、乙醇酸鹽、乳酸鹽、葡糖酸鹽、五倍子酸、乙二酸鹽、鄰苯二甲酸鹽、檸檬酸鹽、琥珀酸鹽、酒石酸鹽、蘋果酸鹽、乙二胺四乙酸、乙二醇、兒茶酚、焦五倍子酸、鞣酸、鏻鹽及膦酸。咸信該基於氧化鈰之CMP漿料提供氧化矽相對於多晶矽之良好選擇性及/或氮化矽相對於多晶矽之良好選擇性。
美國專利申請案US 2007/0175104 A1揭示一種基於氧化鈰之CMP漿料,其包含多晶矽研磨抑制劑,選自具有經任何選自由下列組成之群組之成員取代的N-單取代或N,N-二取代骨架之水溶性聚合物:丙烯醯胺、甲基丙烯醯胺及其α-取代衍生物;聚乙二醇;聚乙烯吡咯啶酮;烷氧基化之直鏈脂族醇及基於乙炔之二醇的氧化乙烯加合物。基於氧化鈰之CMP漿料可含有額外的水溶性聚合物,諸如多醣,如海藻酸、果膠酸、羧甲基纖維素、瓊脂、卡德蘭(curdlan)及普魯蘭(pullulan);聚羧酸,諸如聚天冬胺酸、聚麩胺酸、聚離胺酸、聚蘋果酸、聚甲基丙烯酸、聚醯亞胺酸、聚順丁烯二酸、聚衣康酸、聚反丁烯二酸、聚(對苯乙烯羧酸)、聚丙烯酸、聚丙烯醯胺、胺基聚丙烯醯胺、聚乙醛酸及其鹽;及乙烯基聚合物,諸如聚乙烯醇及聚丙烯醛。據稱該基於氧化鈰之CMP漿料具有高氧化矽對多晶矽之選擇性。
美國專利申請案US 2007/0191244 A1揭示一種基於氧化鈰之CMP漿料,其含有具有30至500之重量平均分子量且含有羥基及羧基或兩者之化合物,諸如檸檬酸鹽、蘋果酸鹽、葡糖酸鹽、酒石酸鹽、2-羥基異丁酸鹽、己二酸鹽、辛酸鹽、琥珀酸鹽、含EDTA之化合物、戊二酸鹽、亞甲基琥珀酸鹽、甘露糖、甘油-半乳-庚糖(glycerol-galacto-heptose)、赤-甘露-辛糖(erythro-manno-octose)、阿拉伯-半乳-壬糖(arabino-galacto-nonose)及麩胺醯胺。該基於氧化鈰之CMP漿料可另外含有線性聚合物酸或具有烷氧基聚伸烷二醇側鏈之接枝型聚合物酸。據稱該基於氧化鈰之CMP漿料達到改良之研磨晶圓之全面平坦度。
美國專利申請案US2007/0218811A1揭示一種基於氧化鈰CMP漿料,其具有4至7.5之pH值且包含分散劑、聚羧酸及100至1000ppm之強酸,該強酸具有pKa值為3.2或小於3.2之第一可解離之酸基。由實例提及,丙烯酸及甲基丙烯酸之聚合物作為陰離子分散劑,聚氧乙烯衍生物作為非離子性分散劑,及聚乙烯四氫咯酮作為陽離子分散劑。明確提及,強酸為硫酸、HCl、硝酸、磷酸、草酸、順丁烯二酸、苦味酸、亞硫酸、硫亞硫酸(thiosulfurous acid)、醯胺基硫酸、氯酸、過氯酸、亞氯酸、氫碘酸、過碘酸、碘酸、氫溴酸、過溴酸、鉻酸、亞硝酸、二膦酸、三聚磷酸、次膦酸(phosphinic acid),吡啶羧酸、膦酸、異菸鹼酸、菸鹼酸、三氯基乙酸、二氯基乙酸、氯基乙酸、氰乙酸、草乙酸、硝基乙酸、溴基乙酸、氟基乙酸、苯氧基乙酸、鄰-溴基苯甲酸、鄰-硝基苯甲酸、鄰-氯基苯甲酸、對-胺苯甲酸、鄰胺苯甲酸、鄰苯二甲酸、反丁烯二酸、丙二酸、酒石酸、檸檬酸、鄰-氯基苯胺、2,2'-聯吡啶、4,4'-聯吡啶、2,6-吡啶二羧酸、丙酮酸、聚苯乙烯磺酸、聚磺酸、麩胺酸、柳酸、天門冬胺酸、2-胺乙基膦酸、離胺酸、精胺酸、異白胺酸、肉胺酸、鳥胺酸、鳥苷、瓜胺酸、酪胺酸、纈胺酸、次黃嘌呤、甲硫胺酸、離胺酸、及白胺酸。據稱該基於氧化鈰之CMP漿料促成有效率高速操作、較簡單製程管理及較小的膜厚度變動(因不同圖形密度所造成的)。
美國專利申請案US 2008/0085602 A1及US 2008/0124913 A1揭示一種基於氧化鈰之CMP漿料,其含有0.001重量%至0.1重量%之選自氧化乙烯-氧化丙烯-氧化乙烯三嵌段共聚物及聚丙烯酸之非離子界面活性劑作為分散劑。據稱該基於氧化鈰之漿料具有高氧化矽及氮化矽對多晶矽之選擇性。
電子裝置,尤其半導體積體電路(IC)之製造需要尤其涉及高選擇性CMP之高精度方法。
雖然先前技藝之基於氧化鈰之CMP漿料可具有令人滿意的氧化物對多晶矽、氧化物對氮化物及氮化物對多晶矽之選擇性且可得到具有良好的全面及局部平坦度之研磨的晶圓(如晶圓內非均勻性(WIWNU)及晶圓間非均勻性(WTWNU)所例示),但IC架構,尤其具有LSI(大規模積體)或VLSI(超大規模積體)之不斷減小之IC尺寸需要持續改良基於氧化鈰之CMP漿料,以便滿足積體電路裝置製造商日益增長之技術及經濟要求。
然而,此持續改良先前技藝之基於氧化鈰之CMP漿料的迫切需要不僅適用於積體電路裝置領域,而且亦需改良在製造下列裝置之領域中之研磨及平坦化功效,其他電子裝置:諸如液晶板、有機電場發光面板、印刷電路板、微型機器、DNA晶片、微型工廠、光伏打電池及磁頭;高精度機械裝置及光學裝置(尤其光學玻璃):諸如光罩、透鏡及稜鏡)、無機導電膜(諸如氧化銦錫(ITO)、光學積體電路、光學交換元件、光學波導、光學單晶(諸如光學纖維端面及閃爍體)、固體雷射單晶、用於藍色雷射LED之藍寶石基材、半導體單晶及用於磁碟之玻璃基材。該等電子及光學裝置之製造亦需要高精度CMP方法步驟。
歐洲專利申請案EP 1 338 636 A1揭示一種基於氧化鈰之CMP漿料,其包含抗凝固劑,其係選自由纖維素、結晶纖維素、纖維素衍生物、二氧化矽、海藻酸鹽、β-萘磺酸鹽福馬林縮合物、磷酸氫鈣、蛋白質、多肽及有機高分子絮凝劑組成之群組;及分散劑或界面活性劑,諸如縮合磷酸鹽,如焦磷酸、焦磷酸鈉、三磷酸鈉或六偏磷酸鈉。然而,其僅揭示玻璃之研磨。
日本專利申請案JP 2005-336400 A揭示一種基於氧化鈰之CMP漿料,其包含水溶性縮合磷酸鹽,諸如焦磷酸鹽、三聚磷酸鹽及六偏磷酸鹽;及水溶性碳酸鹽或碳酸氫鹽。該基於氧化鈰之CMP漿料可另外含有水溶性有機溶劑,諸如甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、乙二醇、丙二醇及1,2,3-丙三醇、酮(諸如丙酮及甲基乙基酮)、四氫呋喃、N,N-二甲基甲醯胺、二甲亞碸及1,4-二烷。據稱該基於氧化鈰之CMP漿料已在研磨準確性、清潔、初始研磨速度及研磨速度方面改良研磨。然而,其僅揭示玻璃之研磨。
日本專利申請案JP 2001-240850 A揭示一種CMP漿料,其含有氧化鋁、氧化鋯或碳化矽作為磨料;氧化烯-氧化乙烯嵌段或隨機共聚物作為分散劑且磷酸鈉或聚磷酸鈉作為「防銹劑」。該CMP漿料用於研磨矽晶圓、玻璃、鋁、陶瓷、合成二氧化矽、石英及藍寶石。
因此,本發明之一目的為提供一種新穎水性研磨組成物,詳言之,一種新穎化學機械研磨(CMP)組成物,特別是一種新穎的基於氧化鈰之CMP漿料,其不再展現先前技藝研磨組成物之缺陷及缺點。
詳言之,新穎水性研磨組成物,尤其是新穎化學機械
研磨(CMP)組成物,特別是新穎的基於二氧化鈰之CMP漿料應展現經顯著改良之氧化物對多晶矽之選擇性且得到具有如晶圓內非均勻性(WIWNU)及晶圓間非均勻性(WTWNU)所例示之卓越的全面及局部平坦度之經研磨的晶圓。因此,其應優異地適於製造具有尺寸小於50nm之結構的IC架構,尤其具有LSI(大規模積體)或VLSI(超大規模積體)之IC。
此外,新穎水性研磨組成物,詳言之新穎化學機械研磨(CMP)組成物且特別是新穎的基於氧化鈰之CMP漿料將不僅格外適用於積體電路裝置領域,而且將最有效且有利地適用於在製造下列裝置之領域中:其他電子裝置,諸如液晶板、有機電致發光板、印刷電路板、微型機器、DNA晶片、微型工廠及磁頭;以及高精度機械裝置及光學裝置,詳言之,光學玻璃(諸如光罩、透鏡及稜鏡)、無機導電膜(諸如氧化銦錫(ITO))、光學積體電路、光學交換元件、光學波導、光學單晶(諸如光學纖維端面及閃爍體)、固體雷射單晶、用於藍色雷射LED之藍寶石基材、半導體單晶及用於磁碟之玻璃基材。
最特別的是,該新穎之基於氧化鈰之CMP漿料應展現高氮化物對多晶矽之選擇性及適中之氧化物對氮化物之選擇性。
本發明之進一步目的為提供一種用於研磨機械、電子及光學裝置基材的新穎方法,該基材材料含有氧化矽介電質及多晶矽膜,可視情況地含有氮化矽膜。
發明摘要
因此,已發現新穎水性研磨組成物,該水性研磨組成物包含
(A)至少一種類型之磨料顆粒,當其分散於不含成分(C)且具有範圍介於3至9之pH值的水性介質中時帶正電,如電泳遷移率所證明;
(B)至少一種水溶性或水分散性聚合物,其係選自由線性及分枝氧化烯均聚物及共聚物所組成之群組;及
(C)至少一種陰離子磷酸鹽分散劑。
在下文中,該新穎水性研磨組成物稱為「本發明之組成物」。
此外,已發現用於研磨機械、電子及光學裝置基材的新穎方法,該方法係藉由使基材材料與本發明之組成物接觸至少一次且研磨該基材材料直至達成所需平坦度為止。
在下文中,用於研磨機械、電子及光學裝置基材材料的新穎方法稱為「本發明之方法」。
本發明之優點
鑒於先前技藝,令熟習該項技藝者驚訝且未能預期的是,本發明之目的可藉由本發明之組成物及本發明之方法來解決。
尤其令人驚訝的是,本發明之組成物展現顯著改良之氧化物對多晶矽之選擇性且得到具有如晶圓內非均勻性(WIWNU)及晶圓間非均勻性(WTWNU)所例示之卓越的全面及局部平坦度之經研磨的晶圓。因此,其優異地適於製造具有尺寸小於50 nm之結構的IC架構,尤其具有LSI(大規模積體)或VLSI(超大規模積體)之IC。
另外,本發明之組成物在長期運輸及儲存期間為穩定的,該穩定性顯著地改良其物流及方法管理。
此外,本發明之組成物不僅格外適用於積體電路裝置領域,而且最有效且有利地適用於在製造下列裝置之領域中:其他電子裝置,諸如液晶板、有機電致發光板、印刷電路板、微型機器、DNA晶片、微型工廠及磁頭;以及高精度機械裝置及光學裝置,特言之,光學玻璃(諸如光罩、透鏡及稜鏡)、無機導電膜(諸如氧化銦錫(ITO))、光學積體電路、光學交換元件、光學波導、光學單晶(諸如光學纖維端面及閃爍體)、固體雷射單晶、用於藍色雷射LED之藍寶石基材、半導體單晶及用於磁碟之玻璃基材。
最特別的是,本發明之組成物亦展現高氮化物對多晶矽之選擇性及適中之氧化物對氮化物之選擇性。
因此,本發明之組成物最尤其適用於本發明之方法。本發明之方法可最有利地用於研磨(詳言之化學機械研磨)電子裝置之基材材料,該等電子裝置諸如液晶板、有機電致發光板、印刷電路板、微型機器、DNA晶片、微型工廠及磁頭;以及高精度機械裝置及光學裝置之基材材料,尤其是光學玻璃(諸如光罩、透鏡及稜鏡)、無機導電膜(諸如氧化銦錫(ITO))、光學積體電路、光學交換元件、光學波導、光學單晶(諸如光學纖維端面及閃爍體)、固體雷射單晶、用於藍色雷射LED之藍寶石基材、半導體單晶及用於磁碟之玻璃基材。
然而,最尤其是,本發明之方法優異地適於研磨含有氧化矽介電質膜及多晶矽膜(可視情況地含有氮化矽膜)之半導體晶圓。本發明之方法得到具有如晶圓內非均勻性(WIWNU)及晶圓間非均勻性(WTWNU)所例示之無盤狀凹陷、杯狀凹陷或熱點(hotspot)之卓越的全面及局部平坦度及均衡性之經研磨的晶圓。因此,該等晶圓優異地適於製造具有尺寸小於50nm之結構的IC架構,尤其具有LSI(大規模積體)或VLSI(超大規模積體)之IC。
本發明之組成物為一種水性組成物。其意指該組成物含有水(尤其超純水)作為主溶劑及分散劑。儘管如此,本發明之組成物可含有至少一種可與水混溶的有機溶劑,但該有機溶劑之量為僅含有不改變本發明之組成物的水性性質之少量。
本發明之組成物較佳含有60重量%至99.95重量%、更佳70重量%至99.9重量%、甚至更佳80重量%至99.9重量%且最佳90重量%至99.9重量%之量的水,該等重量百分比以本發明之組成物的總重量計。
「水溶性」意指本發明之組成物的相關成分或組分可以分子程度溶解於水相中。
「水分散性」意指本發明之組成物的相關成分或組分可分散於水相中且形成穩定的乳液或懸浮液。
本發明之組成物的第一必需組分為至少一種(較佳一
種)類型之磨料顆粒(A)。
當分散於不含下文所述之陰離子磷酸鹽分散劑(C)且具有範圍介於3至9之pH值的水性介質中時,磨料顆粒(A)帶正電。由磨料顆粒(A)之電泳遷移率μ(μm/s)(V/cm)來證明該正電荷。電泳遷移率μ可使用諸如Malvern,Ltd之Zetasizer Nano之儀器直接量測。
磨料顆粒(A)之平均粒徑可大範圍變化,且因此可最有利地調節至本發明之既定組成物及方法的特定要求。如動態雷射光散射所測定之平均粒徑較佳在1至2000nm、較佳1至1000nm、更佳1至750nm且最佳1至500nm之範圍內。
磨料顆粒(A)之粒徑分佈可為單峰、雙峰或多峰。粒徑分佈較佳為單峰以便在本發明之方法期間具有易重現的磨料顆粒(A)之性質特徵及易重現的條件。
此外,磨料顆粒(A)之粒徑分佈可為窄的或寬的。粒徑分佈較佳為窄的,僅具有少量小顆粒及大顆粒,以便在本發明之方法期間具有易重現的磨料顆粒(A)之性質特徵及易重現的條件。
磨料顆粒(A)可具有多種形狀。因此,該等形狀可具有一種或實質上一種類型之形狀。然而,磨料顆粒(A)亦可能具有不同形狀。詳言之,兩種類型形狀不同的磨料顆粒(A)可存在於本發明之既定組成物中。關於形狀本身,其可為立方體、具有斜切邊之立方體、八面體、二十面體、瘤狀(nodule)及具有或不具有突起或凹穴之球體。形狀最佳為無或僅具有極少突起或凹穴之球體。照例偏好此形狀,因為其通常增加磨料顆粒(A)在CMP方法期間對其所暴露之機械力的抗性。
原則上,任何類型之磨料顆粒(A)均可用於本發明之組成物,只要其具有上述性質特徵。因此,磨料顆粒(A)可為有機或無機顆粒或有機-無機混雜顆粒。磨料顆粒(A)較佳為無機顆粒。
原則上,任何類型之無機磨料顆粒(A)均可用於本發明之組成物,只要其具有上述性質特徵。然而,最佳使用含有氧化鈰或由氧化鈰組成之無機磨料顆粒(A)。
含有氧化鈰之磨料顆粒(A)可含有少量其他稀土金屬氧化物。
含有氧化鈰之磨料顆粒(A)較佳為包含一核心之複合顆粒,該核心含有至少一種其他磨料顆粒材料或由至少一種其他磨料顆粒材料組成,其他磨料顆粒材料不同於氧化鈰,詳言之為氧化鋁、二氧化矽二氧化鈦、氧化鋯、氧化鋅及其混合物。
該等複合顆粒(A)可自例如下列文獻中瞭解WO 2005/035688 A1;US 6,110,396;US 6,238,469 B1;US 6,645,265 B1;K. S. Choi等人,Mat. Res. Soc. Symp. Proc.第671卷,2001 Materials Research Society,M5.8.1至M5.8.10;S.-H. Lee等人,J. Mater. Res.,第17卷,第10期,(2002),第2744至2749頁;A. Jindal等人,Journal of the Electrochemical Society,150(5) G314-G318(2003);Z. Lu,Journal of Materials Research,第18卷,第10期,2003年10月,Materials Research Society或S. Hedge等人,Electrochemical and Solid-State Letters,7(12) G316-G318(2004)。
複合顆粒(A)最佳為包含選自由氧化鋁、二氧化矽二氧化鈦、氧化鋯、氧化鋅及其混合物組成之群組且具有20至100 nm核心尺寸之核心的樹莓型塗佈顆粒,其中該核心經具有小於10 nm之粒徑的氧化鈰顆粒塗佈。
本發明之組成物中所用的磨料顆粒(A)之量可大範圍變化,且因此可最有利地調節至本發明之既定組成物及方法的特定要求。本發明之組成物較佳含有0.005至10重量%、更佳0.01至8重量%且最佳0.01至6重量%之磨料顆粒(A),該等重量百分比以本發明之組成物的總重量計。
本發明之組成物之第二必需成分為至少一種(較佳一種)水溶性聚合物(B),其係選自由線性及分枝之氧化烯類(較佳為氧化乙烯及氧化丙烯)均聚物及共聚物組成之群組。
較佳之氧化乙烯-氧化丙烯共聚物(B)可為含有聚氧化乙烯嵌段及聚氧化丙烯嵌段之隨機共聚物、交替共聚物或嵌段共聚物。
在該氧化乙烯-氧化丙烯嵌段共聚物中,聚氧化乙烯較佳具有10至15之親水-親脂平衡(HLB)值。聚氧化丙烯可能具有28至約32之HLB值。
水溶性聚合物(B)為慣用且已知的市售材料。適合之水溶性聚合物(B)描述於下列文獻中:日本專利申請案JP 2001-240850 A,申請專利範圍第2項以及第[0007]至[0014]段、美國專利申請案US 2007/0077865 A1欄頁第1頁第[0008]段至第2頁第[0010]段、美國專利申請案US 2006/0124594 A1第3頁第[0036]段及[0037]及美國專利申請案US 2008/0124913 A1第3頁第[0031]至[0033]段以及申請專利範圍第14項,或其如BASF公司之公司手冊「PluronicTM & TetronicTM Block Copolymer Surfactants,1996」或美國專利US 2006/0213780 A1所示,由BASF公司及BASF SE以商標PluronicTM、TetronicTM及BasensolTM銷售。
最佳使用聚乙二醇(PEG)。
水溶性聚合物(B)及本發明之組成物的濃度可大範圍變化,且因此可最有利地調節至本發明之既定組成物及方法的特定要求。本發明之組成物較佳含有0.001至5重量%,更佳0.005至2.5重量%,甚為更佳0.0075至1重量%以及最佳0.0075至0.5重量%之水溶性聚合物(B)。
本發明之組成物含有至少一種(較佳一種)陰離子磷酸鹽分散劑(C)。
陰離子磷酸鹽分散劑(C)較佳係選自由水溶性縮合磷酸鹽組成之群組。
水溶性縮合磷酸鹽(C)之實例為通式I之偏磷酸之鹽類,尤其是其銨鹽、鈉鹽及鉀鹽:
[M+ n(PO3)n] (I);
及通式II及III之聚磷酸鹽:
M+ nPnO3n+1 (II);
M+H2PnO3n+1 (III);
其中M為銨、鈉及鉀且下標n為2至10,000。關於式I、II及III之聚磷酸鹽,下標n較佳為2至2,000、更佳2至300、最佳2至50、尤其2至15,例如3至8。
尤其適合之水溶性縮合磷酸鹽(C)的實例為格雷姆鹽(Graham's salt)(NaPO3)40-50、CalgonTM(NaPO3)15-20、庫羅爾氏鹽(Kurrol's salt)(NaPO3)n(其中n=約5000)及六偏磷酸銨、六偏磷酸鈉及六偏磷酸鉀。
本發明之組成物中之水溶性陰離子磷酸鹽分散劑(C)之濃度可大範圍變化,且因此可最有利地調節至本發明之既定組成物及方法的特定要求。較佳以使得氧化鈰比陰離子磷酸鹽分散劑(C)之重量比為10至2000(更佳20至1000)之量使用陰離子磷酸鹽分散劑(C)。
本發明之組成物可視情況含有至少一種功能成分(D),其不同於成分或組分(A)、(B)及(C)。
功能成分(D)較佳係選自慣用於基於氧化鈰之CMP漿料中之化合物之群組。此等化合物(D)之實例揭示於例如Y. N. Prasad等人,Electrochemical and Solid-State Letters,9(12) G337-G339(2006);Hyun-Goo Kang等人,Journal of Material Research,第22卷,第3期,2007,第777至787頁;S. Kim等人,Journal of Colloid and Interface Science,319(2008),第48至52頁;S. V. Babu等人,Electrochemical and Solid-State Letters,7(12) G327-G330(2004);Jae-Dong Lee等人,Journal of the Electrochemical Society,149(8) G477-G481,2002;美國專利US 5,738,800、US 6,042,741、US 6,132,637、US 6,218,305 B、US 5,759,917、US 6,689,692 B1、US 6,984,588 B2、US 6,299,659 B1、US 6,626,968 B2、US 6,436,835 B1、US 6,491,843 B1、US 6,544,892 B2、US 6,627,107 B2、US 6,616,514 B1及US 7,071,105 B2;美國專利申請案US 2002/0034875 A1、US 2006/0144824 A1、US 2006/0207188 A1、US 2006/0216935 A1、US 2007/0077865 A1、US 2007/0175104 A1、US 2007/0191244 A1及US 2007/0218811 A1;及日本專利申請案JP 2005-336400 A。
此外,功能成分(D)選自由下列組成之群組:不同於顆粒(D)之有機、無機及有機-無機混雜磨料顆粒;具有下限臨界溶解溫度LCST或上限臨界溶解溫度UCST之材料;氧化劑;鈍化劑;電荷反轉劑;具有至少3個在水性介質中不解離的羥基之有機多元醇;或由至少一種具有至少3個在水性介質中不解離的羥基之單體所形成之聚合物;錯合劑或螯合劑;摩擦劑;穩定劑;流變劑;界面活性劑;金屬陽離子及有機溶劑。
可自例如美國專利申請案US 2008/0254628 A1第4頁第[0054]段或國際申請案WO 2005/014753 A1中瞭解適合之有機磨料顆粒(D)及其有效量,其中其揭示由三聚氰胺及三聚氰胺衍生物(諸如乙醯胍胺、苯并胍胺及二氰二胺)組成之固體顆粒。
可自例如國際專利申請案WO 2005/014753 A1第12頁第1至8行或美國專利US 6,068,787第6欄第41行至第7欄第65行中瞭解適合之無機磨料顆粒(D)及其有效量。
可自例如美國專利申請案US 2008/0254628 A1第4頁第[0054]段或US 2009/0013609 A1第3頁第[0047]段至第6頁第[0087]段中瞭解適合之有機-無機混雜磨料顆粒(D)及其有效量。
可自例如歐洲專利申請案EP 1 036 836 A1第8頁第[0074]段及第[0075]段或美國專利US 6,068,787第4欄第40行至第7欄第45行或US 7,300,601 B2第4欄第18至34行中瞭解適合之氧化劑(D)及其有效量。較佳使用有機及無機過氧化物,更佳使用無機過氧化物。尤其使用過氧化氫。
可自例如美國專利US 7,300,601 B2第3欄第59行至第4欄第9行或美國專利申請案US 2008/0254628 A1跨接第4頁及第5頁之第[0058]段中瞭解適合之鈍化劑(D)及其有效量。
適合之錯合劑或螯合劑(D),其有時亦稱為摩擦劑(參照美國專利申請案US 2008/0254628 A1第5頁第[0061]段)或蝕刻劑(etching agent/etchant)(參照美國專利申請案US 2008/0254628 A1第4頁第[0054]段)及其有效量可自例如美國專利US 7,300,601 B2第4欄第35至48行中瞭解。尤其最佳使用胺基酸(尤其甘胺酸)及此外含有至少一個、較佳兩個且更佳三個一級胺基之二氰二胺及三,(諸如三聚氰胺及水溶性胍胺,尤其三聚氰胺、甲醯胍胺、乙醯胍胺及2,4-二胺基-6-乙基-1,3,5-三)。
可自例如美國專利US 6,068,787第8欄第4至56行中瞭解適合之穩定劑(D)及其有效量。
可自例如美國專利申請案US 2008/0254628 A1第5頁第[0065]段至第6頁第[0069]段中瞭解適合之流變劑(D)及其有效量。
可自例如國際專利申請案WO 2005/014753 A1第8頁第23行至第10頁第17行或自美國專利US 7,300,601 B2第5欄第4行至第6欄第8行中瞭解適合之界面活性劑(D)及其有效量。
可自例如歐洲專利申請案EP 1 036 836 A1第8頁第[0076]段至第9頁第[0078]段中瞭解適合之多價金屬離子(D)及其有效量。
可自例如美國專利US 7,361,603 B2第7欄第32至48行或美國專利申請案US 2008/0254628 A1第5頁第[0059]段中瞭解適合之有機溶劑(D)及其有效量。
展現下限臨界溶解溫度LCST或上限臨界溶解溫度UCST之適合之材料(D)係描述於下列文獻中:例如H. Mori,H. Iwaya,A. Nagai及T. Endo之文章,Controlled synthesis of thermoresponsive polymers derived from L-proline via RAFT polymerization,Chemical Communication,2005,4872-4874;或D. Schmaljohann之文章,Thermo-and pH-responsive polymers and drug delivery,Advanced Drug Delivery Reviews,第58卷(2006),1655-1670或美國專利申請案US 2002/0198328 A1、US 2004/0209095 A1、US 2004/0217009 A1、US 2006/0141254 A1、US 2007/0029198 A1、US 2007/0289875 A1、US 2008/0249210 A1、US 2008/0050435 A1或US 2009/0013609 A1;美國專利US 5,057,560、US 5,788,82及US 6,682,642 B2;國際專利申請案WO 01/60926 A1、WO 2004/029160 A1、WO 2004/0521946 A1、WO 2006/093242 A2或WO 2007/012763 A1;歐洲專利申請案EP 0 583 814 A1、EP 1 197 587 B1及EP 1 942 179 A1;或德國專利申請案DE 26 10 705中。
原則上,可使用習用於CMP領域中之任何已知電荷反轉劑(D)。電荷反轉劑(D)較佳係選自由含有至少一個選自由羧酸酯基、亞磺酸基、硫酸酯基及膦酸酯基組成之群組的陰離子基團之單體化合物、寡聚化合物及聚合化合物組成之群組。
若功能成分(D)存在,則其含量可變化。以相應CMP組成物之總重量計,(D)之總量較佳不超過10 wt.%(「wt.%」意指「重量百分比」)、更佳不超過2 wt.%、最佳不超過0.5 wt.%、尤其不超過0.1 wt.%,例如不超過0.01 wt.%。以相應組成物之總重量計,(D)之總量較佳為至少0.0001 wt.%、更佳至少0.001 wt.%、最佳至少0.008 wt.%、尤其至少0.05 wt.%,例如至少0.3 wt.%。
本發明之組成物可視情況含有至少一種pH調節劑或緩衝劑(E),其本質上不同於成分(A)、(B)及(C)。
可自例如歐洲專利申請案EP 1 036 836 A1第8頁第0080]、[0085]段及第[0086]段;國際專利申請案WO 2005/014753 A1第12頁第19至24行;美國專利申請案US 2008/0254628 A1第6頁第[0073]段或美國專利US 7,300,601 B2第5欄第33至63行中瞭解適合之pH調節劑或緩衝劑(E)及其有效量。pH調節劑或緩衝劑(E)之實例為氫氧化鉀、氫氧化銨、氫氧化四甲基銨(TMAH)、硝酸及硫酸。
若pH調節劑或緩衝劑(E)存在,則含量可變化。以相應CMP組成物之總重量計,(E)之總量較佳不超過20 wt.%、更佳不超過7 wt.%、最佳不超過2 wt.%、尤其不超過0.5 wt.%,例如不超過0.1 wt.%。以相應組成物之總重量計,(E)之總量較佳為至少0.001 wt.%、更佳至少0.01 wt.%、最佳至少0.05 wt.%、尤其至少0.1 wt.%,例如至少0.5 wt.%。
使用前述之pH調節劑(E)將本發明之組成物的pH值較佳設定在3與10之間,更佳在3與8之間,甚至更佳在3與7之間且最佳在5與7之間。
本發明之組成物的製備不展現任何特殊性,而是可藉由將上述成分(A)、(B)及(C)及視情況選用之(D)及/或(E)溶解或分散於水性介質(詳言之,去離子水)中來進行。為此目的,可使用習用及標準混合方法及混合設備,諸如攪拌容器、線上溶解器、高剪切葉輪、超音波混合器、均化器噴嘴或對流混合器。由此獲得之本發明之組成物較佳可經由具有適當篩孔之過濾器過濾以便移除粗粒狀顆粒,諸如精細分散之固體磨料顆粒(A)的聚結物或聚集物。
本發明之組成物優異地適於本發明之方法。
在本發明之方法中,使電子、機械及光學裝置(尤其電子裝置,最佳積體電路裝置)基材材料與本發明之組成物接觸至少一次且研磨(尤其化學及機械研磨)直至獲得所需平坦度為止。
本發明之方法在具有由低k或超低k氧化矽材料組成之隔離層及多晶矽層(視情況地包含氮化矽層)之矽半導體晶圓之CMP中展現出其特殊優勢。
適合之低k或超低k材料及製備絕緣介電層之適合方法描述於例如美國專利申請案US 2005/0176259 A1第2頁第[0025]段至第[0027]段、US 2005/0014667 A1第1頁第[0003]段、US 2005/0266683 A1第1頁段落[0003]及第2頁第[0024]段或US 2008/0280452 A1第[0024]段至第[0026]段或美國專利US 7,250,391 B2第1欄第49至54行或歐洲專利申請案EP 1 306 415 A2第4頁第[0031]段中。
本發明之方法尤其適於淺溝槽隔離(STI),其需要在圖案化晶圓基材上優先於多晶矽選擇性地移除二氧化矽。在此方法中,以介電材料(例如二氧化矽)過量裝填經蝕刻之溝槽,並使用氮化矽障壁膜作為停止層研磨。在此較佳具體實例中,在自障壁膜清除二氧化矽同時使暴露之多晶矽及溝槽氧化矽移除減至最少的情況下結束本發明之方法。
此外,本發明之方法亦尤其適於亦存在氮化矽膜之淺溝槽隔離(STI),因為本發明之組成物展現高氧化物對多晶矽之選擇性結合適中的氧化物對氮化物之選擇性。
因此,本發明之方法展現大於50、較佳大於75及最佳大於100之氧化物對多晶矽之選擇性以及大於10、較佳大於20及最佳大於25之氮化物對多晶矽之選擇性。
氧化物對氮化物之選擇性較佳在3至10之範圍內。
氮化物對多晶矽之選擇性較佳大於10。
本發明之方法不展現特殊性,而是可用習用於具有IC之半導體晶圓製造中之CMP的方法及設備來進行。
如此項技藝中已知者,用於CMP之典型設備由用研磨墊覆蓋的旋轉平台組成。晶圓安裝在載體或夾頭上,使其上端向下面向研磨墊。載體將晶圓緊固在水平位置。此研磨及夾持裝置之特殊佈置亦稱為硬平台設計(hard-platen design)。載體可保留載體墊,其位於載體保留表面與未研磨之晶圓表面之間。此墊可充當晶圓之緩衝墊。
在載體下方,一般亦水平安置較大直徑平台且呈現與待研磨晶圓之表面平行的表面。其研磨墊在平坦化過程期間與晶圓表面接觸。在本發明之CMP方法期間,本發明之組成物以連續流形式或以逐滴方式施用於研磨墊上。
使載體與平台均圍繞自載體及平台垂直延伸之相應軸旋轉。旋轉之載體軸可相對於旋轉之平台仍固定在原位或可相對於平台水平擺動。載體之旋轉方向典型地(但不一定)與平台之旋轉方向相同。載體及平台之旋轉速度一般(但不一定)設定為不同值。
平台之溫度慣常設定為10至70℃之間的溫度。
關於其他詳情,參考國際專利申請案WO 2004/063301 A1,詳言之第16頁第[0036]段至第18頁第[0040]段以及圖1。
藉由本發明之方法可獲得具有包含圖案化之低k及超低k材料層(詳言之二氧化矽層)之IC的半導體晶圓,其具有極佳平坦度。因此,可獲得銅鑲嵌圖案,其亦具有極佳平坦度,且在成品中,IC具有極佳電子功能性。
比較實驗之實施例
實施例1
水性研磨組成物1至6之製備
對於水性研磨組成物1至6之製備,將氧化鈰(如動態雷射光散射所測定,平均粒徑d50為120 nm至140 nm)、聚乙二醇(PEG10K;重量平均分子量:10,000)及六偏磷酸鈉(PP;氧化鈰比PP之重量比=200,下文稱為PP200)分散或溶解於超純水中。所用量彙編於表1中。
實施例2及3以及比較實施例C1至C4
在矽半導體晶圓上之多晶矽層CMP
實施例2使用實施例1中之組成物5。實施例3使用實施例1中之組成物6。
比較實驗C1至C4分別使用實施例1中之組成物1至4。
在下文中,使用以下CMP方法參數:
- 研磨設備:Strasbaugh 6EGnHance(旋轉型);
- 平台速度:90 rpm;
- 載體速度:70 rpm;
- 由Rohm & Haas製造之IC 1000/Suba 400 K凹槽研磨墊;
- 原位修整使用S60 3M金剛石修整器(diamond conditioner);
- 漿料流速:200 ml/min;
- 基材:200 mm熱氧化物、PETEOS、氮化矽及多晶矽晶圓;
- 下壓力:3.5 psi(240毫巴);
- 研磨時間:1分鐘。
藉由雷射干涉測量儀(FilmTekTM 2000)在多晶矽晶圓中心之位置(位置1)及在位置1之周圍4個位置(該等位置至晶圓邊緣之距離相同,位置2至5)量測多晶矽材料移除率(MRR)。
該等位置展現較高之MRR,下文稱其為「熱點」(hot spots)。
表2提供所得MRR之概述。
表2之結果顯而易知:當組成物僅包含氧化鈰時,多晶矽MRR值非常高。PEG10K之添加使平均MRR值降低。然而,如熱點外觀所證,觀察到不均勻的多晶矽移除。PEG10K濃度提高導致範圍縮減及MRR降低。添加PP200亦造成MRR降低,可藉由PEG10K及PP200之協同作用抑制該現象。
此外,相較於比較實驗,在實驗2及3中,吸著在晶圓上之顆粒量顯著地較低。
實施例4及5
含有PP200及PEG10K之水性研磨組成物之選擇性
實施例4使用實施例1之水性研磨組成物5。
實施例5使用含有0.25重量%之氧化鈰及0.05重量%之PEG10K及PP200之研磨組成物。
以所述之方法測定熱氧化物(TOX)、PETEOS、氮化矽及多晶矽晶圓之MRR。所得之MRR彙編於表3中。
經計算之選擇性彙編於表4中。
該等結果顯示該等水性研磨組成物優異地適於含有二氧化矽、氮化矽及多晶矽層之半導體晶圓CMP。因此,氧化物對多晶矽之選擇性特別地高,而氧化物對氮化物之選擇性是在可避免在含有二氧化矽、氮化矽及多晶矽區域之經全面平坦化、異質、經圖案化表面中之碟型凹陷及其他破壞及缺陷之有利範圍內。此外,氮化物對多晶矽之選擇性遠高於10。
觀察該等晶圓經CMP後是否有不想要的殘留膜形成。然而,其並未形成不想要的殘留膜。
實施例6至9
含有0.5重量%氧化鈰、0.1重量%PEG10K及不同PP量之水性研磨組成物之選擇性
以所述之方法測定氧化鈰對PP之比例對熱氧化物(TOX)、PETEOS、氮化矽及多晶矽晶圓之影響。所得之MRR彙編於表5中。
經計算之選擇性彙編於表6中。
該等結果顯示可藉由改變氧化鈰對PP之比例有利地調節MRR及選擇性。可達到特別高的氧化物對多晶矽之選擇性以及高氮化物對多晶矽之選擇性,而氧化物對氮化物之選擇性維持在可避免在含有二氧化矽、氮化矽及多晶矽區域之經全面平坦化、異質、經圖案化表面中之碟型凹陷及其他破壞及缺陷之有利範圍內。
Claims (13)
- 一種水性研磨組成物,該水性研磨組成物包含:(A)至少一種類型之含有氧化鈰或係由氧化鈰所組成的磨料顆粒,當其分散於不含陰離子磷酸鹽分散劑且具有範圍介於3至9之pH值的水性介質中時帶正電,由電泳遷移率所證明;(B)至少一種水溶性聚合物,其係選自由線性及分枝氧化烯均聚物及共聚物所組成之群組;及(C)至少一種陰離子磷酸鹽分散劑,其中該組成物含有0.001至5重量%之量的該水溶性聚合物(B)。
- 根據申請專利範圍第1項之水性研磨組成物,其中以該研磨組成物的總重量計,其含有0.005重量%至10重量%之磨料顆粒(A)。
- 根據申請專利範圍第1項之水性研磨組成物,其中線性及分枝氧化烯均聚物及共聚物(B)係選自由氧化乙烯及氧化丙烯之均聚物及共聚物所組成之群組。
- 根據申請專利範圍第1項之水性研磨組成物,其中線性及分枝氧化烯均聚物及共聚物(B)係選自由氧化乙烯及氧化丙烯之均聚物及共聚物所組成之群組。
- 根據申請專利範圍第3或4項之水性研磨組成物,其中含有作為氧化乙烯之均聚物(B)之聚乙二醇(PEG)。
- 根據申請專利範圍第1或4項之水性研磨組成物,其中陰離子磷酸鹽分散劑(C)係選自由水溶性縮合磷酸鹽組 成之群組。
- 根據申請專利範圍第6項之水性研磨組成物,其中水溶性縮合磷酸鹽(C)係選自由下列組成之群組:通式I之偏磷酸鹽:[M+ n(PO3)n] (I);其中M為銨、鈉及鉀且下標n為2至10,000。
- 根據申請專利範圍第1或4項之水性研磨組成物,其中含有不同於成分(A)、(B)及(C)之至少一種pH調節劑或緩衝劑(E)。
- 根據申請專利範圍第1或4項之水性研磨組成物,其中含有不同於成分(A)、(B)及(C)之至少一種功能成分(D),其中功能成分(D)係選自由下列所組成之群組:不同於顆粒(A)之有機、無機及有機-無機混雜磨料顆粒、具有下限臨界溶解溫度LCST或上限臨界溶解溫度UCST之材料、氧化劑、鈍化劑、電荷反轉劑、含有具有至少2個在水性介質中不解離的羥基之有機多元醇、由至少一種具有至少2個在水性介質中不解離的羥基之單體所形成之寡聚物及聚合物、錯合劑或螯合劑、摩擦劑、穩定劑、流變劑、界面活性劑、金屬陽離子及有機溶劑。
- 一種研磨用於電子、機械及光學裝置基材之方法,該方法係藉由使該基材與水性研磨組成物接觸至少一次且研磨該基材材料直至達成所需平坦度為止,其中使用如申請專利範圍第1至9項中任一項之水性研磨組成物,其中該基材包含至少一層含有至少一種氧化矽介電質材料或係 由至少一種氧化矽介電質材料組成之層及至少一層含有多晶矽或係由多晶矽組成之層,以及氧化物對多晶矽之選擇性大於50。
- 根據申請專利範圍第10項之方法,其中該基材材料另外包含至少一層含有氮化矽或係由氮化矽組成之層,以及氧化物對氮化物之選擇性是在3至6的範圍內。
- 根據申請專利範圍第10或11項之方法,其中該等電子裝置為積體電路裝置、液晶面板、有機電場發光面板、印刷電路板、微型機器、DNA晶片、微型工廠及磁頭;該等機械裝置為高精度機械裝置;及該等光學裝置為諸如光罩、透鏡及稜鏡之光學玻璃、諸如氧化銦錫(ITO)之無機導電膜、光學積體電路、光學交換元件、光學波導、諸如光學纖維端面及閃爍體之光學單晶、固體雷射單晶、用於藍色雷射LED之藍寶石基材、半導體單晶及用於磁碟之玻璃基材。
- 根據申請專利範圍第12項之方法,其中該積體電路裝置含有具有尺寸小於50nm之結構、具有大規模積體或超大規模積體之積體電路。
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2011
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CN103080256B (zh) | 2015-06-24 |
EP2428541A1 (en) | 2012-03-14 |
IL224645A (en) | 2017-11-30 |
SG10201606566SA (en) | 2016-09-29 |
WO2012032451A1 (en) | 2012-03-15 |
US20130168348A1 (en) | 2013-07-04 |
MY175638A (en) | 2020-07-03 |
JP5965906B2 (ja) | 2016-08-10 |
KR20130102587A (ko) | 2013-09-17 |
TW201226491A (en) | 2012-07-01 |
EP2428541B1 (en) | 2019-03-06 |
RU2573672C2 (ru) | 2016-01-27 |
CN103080256A (zh) | 2013-05-01 |
SG11201606187RA (en) | 2016-09-29 |
KR101906135B1 (ko) | 2018-10-10 |
RU2013115237A (ru) | 2014-10-20 |
JP2013540849A (ja) | 2013-11-07 |
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