TWI480123B - 多功能研磨墊 - Google Patents
多功能研磨墊 Download PDFInfo
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- TWI480123B TWI480123B TW099123239A TW99123239A TWI480123B TW I480123 B TWI480123 B TW I480123B TW 099123239 A TW099123239 A TW 099123239A TW 99123239 A TW99123239 A TW 99123239A TW I480123 B TWI480123 B TW I480123B
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- Prior art keywords
- polishing pad
- polishing
- weight
- mixture
- polyamine
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- 238000005498 polishing Methods 0.000 title claims description 100
- 239000000203 mixture Substances 0.000 claims description 64
- 229920000642 polymer Polymers 0.000 claims description 49
- 229920000768 polyamine Polymers 0.000 claims description 36
- 229920001451 polypropylene glycol Polymers 0.000 claims description 34
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 27
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 27
- 229910052802 copper Inorganic materials 0.000 claims description 26
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
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- 230000009467 reduction Effects 0.000 description 4
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- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
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- BSYVFGQQLJNJJG-UHFFFAOYSA-N 2-[2-(2-aminophenyl)sulfanylethylsulfanyl]aniline Chemical compound NC1=CC=CC=C1SCCSC1=CC=CC=C1N BSYVFGQQLJNJJG-UHFFFAOYSA-N 0.000 description 1
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- 229920002396 Polyurea Polymers 0.000 description 1
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- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
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- POAHJTISJZSSFK-UHFFFAOYSA-N chloro(phenyl)methanediamine Chemical compound NC(N)(Cl)C1=CC=CC=C1 POAHJTISJZSSFK-UHFFFAOYSA-N 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
- B24D3/28—Resins or natural or synthetic macromolecular compounds
- B24D3/32—Resins or natural or synthetic macromolecular compounds for porous or cellular structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/34—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents characterised by additives enhancing special physical properties, e.g. wear resistance, electric conductivity, self-cleaning properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
Description
本發明係關於用於研磨或平坦化半導體基板之研磨墊。半導體之生產典型地包括幾個化學機械研磨(CMP)製程。於每個CMP製程中，與研磨溶液(如含有研磨劑之研磨漿料或不含研磨劑之反應液體)組合之研磨墊以平坦化或保持平坦之方式去除多餘材料以用於接收後續層。該等層體之堆疊體以形成積體電路之方式組合。由於對具有更高操作速度、更低漏電電流及減少之功率消耗之裝置的要求，該等半導體裝置之製造變得越來越複雜。在裝置結構方面，可說是更精細的特徵幾何及增加數量的金屬化層。這些越來越嚴格的裝置設計需求迫使採取具有對應提高的圖案密度之越來越小的線間隔。該等裝置之更小規模(scale)及更高復雜性已導致對CMP耗材(如研磨墊及研磨溶液)之更大的要求。此外，隨著積體電路之特徵尺寸減小，CMP引起之缺陷(如括痕)變成更大的問題。再者，積體電路減小之膜厚度需要改進之缺陷率且同時提供晶圓基板之可接受之形貌，該等對形貌之要求需要越來越嚴格之平坦度、線凹化(line dishing)及小特徵陣列腐蝕研磨規格。
從歷史上講，澆鑄之聚胺脂研磨墊已為用於製造積體電路之大多數研磨操作提供機械完整性及化學品抗性。例如，聚胺脂研磨墊具有足夠抗撕裂的拉伸強度及伸長率、防止研磨過程中之磨損問題之抗磨損性以及抵抗強酸性及強腐蝕性研磨溶液之安定性。由陶氏電子材料(Dow Electronic Materials)所提供之IC1000TM
研磨墊代表了適用於研磨多個基板之工業標準聚胺脂研磨墊，如鋁、阻隔材料(barrier material)、電介質、銅、硬掩膜、低-k電介質、鎢及超低-k電介質(IC1000係陶氏電子材料陶氏電子材料或其附屬公司之商標)。
M. J. Kulp於第7,169,030號美國專利案揭示了一族具有高拉伸模數之聚胺脂研磨墊。該等研磨墊對於幾種研磨墊及研磨漿料之組合提供優異的平坦度及缺陷率。例如，該等研磨墊可為研磨氧化矽/氮化矽應用之含鈰之研磨漿料提供優異的研磨效能，如直接淺溝道隔離(shallow trench isolation,STI)研磨應用。為了本說明書的目的，氧化矽係指有用於形成於半導體裝置之電介質之氧化矽、氧化矽化合物及經摻雜之氧化矽製劑；而氮化矽係指有用於半導體應用之氮化矽、氮化矽化合物及經摻雜之氮化矽製劑。不幸的是，對改進研磨性能來說，該等墊對所有用於目前及將來半導體晶圓所含之多個基板層體之研磨漿料不具有通用性。再者，隨著半導體裝置之成本降低，仍然需要更加增強之研磨性能。
對於圖案化(patterned)晶圓而言，非鐵金屬之研磨(如銅研磨)仍然為積體電路及記憶應用之重要需求應用。於半導體之製造中，通常以銅層覆蓋整個晶圓。該研磨墊必須提供優異的大塊銅(bulk copper)之去除，剩下銅互連網絡。仍然需要具有改進之非鐵基板研磨性能(如銅研磨)之研磨墊。由於對性能增強之需要，仍然需要去除具有改進之性能之基板層之研磨墊。
此外，增加研磨墊之去除率可增加產出(throughput)以減少半導體製造工廠之設備底面積及支出。由於對增加效能的需求，仍想要一種研磨墊而以增加之效能來移除基板層。例如，氧化物電介質去除率對於層間電介質("inter-layer dielectric,ILD")或金屬間電介質("inter-metallic dielectric,IMD")研磨過程中之電介質之去除很重要。所用具體類型的電介質氧化物包括下述：BPSG、自矽酸四乙酯(tetraethyloxysilicate)之分解所形成之TEOS、HDP("高密度電漿")及SACVD("次大氣壓化學氣相沈積")。目前仍需要具有提高之去除率以及可接受之缺陷率性能及晶圓均勻度(uniformity)之研磨墊。特別地，需要適於ILD研磨且具有加速之氧化物去除率以及可接受之平坦度及缺陷率研磨性能之研磨墊。
於本發明之一態樣中，提供適於研磨圖案化半導體基板之研磨墊，該圖案化半導體基板含有下述之至少一者：銅、電介質、阻隔及鎢，該研磨墊包括聚合物基質，該聚合物基質係聚醇共混物(polyol blend)、聚胺或聚胺混合物及甲苯二異氰酸酯之聚胺脂反應產物，該聚醇共混物為15至77重量%之總聚丙二醇與聚四亞甲基醚二醇(polytetramethylene ethyl glycol)之混合物，該聚丙二
醇與聚四亞甲基醚二醇之混合物中聚丙二醇與聚四亞甲基醚二醇之重量比為20：1至1：20，該聚胺或聚胺混合物為8至50重量%，該甲苯二異氰酸酯為15至35重量%之總單體或部分反應之甲苯二異氰酸酯單體。
於本發明之另一態樣，提供適於研磨圖案化半導體基板之研磨墊，該圖案化半導體基板含有下述之至少一者：銅、電介質、阻隔及鎢，該研磨墊包括聚合物基質，該聚合物基質係聚醇共混物、聚胺或聚胺混合物及甲苯二異氰酸酯之聚胺脂反應產物，該聚醇共混物為20至75重量%之總聚丙二醇及聚四亞甲基醚二醇之混合物，該聚丙二醇及聚四亞甲基醚二醇之混合物中聚丙二醇與聚四亞甲基醚二醇之重量比為15：1至1：15，該聚胺或聚胺混合物為10至45重量%，該甲苯二異氰酸酯為20至30重量%之總單體或部分反應之甲苯二異氰酸酯單體。
本發明提供適於平坦化半導體、光學及磁性基板之至少一者之研磨墊，該研磨墊包括聚合物基質。特別地，已發現來自聚胺、聚丙二醇(PPG)與聚四伸甲基醚二醇(PTMEG)之共混物、以及甲苯二異氰酸酯之聚胺脂反應產物之聚合基質係提供用於銅及ILD研磨之多功能墊。特別地，於ILD及銅應用上，以該等範圍所製造之墊皆提供比工業標準IC1000研磨墊改進之研磨性能。
本發明之研磨墊對於銅研磨有效能。特別地，該等墊可提高銅去除率且不相應地增加缺陷率。或者，該等墊可降低缺陷率且不相應地降低去除率。為了本說明書的目的，去除率係指以埃()/分鐘表示之去除率。
該等研磨墊特別適於研磨及平坦化例如於層間電介質(ILD)應用中之ILD電介質材料，且亦適於非鐵應用中，如鋁、銅及鎢。該等墊具有比現有墊提高之去除率──尤其於研磨的前30秒。藉由減少自晶圓表面去除特定量的材料所需之研磨時間，該等墊於研磨早期之加速反應使晶圓產出增加成為可能。
使用燻矽(fumed silica)研磨30秒之ILD去除率可大於3750/分鐘。再者，本發明可提供比於相同研磨測試中IC1010TM
聚胺脂研磨墊研磨30秒之去除率高至少10%之去除率(IC1010係陶氏電子材料或其附屬公司之商標)。有利地，本發明研磨墊以含氧化矽研磨劑研磨TEOS片晶圓30秒之去除率係等於或大於IC1000研磨墊以含氧化矽研磨劑研磨TEOS片晶圓30秒及60秒之去除率。IC1000TM
可隨著研磨時間提高TEOS去除率，這是因為其包括易於賦予自組份製得之部分熱塑性特徵之脂肪族異氰酸酯(aliphatic isocaynate)。IC1000研磨墊之熱塑性特徵似乎促使研磨墊與晶圓之間的接觸增加並伴隨著去除率增加，直至出現某最高去除率。增加墊-對-晶圓之接觸面積到甚至更高等級，似乎會因局部凸體對晶圓的接觸壓力降低而降低去除率。
雖然去除率可隨著研磨劑含量之增加而增加，但是不依賴於研磨劑含量之高於IC1010研磨墊之去除率之改善表示研磨性能之重大改進。例如，這會促進提高去除率且具有低缺陷率，並可降低漿料成本。除了去除率，晶圓規模的不均勻度(nonuniformity)亦表示重要的研磨性能考量。典型地，由於經研磨晶圓的均勻度對於獲得最大數量的良好拋光晶片(die)很重要，因晶圓內的不均勻度(within-wafer nonuniformity)應小於6%。
為了本說明書的目的，"聚胺脂"係衍生自二官能度或多官能度異氰酸酯之產物，如聚醚脲、聚異氰脲酸酯(polyisocyanurate)、聚胺脂、聚脲、聚胺脂脲、其共聚物及其混合物。澆鑄聚胺脂研磨墊適合用於平坦化半導體、光學及磁性基板。該等墊之特殊研磨特性部分地來自聚丙二醇(PPG)與聚四亞甲基醚二醇(PTMEG)之共混物、聚胺及甲苯二異氰酸酯之反應產物。已發現控制與聚胺及甲苯二異氰酸酯組合之PPG/PTMEG比可生產具有改進之研磨性能之多功能研磨墊。特別地，該等墊可改進銅、ILD及STI應用之研磨。
聚合物基質來自含有總共15至77重量%之PPG及PTMEG之混合物。為了本說明書的目的，除非另行說明，製劑以重量百分比表示。較佳地，該聚合物基質來自含有總共20至75重量%之PPG及PTMEG之混合物。此外，該混合物含有20：1至1：20之PPG/PTMEG比。較佳地，該混合物含有15：1至1：15之PPG/PTMEG比。2：1至1：2之PPG/PTMEG特別有利於高速銅及ILD研磨。此外，20：1至2：1，較佳地15：1至2：1之PPG/PTMEG比特別有利於低缺陷銅及ILD研磨。類似地，1：20至1：2，以及較佳地1：15至1：2之PPG/PTMEG比也特別有利於低缺陷銅及ILD研磨。
該液體混合物包括15至35重量%之甲苯二異氰酸酯(TDI)之單體或部分反應之單體。為了本說明書的目的，TDI之單體或部分反應之單體表示TDI單體或是在聚胺脂固化之前反應成預聚物之TDI單體的重量%。較佳地，該TDI單體或部分反應之單體佔20至30重量%。視需要地，該芳香族TDI可含有某些脂肪族異氰酸酯。較佳地，該多官能度芳香族異氰酸酯含有少於15重量%之脂肪族異氰酸酯，更佳地，少於12重量%之脂肪族異氰酸酯。最佳地，該混合物僅含有雜質程度的脂肪族異氰酸酯。
能於該TDI範圍生成聚合物之適當的PTMEG系預聚物之特別的實例為Chemtura所製造的Adiprene預聚物LF750D。適當的PPG系預聚物之實例包括Adiprene預聚物LFG740D及LFG963A。此外，LF750D、LFG740D及LFG963A表示其中游離2,4及2,6 TDI單體各自含量小於0.1重量%之低遊離異氰酸酯預聚物且該預聚物比傳統預聚物具有更恒定(consistent)的預聚物分子量分佈。具有改進之預聚物分子量恒定性之“低遊離”預聚物及低遊離異氰酸酯單體可促使更規則的聚合物結構且獲得改進之研磨墊恒定性(consistency)。
該聚合物基質典型地包括下列原料：莫耳比為4：5至5：4之聚胺NH2
與聚醇OH；以及為0.9：1.0至1.1：1.0之聚醇OH對異氰酸酯NCO莫耳比。某些OH基可來自低分子量聚醇或來自水，可能是特意添加或藉由曝露至外來(adventitious)水份。該聚醇或聚胺可部分與異氰酸酯反應以在生成最終聚合物基質之前形成預聚物或於一步製程中一起添加至異氰酸酯。
典型地，該反應混合物含有8至50重量%聚胺或含聚胺混合物。較佳地，該混合物含有10至45重量%聚胺或含聚胺混合物。例如，可將聚胺與醇胺或單胺混合。為了本說明書的目的，聚胺包括二胺及其他多官能度胺。聚胺之實例包括芳香二胺或聚胺，如4,4’-亞甲基-雙-鄰-氯苯胺[MBCA]、4,4’-亞甲基-雙-(3-氯-2,6-二乙基苯胺)[MCDEA]、二甲基硫基甲苯二胺、三亞甲基二醇二-對-胺基苯甲酸酯(trimethyleneglycol di-p-aminobenzoate)、聚四亞甲基氧化物二-對-胺基苯甲酸酯(polytetramethyleneoxide di-p-aminobenzoate)、聚四亞甲基氧化物單-對-胺基苯甲酸酯(polytetramethyleneoxide mono-p-aminobenzoate)、聚環氧丙烷二對胺基苯甲酸酯、聚環氧丙烷單對胺基苯甲酸酯、1,2-雙(2-胺基苯基硫基)乙烷、4,4’-亞甲基-雙-苯胺、二乙基甲苯二胺、5-第三丁基-2,4-甲苯二胺及3-第三丁基-2,6-甲苯二胺、5-第三戊基-2,4-甲苯二胺及3-第三戊基-2,6-甲苯二胺及氯甲苯二胺。MBCA添加為較佳的聚胺。可以單個混合步驟或使用預聚物製造用於研磨墊之胺甲酸乙酯聚合物。
用於製造研磨墊之聚合物組份較佳經選擇以使所得墊之形態安定並可輕易再生。例如，當將4,4’-亞甲基-雙-鄰-氯苯胺[MBCA]與甲苯二異氰酸酯單體或預聚物混合以形成聚胺脂聚合物時，通常控制單胺、二胺及三胺之濃度為有利。控制單胺、二胺及三胺之比例有助於保持化學比率及所得聚合物分子量於恒定的範圍。此外，為了恒定製造，通常控制添加劑(如抗氧化劑)以及雜質(如水)是重要的。例如，由於水與異氰酸酯反應形成二氧化碳氣體，因此控制水濃度可影響會於聚合物基質中形成孔洞之二氧化碳氣泡之濃度。異氰酸酯與外來水反應亦減少與聚胺反應之可用異氰酸酯，從而改變OH或NH2
與NCO之莫耳比以及交聯度(若有過量異氰酸酯基)以及改變所得聚合物分子量。
該聚胺脂聚合物材料較佳形成自甲苯二異氰酸酯與聚四亞甲基醚二醇/聚丙二醇共混物及聚胺之預聚物反應產物。較佳地，該聚胺為芳香族甲苯二異氰酸酯。最佳地，該芳香二胺為4,4’-亞甲基-雙-鄰-氯苯胺或4,4’-亞甲基-雙-(3-氯-2,6-二乙基苯胺)。
該研磨墊呈多孔及無孔或未填充結構皆有用。該完成之研磨墊較佳具有0.4至1.3公克/立方公分(g/cm3
)之密度。對於多孔墊而言，該完成之聚胺脂研磨墊典型地具有0.5至1 g/cm3
之密度。可通過氣體溶解、起泡劑、機力起泡及引入中空微球來添加孔隙度。根據孔隙度及組成物，該研磨墊典型地具有20至70之蕭氏D型(Shore D)硬度。為了本說明書的目的，該蕭氏D型測試包括在測試之前將墊樣品置於50%相對濕度及25℃條件下5天以及使用ASTM D2240摘要出的方法，以改進該硬度測試之再現性。
該孔隙度典型地具有2至50微米(μm)之平均直徑。最佳地，該孔隙度來自圓形中空聚合物顆粒。較佳地，該中空聚合物顆粒具有2至40μm之重量平均直徑。為了本說明書的目的，重量平均直徑表示澆鑄之前之中空聚合物顆粒之直徑，且該顆粒可具有圓形或非圓形之形狀。最佳地，該中空聚合物顆粒具有10至30μm之重量平均直徑。
擴大的中空聚合物顆粒之重量平均直徑之標稱範圍(nominal range)為15至90μm。再者，高孔隙度與小孔徑之組合可特別地有益於降低缺陷率。然而，若孔隙度變得很高，研磨墊之機械完整性及強度將減弱。例如，添加構成30至60體積%之研磨層之2至50μm重量平均直徑之中空聚合物顆粒有助於缺陷率之降低。再者，保持35及55體積%間或具體地35及50體積%之孔隙度可助於提升之去除率。為了本說明書的目的，體積百分比孔隙度表示以下列方法確定之孔洞的體積百分比：1)自無孔隙度之聚合物之標稱密度減去所測量到的製劑密度，以確定每立方公分製劑所“失去”之聚合物之質量；然後，2)將所“失去”之聚合物之質量除以無孔隙度之聚合物之標稱密度，以確定每立方公分製劑所失去之聚合物之體積並將之乘以100而轉換為孔隙度體積百分比(文中有稱為體積百分比孔隙度之情形)。或者，製劑中孔洞之體積百分比或體積百分比孔隙度可以下列方法確定：1)將100 g減去於100 g製劑中該中空聚合物顆粒之質量以得到於100 g製劑之聚合物基質之質量；2)將該聚合物基質之質量除以該聚合物之標稱密度以得到於100 g製劑中聚合物基質之體積；3)將100 g製劑中該中空聚合物顆粒之質量除以中空聚合物顆粒標稱密度以確定於100g製劑中該中空聚合物顆粒之體積；4)將於100g製劑中該聚合物之體積與於100g製劑中該中空顆粒或孔洞之體積相加以確定100g製劑之體積；然後，5)將於100g製劑中該中空顆粒或孔洞之體積除以100g製劑之總體積並乘以100以獲得於製劑中孔洞或孔隙度之體積百分比。雖然第二種方法比第一種方法(其中處理過程中諸如反應放熱之參數可能使得中空聚合物顆粒或微球擴大超過其標稱“擴大體積”)獲得較低數值的孔洞或孔隙度之體積百分比，但是該兩種方法將獲得相似的孔洞或孔隙度之體積百分比數值。由於孔洞尺寸之減小侵向於增加具體孔洞或孔隙度之研磨率，因此控制澆鑄過程中之放熱以防止預擴大之中空聚合物顆粒或微球之進一步擴大是很重要的。例如，澆鑄至室溫模具中、控制餅高度、降低預聚物溫度、降低聚胺或聚醇之溫度、減少NCO及限制遊離TDI單體皆有助於減少由反應異氰酸酯所產生之放熱。
對於大多數傳統多孔研磨墊而言，研磨墊修整(conditioning)(如鑽石盤修整)用以增加去除率且改善晶圓規模的不均勻度。雖然修整可周期性進行(如於每個晶圓後30秒)或以連續方式進行，但是連續修整有利於建立穩定狀態之研磨條件，以提供改進之去除率控制。該修整典型地提高研磨墊去除率並防止典型地與研磨墊表面之磨損有關之去除率之降低。特別地，研磨劑修整形成粗糙表面，該粗糙表面可於研磨過程中困住燻矽顆粒。除了修整，凹槽及穿孔可進一步有利於漿料之分佈、研磨均勻度、碎片去除及基板去除率。
聚合物墊的材料係藉由將各種濃度之異氰酸酯(作為胺甲酸乙酯預聚物)與4,4’-亞甲基-雙-鄰氯苯胺[MBCA]混合(49℃預聚物，115℃ MBCA)以作為本發明之實施例(比較例包括於43至63℃預聚物)。特別地，基於PTMEG及PPG之甲苯二異氰酸酯預聚物之混合物提供具有改進之研磨特性之研磨墊。在混合該預聚物及鏈伸長劑之前或之後將胺甲酸乙酯/多官能度胺混合物與中空聚合物微球(由AkzoNobel所製造之551DE20d60或551DE40d42)混合。該中空聚合物微球在添加多官能度胺之前與預聚物於60 rpm混合再於4500 rpm混合該混合物，或著該中空聚合物微球添加至於3600 rpm之混合頭之胺甲酸乙酯/多官能度胺混合物。該等微球具有15至50μm之重量平均直徑(範圍為5至200μm)。將最終混合物轉移至模具並允許其膠化約15分鐘。
之後，將該模具置於固化爐中以如下所示之周期固化：自室溫梯度升高溫度至設定點104℃，30分鐘，於104℃，15.5小時並於降低至21℃之設定點，2小時。之後，於室溫下將鑄模製品割成薄片並機械加工而於表面中製造大孔道凹槽──於較高溫度切割可改進表面粗糙度及薄片厚度均勻性。如表所示，樣品1至42表示本發明之研磨墊，樣品A至M表示比較例。
孔洞量(pore level)係如表2以標稱重量%表示以獲得更統一性地理解之孔洞體積，這是因為不同的中空微球類型及尺寸積對於相同的孔洞體積具有不同的密度。所有孔洞量皆以Expancel 551 DE40d42重量百分比表示。
對於銅研磨測試而言，實施例研磨墊厚度為80密耳(mil)(2.0毫米(mm))，開設節距為120 mil(3.0 mm)、寬為20 mil(0.51 mm)、深為30 mil(0.76 mm)之圓形凹槽以及覆加的x-y軸凹槽圖案(具有580 mil(14.7mm)節距)，並堆疊於SP2310次墊上。將該等墊於獲得自Applied Materials,Inc.之研磨機上測試。使用AD3BG150830修整盤於9磅下壓力60分鐘完成初始墊的初始運轉(break-in)，之後，使用93 rpm平臺轉速、87 rpm晶圓載體頭轉速及3磅/平方吋(psi)(20.7千帕(kPa))下壓力研磨20個銅仿真(dummy)晶圓各60秒。研磨漿料為EPL2361並以200毫升(ml)/分鐘供應於研磨墊表面上，且既用於初始墊之初始運轉又用於所有晶圓研磨。於晶圓間使用墊清洗劑EPL8105，以自墊表面去除銅殘質。
研磨銅片晶圓之研磨製程的去除率及缺陷率以上述研磨仿真晶圓之相同方法進行。使用實施例墊之每次測試亦包括使用CUP4410墊(一種具有與實施例墊所用相同之凹槽及次墊之IC1000系墊)研磨晶圓作為基準線。於所有表格中所進行的標準化係使用於該測試中使用IC1000型墊所研磨晶圓之研磨數據作為標準化的基礎，其負責一般原因所致變化。上述Diagrid修整器係用於在研磨測試中之研磨墊鑽石修整，係使用全原位修整製程(full in-situ conditioning process)，7磅(48.3 kPa)下壓力。
去除率之測量係藉由使用CDE Corporation ResMap RS200工具比較研磨前晶圓測量值與研磨後晶圓膜厚度測量值而完成。對於表3所示之墊而言，缺陷率係使用Applied Materials OrbotTM
WF-720工具以刮痕方法(scratch recipe)測量。之後，將識別出的缺陷使用萊卡顯微鏡觀察並計算刮痕、鑿孔及顫動擦痕。微刮痕及微顫動擦痕定義為<10 μm者，而刮痕及顫動擦痕定義為10 μm者。
實施例2至4之墊具有與CUP4410墊類似之去除率，但其刮痕及顫動擦痕數少於CUP4410墊之刮痕及顫動擦痕數之1/3。實施例22至28顯示高於CUP4410之去除率且實施例22至27亦顯著降低缺陷率。
對於表4所示之墊而言，以研磨表3之墊之方法進行研磨，但使用KLA-Tencor SP1TBI工具測量缺陷率，並使用上述萊卡顯微鏡進行缺陷評論。亦測試圖案化晶圓，本發明之研磨墊可提供與CUP4410墊相當或改進之平坦化、碟化及侵蝕。
實施例10至15、23、24、27、40及41之墊具有提升之去除率及顯著降低之缺陷率。實施例16至21之墊具有與CUP4410相似之去除率以及80-95%之較少缺陷。實施例29具有比CUP4410提升之去除率以及80%之較少缺陷。
將表5所示之實施例研磨墊於來自Applied Materials,Inc.之研磨機上測試，使用93 rpm之平臺轉速、87 rpm之晶圓載體頭轉速及5 psi(34.5 kPa)之下壓力研磨TEOS片晶圓。研磨漿料為ILD3225，其與去離子水形成1:1混合物並以150 ml/分鐘之速度供應於研磨墊表面上。將AD3BG150855修整盤用於研磨墊的鑽石修整，係使用原位修整製程。將TEOS片晶圓研磨30秒或60秒，使用實施例墊之每次測試亦包括使用IC1010墊研磨晶圓而作為基準線。最大重點放在相對於IC1010研磨墊之30秒研磨速度，因為較標準研磨墊它們將對於減少研磨時間具有最大的功效。研磨結果如表5所示。
與IC1010墊研磨相比，實施例22及23墊的30秒之去除率提高15%，研磨60秒之去除率提高10%，但實施例22及23墊卻提供約50%之較少缺陷。實施例27及實施例30至33之墊具有與IC1010相似之去除率但卻提供較少缺陷。
本發明之多功能聚胺脂研磨墊有助於大量研磨應用之研磨。例如，特定的PPG/PTMEG-聚胺-TDI研磨墊對高速率銅、低缺陷率銅、圖案化晶圓、TEOS、高速率TEOS、低缺陷率TEOS及STI研磨應用有效。特別地，該研磨墊可提高銅及TEOS應用之去除率且具有與單聚醇IC1000研磨墊相比為相當或提升之缺陷率。類似地，該研磨墊可降低銅及TEOS應用之缺陷率且具有與單聚醇IC1000研磨墊相比為相當或提升之去除率。
Claims (9)
- 一種適於研磨圖案化半導體基板之研磨墊，該圖案化半導體基板含有下述之至少一者：銅、電介質、阻隔及鎢，該研磨墊包括聚合物基質，該聚合物基質係由聚胺脂反應產物所組成，該聚胺脂反應產物係由聚醇共混物、聚胺或聚胺混合物及甲苯二異氰酸酯所組成，該聚醇共混物為15至77重量%之總聚丙二醇與聚四亞甲基醚二醇之混合物，且該聚丙二醇與聚四亞甲基醚二醇之混合物中聚丙二醇與聚四亞甲基醚二醇之重量比為20：1至1：20，該聚胺或聚胺混合物於液體混合物中為8至50重量%，該甲苯二異氰酸酯為20至30重量%之總甲苯二異氰酸酯單體或部分反應之甲苯二異氰酸酯單體，所有重量百分比係以該聚合物基質之總重為基準計。
- 如申請專利範圍第1項所述之研磨墊，其中，該聚丙二醇與該聚四亞甲基醚二醇之重量比為2：1至1：2。
- 如申請專利範圍第1項所述之研磨墊，其中，該聚丙二醇與該聚四亞甲基醚二醇之重量比為20：1至2：1。
- 如申請專利範圍第1項所述之研磨墊，其中，該聚丙二醇與該聚四亞甲基醚二醇之重量比為1：20至1：2。
- 如申請專利範圍第1項所述之研磨墊，其中，該研磨墊具有20至70之蕭氏D型硬度。
- 一種適於研磨圖案化半導體基板之研磨墊，該圖案化半導體基板含有下述之至少一者：銅、電介質、阻隔及鎢，該研磨墊包括聚合物基質，該聚合物基質係由聚胺脂反 應產物所組成，該聚胺脂反應產物係由聚醇共混物、聚胺或聚胺混合物及甲苯二異氰酸酯所組成，該聚醇共混物為20至75重量%之總聚丙二醇及聚四亞甲基醚二醇之混合物，該聚丙二醇及聚四亞甲基醚二醇之混合物中聚丙二醇與聚四亞甲基醚二醇之重量比為15：1至1：15，該聚胺或聚胺混合物於液體混合物中為10至45重量%，該甲苯二異氰酸酯為20至30重量%之總甲苯二異氰酸酯單體或部分反應之甲苯二異氰酸酯單體，所有重量百分比係以該聚合物基質之總重為基準計。
- 如申請專利範圍第6項所述之研磨墊，其中，該聚丙二醇與該聚四亞甲基醚二醇之重量比為15：1至2：1。
- 如申請專利範圍第6項所述之研磨墊，其中，該聚丙二醇與該聚四亞甲基醚二醇之重量比為1：15至1：2。
- 如申請專利範圍第6項所述之研磨墊，其中，該研磨墊具有20至70之蕭氏D型硬度。
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- 2010-07-22 DE DE102010031850A patent/DE102010031850A1/de active Pending
- 2010-07-23 KR KR1020100071273A patent/KR101630464B1/ko active IP Right Grant
- 2010-07-23 JP JP2010165580A patent/JP5991503B2/ja active Active
- 2010-07-23 CN CN2010102407758A patent/CN101961854A/zh active Pending
- 2010-07-26 FR FR1056116A patent/FR2948308B1/fr active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101961854A (zh) | 2011-02-02 |
| JP5991503B2 (ja) | 2016-09-14 |
| US8697239B2 (en) | 2014-04-15 |
| DE102010031850A1 (de) | 2011-01-27 |
| FR2948308A1 (fr) | 2011-01-28 |
| US20110021123A1 (en) | 2011-01-27 |
| FR2948308B1 (fr) | 2015-05-22 |
| KR20110010573A (ko) | 2011-02-01 |
| JP2011040737A (ja) | 2011-02-24 |
| TW201107081A (en) | 2011-03-01 |
| KR101630464B1 (ko) | 2016-06-14 |
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