TWI609072B - 安定可濃縮化學機械研磨組成物及其相關方法 - Google Patents
安定可濃縮化學機械研磨組成物及其相關方法 Download PDFInfo
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- TWI609072B TWI609072B TW101106931A TW101106931A TWI609072B TW I609072 B TWI609072 B TW I609072B TW 101106931 A TW101106931 A TW 101106931A TW 101106931 A TW101106931 A TW 101106931A TW I609072 B TWI609072 B TW I609072B
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- Prior art keywords
- mechanical polishing
- chemical mechanical
- water
- polishing composition
- soluble
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- 238000005498 polishing Methods 0.000 title claims description 185
- 239000000126 substance Substances 0.000 title claims description 170
- 239000000203 mixture Substances 0.000 title claims description 166
- 238000000034 method Methods 0.000 title claims description 27
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- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- 239000010949 copper Substances 0.000 claims description 37
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 35
- 239000003112 inhibitor Substances 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 29
- 229910052802 copper Inorganic materials 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 28
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims description 26
- 239000004065 semiconductor Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- 239000011574 phosphorus Substances 0.000 claims description 25
- 239000007800 oxidant agent Substances 0.000 claims description 22
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- 239000002904 solvent Substances 0.000 claims description 19
- 239000012964 benzotriazole Substances 0.000 claims description 18
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- 150000001340 alkali metals Chemical class 0.000 claims description 11
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims description 10
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 8
- 239000000347 magnesium hydroxide Substances 0.000 claims description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 8
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims description 8
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical group OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 7
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 7
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 7
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- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 7
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 7
- HRQDCDQDOPSGBR-UHFFFAOYSA-M sodium;octane-1-sulfonate Chemical group [Na+].CCCCCCCCS([O-])(=O)=O HRQDCDQDOPSGBR-UHFFFAOYSA-M 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
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- 238000007865 diluting Methods 0.000 claims description 5
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
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- 238000011068 loading method Methods 0.000 claims description 3
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 17
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- 150000003839 salts Chemical class 0.000 description 7
- -1 sodium alkyl sulfate Chemical class 0.000 description 7
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 6
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- DNUFCIOKWJELSH-UHFFFAOYSA-O diazanium dioxido(oxo)phosphanium Chemical compound [NH4+].[NH4+].[O-][P+]([O-])=O DNUFCIOKWJELSH-UHFFFAOYSA-O 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
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- SJVZUJVRHXYCSP-UHFFFAOYSA-M potassium;octane-1-sulfonate Chemical compound [K+].CCCCCCCCS([O-])(=O)=O SJVZUJVRHXYCSP-UHFFFAOYSA-M 0.000 description 1
- SDQCGKJCBWXRMK-UHFFFAOYSA-N propan-2-yl 4-methylbenzenesulfonate Chemical compound CC(C)OS(=O)(=O)C1=CC=C(C)C=C1 SDQCGKJCBWXRMK-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 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
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical compound S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- CZPRKINNVBONSF-UHFFFAOYSA-M zinc;dioxido(oxo)phosphanium Chemical compound [Zn+2].[O-][P+]([O-])=O CZPRKINNVBONSF-UHFFFAOYSA-M 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
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- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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- 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
- C09G1/16—Other polishing compositions based on non-waxy substances on natural or synthetic resins
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- 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
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- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本發明係一般有關化學機械研磨領域。具體而言,本發明係有關一種安定可濃縮化學機械研磨組成物;一種製造該化學機械研磨組成物的方法以及一種半導體材料之化學機械研磨方法,以及,更具體而言,係一種在半導體晶圓上互連金屬之化學機械研磨方法。
典型上,半導體晶圓係含有介電層的矽晶圓,該介電層含有多個溝槽,該多個溝槽經排列於該介電層中而形成供電路互連之圖案。該圖案之排列通常具有鑲嵌結構(damascene structure)或雙鑲嵌結構。阻障層(barrier layer)覆蓋該圖案化之介電層,以及金屬層覆蓋該阻障層。該金屬層具有至少足夠厚度,以使用金屬填滿該圖案化之溝槽以形成電路互連。
化學機械研磨製程通常包含多種研磨步驟。例如,第一步驟係於高初始速率移除過多的互連金屬,諸如銅。在該第一步驟移除後,第二步驟研磨可以移除殘留在於該金屬互連外之阻障層上之金屬。接續之研磨係自半導體晶圓之下方介電層移除該阻障層,以在該介電層以及該金屬互連上提供平坦的經研磨之表面。
半導體基板上溝槽或凹槽中的金屬提供形成金屬電路之金屬線。有待克服的問題之一係該研磨操作傾向於自每一個溝槽或凹槽移除金屬,造成該等金屬的下凹陷碟化
(dishing)。碟化非所欲者,蓋因其會造成該金屬電路中臨界維度(critical dimensions)之差異。為了減少碟化,研磨係於較低研磨壓力進行。然而,僅減少該研磨壓力需要使研磨持續較長的時間。然而,碟化仍將在整個延長的期間持續產生。
為了提供針對獨特之客製需求之經強化可修整性(tailorability),以及為了提供改善之物流運送性質(例如,較低運輸成本,減少之體積產量),其通常欲以濃縮形式提供化學機械研磨配方。設計用於移除過多的互連金屬用的傳統的化學機械研磨配方,典型上包含以唑為基底之抑制劑。當該等以唑為基底之抑制劑當以較高濃度被含括時,表現出聚結以及從溶液中沉澱出來的傾向。
Comeau等人揭露了一種在將BTA含括入研磨配方前先過濾BTA的製程。具體而言,Comeau等人揭露了一種用於形成研磨漿之溶液,其可包含溶在離子性界面活性劑(諸如烷基硫酸鈉溶液)中的1H-苯并三唑(BTA),以及或許為聚丙烯酸(PAA)溶液。該溶液可以被過濾以及被使用於研磨漿中。此項溶解BTA的嘗試產生在無增加外來成分至該漿料中或增加安全危險性之研磨漿中之高BTA濃度。此外,該溶液因為非常安定而易於運輸(例如,可以冷凍以及解凍),且相較傳統的嘗試具有較少的體積。更進一步地,因為已移除可能造成刮痕的粒子,使得該研磨漿之功效有著大幅改善。
Comeau等人揭露的溶液係可用在該化學機械研磨配
方製造的成分。傳統的化學機械研磨配方係用於研磨半導體晶圓金屬互連,然而,含有多種額外的成分以提供該配方所欲之研磨性質。這些額外的成分亦可在濃度上影響該最終配方之安定性。
例如,Wang在美國專利第7,086,935號中揭示用於圖案化之晶圓無研磨劑銅配方之使用,該配方含有甲基纖維素、丙烯酸/甲基丙烯酸共聚物、苯并三唑(BTA)以及可混溶(miscible)之溶劑。此配方可以在少量銅碟化下移除以及清潔銅,但在快速研磨期間,該配方在研磨墊以及晶圓上沉澱出綠色Cu-BTA化合物。這些沉澱物需要對該研磨墊進行研磨後清理(post-polishing cleaning),以避免與膠狀沉澱物有關之研磨移除速率的下降;以及該配方要求對該晶圓進行研磨後清理以避免缺陷產生。這些清潔步驟要求強力以及耗成本的清潔溶液,以及有因延遲的晶圓輸出產量所造成之相關的「所有權成本(cost of ownership)」。
一種改善之配方(緩和對該綠色沉澱物之憂慮)係揭示於Thomas等人之美國專利申請案公開第2009/0215266號。Thomas等人揭露一種以研磨墊研磨含有銅互連金屬之圖案化半導體晶圓的方法。該方法包含下列:a)提供水性研磨溶液,該研磨溶液含有苯并三唑(BTA)抑制劑以及銅錯合化合物以及水;b)用該水性研磨溶液以及該研磨墊以溶解銅形成Cu+1離子之方式研磨該圖案化之晶圓,如果該水性溶液不含有該錯合化合物,該Cu+1離子及BTA抑制劑具有之濃度為其中[BTA]*[Cu+1]>Cu-BTA沉澱物的
Ksp;以及c)氧化至少部分該銅離子以防止該研磨溶液沉澱出該Cu-BTA沉澱物。
許多傳統的化學機械研磨配方類似於那些Thomas等人例示者,含有銨及與其相關之環境與安全問題(在製造以及使用該研磨配方之期間皆是)。
因此,所需要的是一種化學機械研磨組成物以及一種含有金屬互連之圖案化之半導體晶圓的化學機械研磨的方法,其中,該化學機械研磨組成物含有唑抑制劑且係安定可濃縮;以及,較佳為無銨(即為,<0.001重量%(wt%))。
本發明係提供一種有用於化學機械研磨含有互連金屬之半導體晶圓的化學機械研磨組成物,其包括(基本上組成為)下列起始成分:水;唑抑制劑;鹼金屬有機界面活性劑;增溶劑(hydrotrope);含磷試劑;水溶性纖維素;視需要地,非醣類水溶性聚合物;視需要地,式I之水溶性酸化合物:
其中,R係選自氫以及C1-5烷基、以及其中,x係1或2;視需要地,錯合劑;視需要地,氧化劑;視需要地,有機溶劑;以及,視需要地,研磨劑。
本發明係提供一種製備本發明之化學機械研磨組成物
的方法,其包括:提供水;提供唑抑制劑;提供鹼金屬有機界面活性劑;提供增溶劑;提供含磷試劑;提供水溶性纖維素;視需要地,提供視需要的非醣類水溶性聚合物;視需要地,提供視需要的式I之水溶性酸化合物:
其中,R係選自氫以及C1-5烷基、以及其中,x係1或2;視需要地,提供視需要的錯合劑;視需要地,提供視需要的氧化劑;視需要地,提供視需要的有機溶劑;視需要地,提供視需要的研磨劑;組合該水、鹼金屬有機界面活性劑、增溶劑、水溶性纖維素、任何視需要的非醣類水溶性聚合物、任何視需要的式I之水溶性酸化合物、任何視需要的錯合劑、任何視需要的氧化劑、任何視需要的有機溶劑以及任何視需要的研磨劑而形成混合物;以及,添加該唑抑制劑以及該含磷試劑至該混合物中,而形成化學機械研磨組成物。
本發明係提供一種用於基板之化學機械研磨方法,其包括:提供基板,其中,該基板係具有銅互連之半導體晶圓;提供本發明之化學機械研磨組成物;視需要地,添加氧化劑至該化學機械研磨組成物中;提供化學機械研磨墊;以0.69至34.5千帕(kPa)之向下力在該化學機械研磨
墊以及該基板間之界面產生動態接觸;以及將該化學機械研磨組成物分注至該化學機械研磨墊上之該化學機械研磨墊與該基板間之界面處或該界面附近;其中,該化學機械研磨組成物具有透過添加磷酸、氫氧化鎂以及氫氧化鋰中之至少一種而調整至pH為2至6之pH。
本發明係提供一種用於基板之化學機械研磨方法,其包括:提供基板,其中,該基板係具有銅互連之半導體晶圓;提供呈濃縮物之本發明化學機械研磨組成物;以水稀釋該化學機械研磨組成物;視需要地,添加氧化劑至該化學機械研磨組成物中;提供化學機械研磨墊;以0.69至34.5 kPa之之向下力在該化學機械研磨墊以及該基板間之界面產生動態接觸;以及將該化學機械研磨組成物分注至該化學機械研磨墊上之該化學機械研磨墊與該基板間之界面處或該界面附近;其中,該化學機械研磨組成物具有透過添加磷酸、氫氧化鎂以及氫氧化鋰中之至少一者而調整至pH為2至6之pH。
本發明係提供一種用於基板之化學機械研磨方法,其包括:提供基板,其中,該基板係具有銅互連之半導體晶圓;提供本發明之化學機械研磨組成物,其中,該化學機械研磨組成物呈8倍濃縮物提供;以水稀釋該化學機械研磨組成物以使該稀釋後所具之起始成分之承載量如下:0.2至0.4 wt%之苯并三唑;0.05至1 wt%之辛烷磺酸鈉;0.45至1 wt%之增溶劑,其係選自甲苯磺酸鈉、二甲苯磺酸鈉以及其混合物;0.5至2 wt%之含磷試劑,其係選自磷酸三
鉀、磷酸氫二鉀、磷酸二氫鉀以及其混合物;0.1至1 wt%之羧甲基纖維素;0.05至1 wt%之甲基丙烯酸以及丙烯酸之共聚物;0.4至2 wt%之亞胺基二乙酸(imiodiacetic acid);以及,0.1至0.5 wt%之蘋果酸;添加氧化劑至該化學機械研磨組成物中;提供化學機械研磨墊;以0.69至34.5 kPa之之向下力在該化學機械研磨墊以及該基板間之界面產生動態接觸;以及將該化學機械研磨組成物分注至該化學機械研磨墊上之該化學機械研磨墊與該基板間之界面處或該界面附近;其中,該化學機械研磨組成物具有透過添加磷酸、氫氧化鎂以及氫氧化鋰中之至少一者而調整至pH為2至6之pH;以及,其中,在200毫米(mm)研磨機上,以平台(platen)平坦化速度每分鐘61轉(revolution)、載體速度每分鐘57轉、化學機械研磨組成物流動速率200毫升(ml)/分鐘、以及標稱向下力(nominal down force)13.8 kPa,該化學機械研磨組成物呈現至少4,000Å/分鐘之銅移除速率,其中該化學機械研磨墊包括含有聚合物空心(polymeric hollow)核微粒子之聚氨酯研磨層以及覆膜子墊(coated film subpad)。
本發明之化學機械研磨組成物當濃縮至>4倍(使用當下濃度)較佳為至>8倍時為安定。此特徵給予該化學機械研磨組成物重要之價值。考量到涉及之製程流量減少(亦即,減少水的體積),該機械研磨組成物使得能用較小之製造占地面積。該機械研磨組成物亦能有較低運輸以及儲存
成本。最後,該機械研磨組成物提供對末端使用者而言較佳之操作彈性,而可在使用當下客製化學機械研磨,以符合他們的獨特操作要求。
本說明書以及隨附之申請專利範圍裡,關於本發明之化學機械研磨組成物的使用中,術語「可濃縮」意指該化學機械研磨組成物可以以較少的水被製造,儲存以及運輸,該較少水量係相較於其在使用當下包含在該化學機械研磨組成物中之水量而言。
本說明書以及隨附之申請專利範圍裡,關於本發明之化學機械研磨組成物的使用中,術語「使用當下(point of use)」意指該化學機械研磨組成物用於研磨基板之時間點。
本說明書以及隨附之申請專利範圍裡,關於本發明之化學機械研磨組成物的使用中,術語「無銨」意指該化學機械研磨組成物含有<0.001 wt%的銨(更佳為,<0.0001 wt%的銨)。
本發明之化學機械研磨組成物係可濃縮以及在濃縮形式保持安定。例如,本發明之化學機械研磨組成物可呈>4倍使用當下(較佳為>8倍)濃縮物提供(參照,例如,實施例中的表3)。為了達到使本發明更易於明瞭之目的,將在此詳述有關於本發明之化學機械研磨組成物之使用當下之組成物。然而,本領域中具有通常技術者將理解如何改變本發明之化學機械研磨組成物的配方成其濃縮物(亦即,該化學機械研磨組成物之濃縮形式)。
用於本發明之該化學機械研磨方法之化學機械研磨組
成物之特定配方的選擇,係提供目標金屬互連移除速率及可濃縮性以及安定性兩者之關鍵。
適用於本發明之該化學機械研磨方法的化學機械研磨用基板包括半導體基板,較佳為具有金屬互連(諸如銅或銅合金)的半導體基板;更佳為具有金屬互連(諸如具有銅或銅合金及下方介電層)的半導體基板。
本發明之化學機械研磨組成物較佳依賴餘量之去離子水或蒸餾水,以限制意外雜質。
本發明之化學機械研磨組成物含有抑制劑,以控制藉由靜態蝕刻(static etch)或其他移除機制進行之非鐵金屬移除速率,諸如銅互連移除速率。調整該抑制劑之濃度而藉由保護該金屬免於被靜態蝕刻而調整該互連金屬移除速率。較佳為該化學機械研磨組成物含有0.01至15 wt%,更佳為0.1至5 wt%,尤佳為0.2至0.4 wt%的抑制劑。最佳為該化學機械研磨組成物含有0.2至1.0 wt%抑制劑。視需要地,該抑制劑包括抑制劑之混合物。較佳為該抑制劑係選自唑抑制劑,其對於研磨具有銅以及銀互連的晶圓特別有效。更佳為該抑制劑係選自苯并三唑(BTA)、巰基苯并三唑(MBT)、甲苯并三唑(tolytriazole,TTA)、咪唑以及其組合物。唑抑制劑組合物可以增加或減少銅移除速率。最佳為該抑制劑係BTA,其為對銅以及銀特別有效之抑制劑。
本發明之化學機械研磨組成物包括界面活性劑。較佳為該化學機械研磨組成物包括0.01至5 wt%,更佳為0.05
至1 wt%,尤佳為0.1至1 wt%,最佳為0.2至0.8 wt%之界面活性劑。較佳為該界面活性劑係鹼金屬有機磺酸鹽。更佳為該界面活性劑係鹼金屬有機磺酸鹽,其中,該鹼金屬係選自鈉、鉀、鋰以及鎂;以及,其中,該有機部份係具有2至16個碳原子的脂族基。尤佳為該界面活性劑係選自辛烷磺酸鈉、辛烷磺酸鉀、辛烷磺酸鋰、十二烷磺酸鈉、十二烷磺酸鉀以及十二烷磺酸鋰。最佳為該界面活性劑係辛烷磺酸鈉。
本發明之化學機械研磨組成物較佳為包括增溶劑。較佳為該化學機械研磨組成物包括0.05至5 wt%,更佳為0.1至5 wt%,尤佳為0.1至1 wt%,最佳為0.45至1 wt%增溶劑。較佳為該增溶劑係選自苯磺酸鹽、烷基苯磺酸鹽類(例如,甲苯磺酸鹽、異丙苯磺酸鹽(cumene sulfonate))以及二烷基苯磺酸鹽類(例如,二甲苯磺酸鹽、異丙基甲苯磺酸鹽(cymene sulfonate))以及其鹽類。更佳為,該增溶劑係選自苯磺酸鹽;甲苯磺酸鹽;異丙苯磺酸鹽;二甲苯磺酸鹽;異丙基甲苯磺酸鹽;以及,其鈉、鋰、鈣、鉀以及銨鹽類。尤佳為本發明之無銨化學機械研磨組成物中,該增溶劑係選自苯磺酸鹽;甲苯磺酸鹽;異丙苯磺酸鹽;二甲苯磺酸鹽;異丙基甲苯磺酸鹽;以及,其鈉、鋰、鈣以及鉀鹽類。尤尚佳為該增溶劑係選自甲苯磺酸鈉以及二甲苯磺酸鈉。最佳為該增溶劑係二甲苯磺酸鈉。
本發明之化學機械研磨組成物包含含磷化合物。較佳為該化學機械研磨組成物包括0.01至15 wt%,更佳為0.05
至10 wt%,尤佳為0.1至5 wt%,最佳為0.5至2 wt%的含磷化合物。為達本說明書之目的,「含磷」化合物係任何含有磷原子的化合物。較佳為該含磷化合物係選自磷酸化合物(phosphate)、焦磷酸化合物(pyrophosphate)、多磷酸化合物(polyphosphate)、膦酸化合物(phosphonate),包含其酸類、鹽類、混合酸鹽類、酯類、偏酯(partial ester)類、混合酯類、以及其混合物。更佳為該含磷化合物係選自磷酸鋅、焦磷酸鋅、多磷酸鋅、膦酸鋅、磷酸二氫銨、磷酸氫二銨、磷酸三銨、焦磷酸銨、多磷酸銨、膦酸銨、膦酸二銨、焦磷酸二銨、多磷酸二銨、膦酸二銨、磷酸胍、焦磷酸胍、多磷酸胍、膦酸胍、磷酸鐵、焦磷酸鐵、多磷酸鐵、膦酸鐵、磷酸鈰、焦磷酸鈰、多磷酸鈰、膦酸鈰、磷酸伸乙二胺、磷酸哌(piperazine phosphate)、焦磷酸哌、膦酸哌、磷酸三聚氰胺、磷酸二(三聚氰胺)、焦磷酸三聚氰胺、多磷酸三聚氰胺、膦酸三聚氰胺、磷酸蜜白胺(melam phosphate)、焦磷酸蜜白胺(melam pyrophosphate)、多磷酸蜜白胺(melam polyphosphate)、膦酸蜜白胺(melam phosphonate)、磷酸蜜勒胺(melem phosphate)、焦磷酸蜜勒胺(melem pyrophosphate)、多磷酸蜜勒胺(melam polyphosphate)、膦酸蜜勒胺(melam phosphonate)、磷酸雙氰胺(dicyanodiamide phosphate)、磷酸脲、磷酸鉀、其等之酸類、鹽類、混合酸鹽類、酯類、偏酯類、混合酯類、以及其混合物。尤佳為該含磷化合物係選自氧化膦(phosphine oxide),硫化膦以及磷雜環己烷(phosphorinanes)
以及膦酸酯、亞磷酸酯(phosphite)以及次磷酸酯(phosphinate)、其等之酸類、鹽類、混合酸鹽類、酯類、偏酯類以及混合酯類。尚更佳為該含磷化合物係選自磷酸三銨、磷酸氫二銨、磷酸二氫銨、磷酸三鉀、磷酸氫二鉀、磷酸二氫鉀以及其組合物。尤尚佳為該含磷化合物係選自磷酸二氫銨、磷酸三鉀、磷酸氫二鉀、磷酸二氫鉀。最佳為該化學機械研磨組成物係無銨,其中,該含磷化合物係選自磷酸三鉀、磷酸氫二鉀、磷酸二氫鉀以及其混合物。
本發明之化學機械研磨組成物含有水溶性纖維素。較佳為該化學機械研磨組成物含有0.05至15 wt%,更佳為0.1至5 wt%,尤佳為0.1至1 wt%之水溶性纖維素。較佳為該水溶性纖維素係以羧酸官能性改性之水溶性改性纖維素。例示性改性纖維素包含陰離子性膠,諸如下列中至少一者:瓊脂膠、阿拉伯膠、甘地膠(ghatti gum)、刺梧桐膠(karaya gum)、古亞膠(guar gum)、果膠、刺槐豆膠(locust bean gum)、黃蓍膠(tragacanthgum)、羅晃子膠(tamarind gum)、鹿角菜膠(carrageenan gum)、以及三仙膠(xantham gum)、改性澱粉、海藻酸、甘露糖醛酸(mannuronic aicd)、古羅糖醛酸(guluronic aicd)、以及其衍生物以及共聚物。最佳為該水溶性改性纖維素係羧甲基纖維素(CMC)。較佳為該CMC具有0.1至3.0的取代度及1,000至1,000,000的重量平均分子量(Mw),更佳為該CMC具有0.7至1.2的取代度及40,000至250,000的重量平均分子量。為達本說明書之目的,CMC之取代度係纖維素分子中每一個脫水
葡萄糖單元上羥基被取代之數目。該取代度可以被想作為該CMC中羧酸基的「密度」的度量。
本發明之化學機械研磨組成物視需要地含有非醣類水溶性聚合物。該化學機械研磨組成物含有0至5 wt%,較佳為0.05至5 wt%,更佳為0.05至3 wt%,最佳為0.05至1 wt%非醣類水溶性聚合物。
該非醣類水溶性聚合物較佳包含丙烯酸聚合物、甲基丙烯酸聚合物以及利用丙烯酸單體或甲基丙烯酸單體合成之共聚物。為達本說明書之目的,該非醣類水溶性聚合物亦包含多種分子量之聚合物以及低分子量之寡聚合物。共聚物包含那些形成自丙烯酸以及甲基丙烯酸之組合者;以及具體而言,形成自莫耳比在1:30至30:1之範圍;較佳為在1:9至9:1之範圍;以及最佳為約2:3之丙烯酸與甲基丙烯酸之共聚物。該共聚物較佳具有在1K至1000K之範圍(K=千)之重量平均分子量;較佳為在10K至500K之範圍。
或者,該非醣類水溶性聚合物係兩性聚合物,諸如形成自丙烯酸或甲基丙烯酸的共聚物。本說明書中所稱之兩性聚合物係由親水性片段以及疏水性片段組成之嵌段共聚物(block copolymer)。該疏水性片段可以為碳數於2至250變化之聚合鏈片段。為達本說明書之目的,碳數係表示親水性片段之碳原子數目。較佳為該碳數係5至100以及最佳為5至50。該親水性片段係離子性。該親水性片段之單體單元的數量較佳為於1至100變化。
該兩性聚合物之較佳的數目平均分子量係50至5,000,本說明書中之兩性聚合物係以其數目平均分子量標示以及具體為藉由使用配有折射率檢測器以及磷酸鈉緩衝洗提液之TSK-GEL pn/08025 GMPWx以及TSK-GEL pn/08020 G2500PWx串聯管柱,進行水性膠滲透層析鑑定。更佳為該數目平均分子量介於50以及4,000之間以及最佳為該數目平均分子量介於100以及3,000之間。離子性片段包含陽離子性、陰離子性、以及兩性離子(聚兩性電解質以及聚甜菜鹼)。較佳為該親水性片段係陰離子性,諸如,聚丙烯酸或聚甲基丙烯酸。該親水性片段較佳為含有聚丙烯酸、聚甲基丙烯酸或丙烯酸以及甲基丙烯酸之共聚物。該等片段組合而成之共聚物製造出與其分別之均聚物(homopolymers)不同的性質,其易於清理而無過多的金屬互連的碟化。該聚合物之疏水性端可包含烴鏈或烷基硫醇。最佳為該疏水性以及親水性片段以嵌段共聚物之形態組合。
本發明之化學機械研磨組成物視需要地含有依據式I之水溶性酸化合物:
其中,R係選自氫以及C1-5烷基、以及其中,x係1或2。較佳為該化學機械研磨組成物含有0至10 wt%;較佳為0.05至5 wt%,更佳為0.4至2 wt%之式I之水溶性酸化合物。較佳為該式I之水溶性酸化合物係選自亞胺基二乙酸(IDA)、乙二胺四乙酸(EDTA)、以及其組合物。最佳為該式I之水溶性酸化合物係IDA。
該式I之水溶性酸化合物有能力錯合具有單價(+1)的銅離子以及二價(+2)銅離子。於研磨期間,該水溶性酸化合物傾向與足夠數量之銅離子錯合以減少Cu-BTA沉澱物之形成以及控制該Cu+2離子之形成速率,如下列式(2)所示:2Cu+ → Cu0+Cu+2 (2)
為達本說明書之目的,Cu-BTA沉澱物包含非液體,諸如固體、膠體以及聚合物,且可包含Cu+2離子、尖晶石(spinel)沉澱物、類尖晶石沉澱物以及雜質。自研磨經驗來看,當該銅離子(+1)以及BTA之濃度之乘積在該研磨條件下超過Ksp時,會形成不可溶之Cu-BTA沉澱物。該Cu-BTA在酸性研磨溶液中發生沈澱一事係遵循下列平衡式(1):BTAH+Cu+ ← (慢) (快) → Cu-BTA+H+ (1)
本發明之化學機械研磨組成物視需要地含有非鐵金屬之錯合劑。該錯合劑可以促進金屬膜(諸如銅)之移除速率。較佳為該化學機械研磨組成物含有0至15 wt%,更佳為0.01至5 wt%,尤佳為0.1至5 wt%,最佳為0.1至0.5 wt%之錯合劑。例示性錯合劑包含,例如,乙酸、檸檬酸、乙醯乙酸乙酯、甘醇酸、乳酸、蘋果酸、草酸、水楊酸、
二乙基二硫代胺基甲酸鈉(sodium diethyl dithiocarbamate)、琥珀酸、酒石酸、硫代甘醇酸、甘胺酸、丙胺酸、天門冬胺酸、伸乙基二胺、三甲基二胺、丙二酸、戊二酸、3-羥基丁酸、丙酸、酞酸、異酞酸、3-羥基水楊酸、3,5-二羥基水楊酸、五倍子酸(gallic acid)、葡萄糖酸、兒茶酚(pyrocatechol)、五倍子酚(pyrogallol)、鞣酸(tannic acid)、包含其鹽類以及混合物。較佳為該錯合劑係選自乙酸、檸檬酸、乙醯乙酸乙酯、甘醇酸、乳酸、蘋果酸、草酸以及其組合物。最佳為該錯合劑係蘋果酸。
本發明之化學機械研磨組成物視需要地含有氧化劑。在一些具體實施例中,該化學機械研磨組成物含有0至25 wt%,較佳為1至15 wt%,更佳為5至10 wt%之氧化劑。在一些具體實施例中該氧化劑係選自過氧化氫(H2O2)、單過硫酸鹽、碘酸鹽,過酞鎂、過乙酸以及其他的過酸、過硫酸鹽、溴酸鹽、過碘酸鹽、硝酸鹽、鐵鹽、鈰鹽、Mn(III)鹽、Mn(IV)鹽、Mn(VI)鹽、銀鹽、銅鹽、鉻鹽、鈷鹽、鹵素、次氯酸鹽以及其混合物。在一些具體實施例中,該氧化劑係過氧化氫。當該化學機械研磨組成物含有非安定氧化試劑(諸如過氧化氫)時,其係較佳在使用當下將該氧化劑包含在該化學機械研磨組成物中。
本發明之化學機械研磨組成物視需要地含有可與水混溶之醇或酮。該可與水混溶之醇或酮,在經改性之纖維素化合物存在時,幫助促進可接受之金屬移除速率以及以低碟化清潔銅金屬。典型上,可與水混溶之醇或酮包含下列
至少一者:甲醇、乙醇、1-丙醇、2-丙醇、乙二醇、1,2-丙二醇、丙三醇、丙酮、以及甲基乙基酮。較佳為該組成物含有0至10 wt%,更佳為0.005至10 wt%,尤佳為0.01至7.5 wt%,最佳為0.02至5 wt%之可與水混溶之醇或酮。
本發明之化學機械研磨組成物視需要地含有0至3 wt%研磨劑以促進金屬層移除。在此範圍內,其欲具有以少於或等於1重量百分比的量存在之研磨劑。最佳為該研磨組成物係無研磨劑。
該研磨劑具有小於或等於500奈米(nm)之平均粒徑以防止過多的金屬碟化及介電質侵蝕並改善平坦化。為達本說明書之目的,粒徑意指該研磨劑之平均粒徑。更佳為,其欲使用具有少於或等於100nm之平均粒徑之膠體研磨劑。再者,在膠體氧化矽(colloidal silica)具有小於或等於70nm之平均粒徑時發生所欲之減少的介電質侵蝕以及金屬碟化。此外,該較佳之膠體研磨劑可包含添加劑,諸如分散劑、界面活性劑、緩衝劑、以及殺生物劑以提升該膠體研磨劑之安定性。一種這樣的矽體石研磨劑膠體氧化矽,取自Clariant S.A.(Puteaux,France)。亦可利用其他的研磨劑,包含那些研磨劑的燻型(fumed)、沉澱型、聚結型研磨劑等。
該化學機械研磨組成物視需要地包含用於金屬互連層之「機械」移除的研磨劑。研磨劑之例包含無機氧化物、無機氫氧化物、無機氫氧化物氧化物(inorganic hydroxide oxide)、金屬硼化物、金屬碳化物、金屬氮化物、聚合物
粒子以及包括該前述者中之至少一者的混合物。適合的無機氧化物包含,例如,氧化矽(SiO2)、礬土(Al2O3)、氧化鋯(ZrO2)、二氧化鈰(CeO2)、二氧化錳(MnO2)、二氧化鈦(TiO2)或包括該前述氧化物中之至少一者的組合物。適合的無機氫氧化物氧化物包含,例如,氫氧化鋁氧化物(「水鋁礦」,(boehmite))。若有需要,亦可利用該等無機氧化物之改性型式(modified form),諸如,塗佈有機聚合物之無機氧化物粒子以及塗佈無機之粒子。適合的金屬碳化物、硼化物以及氮化物包含,例如,碳化矽、氮化矽、碳氮化矽(SiCN)、碳化硼、碳化鎢、碳化鋯、硼化鋁、碳化鉭、碳化鈦,或包括該前述金屬碳化物、硼化物以及氮化物中至少一者的組合物。若有需要,亦可使用金剛石作為研磨劑。替代性研磨劑亦包含聚合物粒子、經塗佈聚合物粒子、以及界面活性劑安定粒子。若有利用研磨劑的話,該較佳之研磨劑係氧化矽。
本發明之化學機械研磨組成物在廣泛pH範圍內皆提供功效。本發明之化學機械研磨組成物之有用的pH範圍自2延伸至5。在本發明一些具體實施例中,該化學機械研磨組成物在使用當下呈現pH係2至5,較佳為2至4,更佳為2.5至4。適合用於調整本發明之化學機械研磨組成物之pH之酸類包含,例如,硝酸、硫酸、鹽酸、以及磷酸;較佳為磷酸。適合用於調整本發明之化學機械研磨組成物之pH之鹼類包含,例如,氫氧化銨、氫氧化鎂、氫氧化鋰以及氫氧化鉀。較佳為本發明之化學機械研磨組
成物係無銨,其中,適合用於調整該pH之鹼類係選自氫氧化鎂以及氫氧化鋰。
本發明之化學機械研磨組成物較佳為在濃縮形式(即為,在>4倍使用當下濃度;更佳為在>8倍使用當下濃度)呈現儲存安定性。本說明書以及隨附之申請專利範圍裡,術語「儲存安定性」意指該濃縮物儲存在55℃至少5天後仍保持視覺上澄清且無觀察到固體沉澱出。
在製備本發明之化學機械研磨組成物的方法中,該化學機械研磨組成物之多種成分係較佳為依順序組合在一起,該順序使得最大化其中將添加有唑抑制劑以及含磷試劑之水之體積。最佳為該唑抑制劑以及該含磷試劑係最後添加至本發明之化學機械研磨組成物的製備的成分。
較佳為在本發明之用於基板之化學機械研磨方法中,其包括:提供基板;提供本發明之化學機械研磨組成物;視需要地,添加氧化劑至該化學機械研磨組成物中;提供化學機械研磨墊;以0.69至34.5 kPa之向下力在該化學機械研磨墊以及該基板間之界面產生動態接觸;以及將該化學機械研磨組成物分注至該化學機械研磨墊上之該化學機械研磨墊與該基板間之界面處或該界面附近;其中,該化學機械研磨組成物具有透過添加磷酸、氫氧化鎂以及氫氧化鋰中之至少一種而調整至pH為2至6之pH。該基板係半導體基板。較佳為該基板係具有金屬互連之半導體基板,該金屬互連諸如銅、銀、鋁、鎢、鉑、鈀、金、銥以及其合金(更佳為銅或銅合金)。尤佳為該基板係具有金屬
互連及下方介電層之半導體基板。最佳為該基板係具有銅互連及下方介電層之半導體基板。為達本說明書之目的,術語介電質意指具有介電常數(k)之半導體材料,包含低k以及超低k介電材料。本發明之化學機械研磨組成物以及方法係對防止多種晶圓要素之侵蝕優異者,該等晶圓要素諸如,多孔以及非多孔低k介電質、有機以及無機低k介電質、有機矽酸鹽玻璃(OSG)、氟矽酸鹽玻璃(FSG)、碳摻雜氧化物(CDO)、四乙基原矽酸鹽(TEOS)以及衍生自TEOS的氧化矽。本發明之化學機械研磨組成物亦可用於電化學機械研磨(ECMP)。
較佳為在本發明之方法中,本發明之化學機械研磨組成物係以濃縮物提供(更佳為>4倍使用當下濃度之濃縮物;最佳為>8倍使用當下濃度之濃縮物);其中,該方法復包括:以水稀釋該化學機械研磨組成物;視需要地,添加氧化劑至該化學機械研磨組成物中;提供化學機械研磨墊;以0.69至34.5 kPa之向下力在該化學機械研磨墊以及該基板間之界面產生動態接觸;以及將該化學機械研磨組成物分注至該化學機械研磨墊上之該化學機械研磨墊與該基板間之界面處或該界面附近;其中,該化學機械研磨組成物具有透過添加磷酸、氫氧化鎂以及氫氧化鋰中之至少一種而調整pH至pH為2至6之pH。
較佳為在本發明用於該基板之化學機械研磨之方法中,其包括:提供基板,其中,該基板係具有銅互連之半導體晶圓;提供本發明之化學機械研磨組成物,其中,該
化學機械研磨組成物以8倍濃縮物提供之;以水稀釋該化學機械研磨組成物,以使稀釋後之起始成分之承載量如下所示:0.2至0.4 wt%之苯并三唑;0.05至1 wt%之辛烷磺酸鈉;0.45至1 wt%之增溶劑,其係選自甲苯磺酸鈉、二甲苯磺酸鈉以及其混合物;0.5至2 wt%之含磷試劑,其係選自磷酸三鉀、磷酸氫二鉀、磷酸二氫鉀以及其混合物;0.1至1 wt%之羧甲基纖維素;0.05至1 wt%之甲基丙烯酸以及丙烯酸之共聚物;0.4至2 wt%之亞胺基二乙酸;以及,0.1至0.5 wt%之蘋果酸;添加氧化劑至該化學機械研磨組成物中;提供化學機械研磨墊;以0.69至34.5 kPa之向下力在該化學機械研磨墊以及該基板間之界面產生動態接觸;以及將該化學機械研磨組成物分注至該化學機械研磨墊上之該化學機械研磨墊與該基板間之界面處或該界面附近;其中,該化學機械研磨組成物具有透過添加磷酸、氫氧化鎂以及氫氧化鋰中之至少一者而調整至pH為2至6之pH;以及,其中,該化學機械研磨組成物在200mm研磨機上以平台每分鐘61轉、載體速度每分鐘57轉、化學機械研磨組成物流動速率200ml/分鐘、以及標稱向下施力(nominal down force)13.8 kPa之下呈現至少4,000Å/分鐘之銅移除速率,其中該化學機械研磨墊包括含有聚合物空心核微粒子之聚氨酯研磨層以及覆膜子墊。
本發明之化學機械研磨組成物以及方法係特別有用於具有銅互連的半導體晶圓之化學機械研磨,較佳為具有銅互連及下方介電層。即使,咸信本發明之化學機械研磨組
成物亦適合於研磨含有其他導體金屬互連,諸如鋁、鎢、鉑、鈀、金、或銥;阻障層或線性膜,諸如鉭、氮化鉭、鈦、或氮化鈦;以及下方介電層的半導體晶圓。為達本說明書之目的,術語介電質意指具介電常數(k)之半導體材料,其包含低k以及超低k介電材料。本發明之化學機械研磨組成物以及方法係對防止多種晶圓要素之侵蝕優異者,該等晶圓要素諸如,多孔以及非多孔低k介電質、有機以及無機低k介電質、有機矽酸鹽玻璃(OSG)、氟矽酸鹽玻璃(FSG)、碳摻雜氧化物(CDO)、四乙基原矽酸鹽(TEOS)以及衍生自TEOS的氧化矽。本發明之化學機械研磨組成物亦可用於電化學機械研磨(ECMP)。
下列實施例中將詳細描述一些本發明之具體實施例。
(以下又分別稱為PA、PB及SC)
被用於研磨比較實施例PA至PB以及研磨實施例P1至P17以及該安定性比較實施例SC以及安定性實施例S1至S17的化學機械研磨組成物係藉由組合列於表1的成分與量製備(以及該研磨比較實施例PA至PB及研磨實施例P1至P17復添加H2O2至9 wt%濃度)。
每個實施例中之研磨實驗係使用表2所述之配方(於研磨前將濃縮之配方稀釋至1X POU濃度)在銅覆晶圓上進行研磨。在裝設有ISRM偵測系統之Applied materials,Inc.Reflexion 200mm研磨機上,使用取得自羅門哈斯電子材料CMP公司之有K7細溝槽圖案之VisionPadTM5000聚氨酯研磨墊,以向下力條件為2.0磅/平方英吋(psi)(13.8 kPa)、研磨溶液流動速率為200ml/分鐘,平台速度為每分鐘61轉(61 RPM)、以及載體速度為57 RPM,伴隨研磨溶液施加在自該研磨墊中心3.5吋(8.89公分)之處研磨。使用Diagrid® AD3BG-150855金剛石墊修整器(conditioner)(可自Kinik Company商購取得)修整該研磨墊。於研磨前,在該修整器中使用向下力為9.0 psi(62.1 kPa),20分鐘,接著向下力為7.0 psi(48.3 kPa)20分鐘切入(break in)該研磨墊。在一晶圓與下一晶圓間,進一步使用向下力7.0為psi(48.3 kPa)修整該研磨墊。該銅移除速度係使用Jordan Valley JVX-5200T測量工具予以測量。該結果係提供於表2。
表3所述的研磨組成物的安定性係藉由將所述之樣品儲存在所述之溫度下五天以及觀察經老化材料的澄清度來評估。非安定配方一旦儲存在所述之條件下,將觀察到變成混濁或形成沉澱物。
Claims (7)
- 一種有用於化學機械研磨含有互連金屬之半導體晶圓的化學機械研磨組成物,其包括下列起始成分:水;唑抑制劑;鹼金屬有機界面活性劑,其中,該鹼金屬有機界面活性劑為辛烷磺酸鈉;增溶劑,其係選自甲苯磺酸鈉、二甲苯磺酸鈉以及其混合物之群組;含磷試劑;水溶性纖維素;視需要地,非醣類水溶性聚合物;視需要地,式I之水溶性酸化合物:
- 如申請專利範圍第1項所述之化學機械研磨組成物,其中,該化學機械研磨組成物包括下列起始成分:水;0.1至5wt%之該唑抑制劑;0.05至1wt%之該辛烷磺酸鈉;0.05至5wt%之該增溶劑,其係選自甲苯磺酸鈉、二甲苯磺酸鈉以及其混合物之群組;0.1至5wt%之該含磷試劑;0.1至5wt%之該水溶性纖維素;0.05至5wt%之該非醣類水溶性聚合物;0.05至5wt%之式I之該水溶性酸化合物:
- 如申請專利範圍第1項所述之化學機械研磨組成物,其中,該化學機械研磨組成物包括下列起始成分:水;0.1至5wt%之該唑抑制劑,其中,該唑抑制劑為苯并三唑;0.05至1wt%之該辛烷磺酸鈉;0.1至1wt%之該增溶劑,其係選自甲苯磺酸鈉、二甲苯磺酸鈉以及其混合物之群組;0.1至5wt%之該含磷試劑,其中,該含磷試劑係選自磷酸三鉀、磷酸氫二鉀、磷酸二氫鉀以及其混合物之群組;以及0.1至5wt%之該水溶性纖維素,其中,該水溶性纖維素為羧甲基纖維素;0.05至3wt%之該非醣類水溶性聚合物,其中,該非醣類水溶性聚合物為甲基丙烯酸以及丙烯酸之共聚物;0.05至5wt%之式I之該水溶性酸化合物,其中,該式I之水溶性酸化合物為亞胺基二乙酸;0.1至5wt%之該錯合劑,其中,該錯合劑為蘋果酸;以及 0至25wt%之該氧化劑;其中,該化學機械研磨組成物含有<0.001wt%的銨。
- 一種製備申請專利範圍第1項所述之化學機械研磨組成物的方法,其包括:提供水;提供唑抑制劑;提供鹼金屬有機界面活性劑,其中,該鹼金屬有機界面活性劑為辛烷磺酸鈉;提供增溶劑,其中,該增溶劑係選自甲苯磺酸鈉、二甲苯磺酸鈉以及其混合物之群組;提供含磷試劑;提供水溶性纖維素;視需要地,提供視需要的非醣類水溶性聚合物;視需要地,提供視需要的式I之水溶性酸化合物:
- 一種用於基板之化學機械研磨方法,其包括:提供基板,其中,該基板係具有銅互連之半導體晶圓;提供申請專利範圍第1項所述之化學機械研磨組成物;視需要地,添加氧化劑至該化學機械研磨組成物中;提供化學機械研磨墊;以0.69至34.5kPa之向下力在該化學機械研磨墊以及該基板間之界面產生動態接觸;以及將該化學機械研磨組成物分注至該化學機械研磨墊上之該化學機械研磨墊與該基板間之該界面處或該界面附近;其中,該化學機械研磨組成物具有透過添加磷 酸、氫氧化鎂以及氫氧化鋰中之至少一種而調整至pH為2至6之pH。
- 如申請專利範圍第5項所述之化學機械研磨方法,其中,所提供之該化學機械研磨組成物係濃縮形式;以及其中,該方法復包括:以水稀釋該化學機械研磨組成物。
- 如申請專利範圍第5項所述之化學機械研磨方法,其中,該化學機械研磨組成物以8倍濃縮物提供;以及其中,該方法復包括:以水稀釋該化學機械研磨組成物以使稀釋後之起始成分之承載量如下所示:0.2至0.4wt%之唑抑制劑,其中,該唑抑制劑為苯并三唑;0.05至1wt%之辛烷磺酸鈉;0.45至1wt%之增溶劑,其係選自甲苯磺酸鈉、二甲苯磺酸鈉以及其混合物之群組;0.5至2wt%之含磷試劑,其中,該含磷試劑係選自磷酸三鉀、磷酸氫二鉀、磷酸二氫鉀以及其混合物之群組;0.1至1wt%之水溶性纖維素,其中,該水溶性纖維素為羧甲基纖維素;0.05至1wt%之非醣類水溶性聚合物,其中,該非醣類水溶性聚合物為甲基丙烯酸以及丙烯酸之共聚物; 0.4至2wt%之式I之水溶性酸化合物,其中,該式I之水溶性酸化合物為亞胺基二乙酸;以及0.1至0.5wt%之錯合劑,其中,該錯合劑為蘋果酸;以及添加氧化劑至該化學機械研磨組成物中。
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WO2014045937A1 (ja) * | 2012-09-18 | 2014-03-27 | 株式会社フジミインコーポレーテッド | 研磨用組成物 |
JP6549927B2 (ja) * | 2015-07-24 | 2019-07-24 | 株式会社ディスコ | ホウ素化合物を添加した切削砥石 |
KR102649676B1 (ko) | 2017-03-14 | 2024-03-21 | 가부시키가이샤 후지미인코퍼레이티드 | 연마용 조성물, 그 제조 방법, 그리고 이것을 사용한 연마 방법 및 기판의 제조 방법 |
KR102611598B1 (ko) * | 2017-04-27 | 2023-12-08 | 주식회사 동진쎄미켐 | 화학-기계적 연마용 슬러리 조성물 |
WO2020091242A1 (ko) * | 2018-10-31 | 2020-05-07 | 영창케미칼 주식회사 | 구리 배리어층 연마용 슬러리 조성물 |
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CN112920716A (zh) * | 2021-01-26 | 2021-06-08 | 中国科学院上海微系统与信息技术研究所 | 一种用于氮化钛化学机械抛光的组合物及其使用方法 |
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FR2972196A1 (fr) | 2012-09-07 |
FR2972196B1 (fr) | 2017-05-19 |
US8435896B2 (en) | 2013-05-07 |
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