CN101760137A - 去除聚合物阻挡层的抛光浆液 - Google Patents
去除聚合物阻挡层的抛光浆液 Download PDFInfo
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- CN101760137A CN101760137A CN200910265947A CN200910265947A CN101760137A CN 101760137 A CN101760137 A CN 101760137A CN 200910265947 A CN200910265947 A CN 200910265947A CN 200910265947 A CN200910265947 A CN 200910265947A CN 101760137 A CN101760137 A CN 101760137A
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- 239000002002 slurry Substances 0.000 title claims abstract description 52
- 238000005498 polishing Methods 0.000 title claims abstract description 46
- 230000004888 barrier function Effects 0.000 title description 19
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims abstract description 25
- 239000004065 semiconductor Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
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- 230000003068 static effect Effects 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 230000000903 blocking effect Effects 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
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- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
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- 239000003989 dielectric material Substances 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
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- 239000000084 colloidal system Substances 0.000 claims description 9
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 9
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- 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 4
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- ZZTURJAZCMUWEP-UHFFFAOYSA-N diaminomethylideneazanium;hydrogen sulfate Chemical compound NC(N)=N.OS(O)(=O)=O ZZTURJAZCMUWEP-UHFFFAOYSA-N 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- APLYTANMTDCWTA-UHFFFAOYSA-L magnesium;phthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O APLYTANMTDCWTA-UHFFFAOYSA-L 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
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- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
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- 150000007524 organic acids Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
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- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical compound C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- 150000003112 potassium compounds Chemical class 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 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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- 230000002829 reductive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 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
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical compound S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 description 1
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- 235000015523 tannic acid Nutrition 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
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- 229940095064 tartrate Drugs 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
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- CZPRKINNVBONSF-UHFFFAOYSA-M zinc;dioxido(oxo)phosphanium Chemical compound [Zn+2].[O-][P+]([O-])=O CZPRKINNVBONSF-UHFFFAOYSA-M 0.000 description 1
Classifications
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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
- 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
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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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
- 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
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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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
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- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (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)
Abstract
一种水性浆液,可用来对包含铜互连的半导体基片进行化学机械抛光。所述抛光浆液包含:0-25重量%的氧化剂,1-50重量%的磨粒,0.001-10重量%的用来减少铜互连的静态蚀刻的抑制剂,0.001-5重量%的具有以下结构式的聚(甲基乙烯基醚):
Description
技术领域
本发明涉及一种可用来对包含铜互连的半导体基片进行化学机械抛光的水性浆液以及一种使用该水性浆液对包含铜互连的半导体基片进行化学机械抛光的方法。
背景技术
随着超大规模集成电路(ULSI)技术向着更小的线宽发展,对常规的化学机械抛光(CMP)法的一体化提出了新的挑战。另外,要引入低k和超低k电介质膜,需要使用更温和的CMP工艺,这是因为这些膜的机械强度低,与相邻层的粘着性较差。另外,针对缺陷的日益严格的技术要求对用于低k膜的抛光浆液提出了另外的要求。
将各种低k膜结合到ULSI中可能需要许多额外的步骤,还需要引入新的技术,例如超临界清洁、电介质和金属覆盖层、共形沉积阻挡层和铜、用低的向下作用力和无磨料浆液进行化学机械平面化。除了这些技术选择以外,ULSI制造者必需针对产量、可靠性、机械强度和性能(即电阻-电容(RC)延迟造成的功率耗散)考虑和解决工艺复杂性的问题。
围绕实施低k材料的复杂性为阻挡层CMP工艺带来了更大的挑战,因此需要能够控制复杂的输入变量,达到稳定的高产量。调节工艺变量可有助于减小低k膜上的抛光变化。但是,最好在阻挡层CMP浆液中加入低k电介质专用的表面活性剂,且所述表面活性剂具有工艺可调节性能的可调节性。例如,Thomas等在美国专利公开第2007/0051917号中揭示了一种浆液,其对聚乙烯基吡咯烷酮和磷酸盐的量进行调节,以控制氮化钽、铜和碳掺杂的氧化物(CDO)的去除速率。调节聚乙烯基吡咯烷酮和二氧化硅的量,可以控制氮化钽(阻挡层)/CDO(超低k电介质)去除速率之比。不幸的是,对于一些应用这些浆液的阻挡层去除速率不足。
人们需要一种抛光浆液,使其能够达到调节阻挡层/超低k电介质的去除,同时不会使铜去除速率过高。另外,人们需要一种能够除去阻挡层、同时控制低k电介质腐蚀的浆液。
发明内容
本发明的一个方面提供了一种可用来对包括铜互连的半导体基片进行化学机械抛光的水性浆液,其包含0-25重量%的氧化剂,1-50重量%的磨粒,0.001-10重量%的用来减少铜互连的静态蚀刻的抑制剂,0.001-5重量%的具有以下结构式的聚(甲基乙烯基醚):
所述聚(甲基乙烯基醚)是水溶性的,n的数值至少为5,0-10重量%的在抛光过程中形成的铜配位剂,以及余量的水。
本发明的另一个方面提供了一种可用来对包括铜互连的半导体基片进行化学机械抛光的水性浆液,其包含0-20重量%的氧化剂,5-50重量%的磨粒,0.005-10重量%的用来减少铜互连的静态蚀刻的抑制剂,0.005-5重量%的具有以下结构式的聚(甲基乙烯基醚):
所述聚(甲基乙烯基醚)是水溶性的,n的数值至少为10,0-10重量%的在抛光过程中形成的铜配位剂,以及余量的水;所述水性浆液的pH值至少为8。
本发明的另一个方面提供了一种对半导体基片进行抛光的方法,所述半导体基片包括阻挡层、TEOS层和低k电介质层,所述方法包括以下步骤:在抛光垫上施加抛光浆液,所述抛光浆液具有以下组成:0-25重量%的氧化剂,1-50重量%的磨粒,0.001-10重量%的用来减少铜互连的静态蚀刻的抑制剂,0.001-5重量%的具有以下结构式的聚(甲基乙烯基醚):
所述聚(甲基乙烯基醚)是水溶性的,n的数值至少为5,0-10重量%的在抛光过程中形成的铜配位剂,以及余量的水;将所述半导体基片压靠在所述抛光垫上;在抛光垫和半导体基片之间产生运动,以便以阻挡层/碳掺杂氧化物层去除速率之比至少为1∶1的选择性除去阻挡层,所述去除速率以埃/分钟为单位测量。
具体实施方式
已发现,通过向铜阻挡层浆液添加聚(甲基乙烯基醚),可以减小碳掺杂的氧化物的去除速率,同时不会对半导体基片上的铜去除速率造成负面影响。对于本说明书来说,半导体基片包括具有金属导体互连和电介质材料的晶片,所述金属导体互连和电介质材料通过某种方式由绝缘层隔开,使得可以产生特殊的电信号。另外,这些浆液允许增大磨料含量,以进一步提高阻挡层去除速率,同时不对低k材料或铜的去除速率造成负面影响。最后,这些浆液提供了调节阻挡层、铜和电介质去除速率的平台,以满足各种各样要求的半导体应用。
已经发现,水溶性聚(甲基乙烯基醚)对碳掺杂的氧化物之类的低k电介质的去除速率的降低具有很大的影响。聚(甲基乙烯基醚)具有以下结构式:
n的值至少为5,优选至少为10,最优选至少为20。如果n过高,则聚(甲基乙烯基醚)的水溶性会下降。另外,因为共聚物配方会有不利的抛光影响,很重要的是所述聚(甲基乙烯基醚)聚合物仅含附带的杂质。聚(甲基乙烯基醚)在0.001-5重量%的浓度下可以是有效的。除非另外特别说明,本说明书中所有的浓度都以重量百分数表示。较佳的是,所述浆液的聚(甲基乙烯基醚)的浓度为0.005-5重量%。最佳的是,所述浆液的聚(甲基乙烯基醚)的浓度为0.01-1重量%。
所述浆液还任选包含0-3重量%的聚乙烯吡咯烷酮,用来除去阻挡层,同时对低k电介质膜具有选择性的去除速率。任选地,所述浆液包含0-2重量%的聚乙烯吡咯烷酮。例如,所述浆液任选包含0.01-1.5重量%的聚乙烯基吡咯烷酮。对于要求在除去阻挡层的同时具有适中的低k电介质去除速率的应用,所述浆液优选包含小于0.4重量%的聚乙烯吡咯烷酮。对于要求在除去阻挡层的同时具有低的低k电介质去除速率的应用,所述浆液优选包含至少0.4重量%的聚乙烯吡咯烷酮。这种非离子型聚合物有助于对低k和超低k电介质膜(通常是疏水性的)和硬掩模覆盖层膜进行抛光。
所述聚乙烯吡咯烷酮的重均分子量优选为1,000-1,000,000。对于本说明书来说,重均分子量表示通过凝胶渗透色谱法测量的分子量。所述浆液的分子量更优选为1,000-500,000,最优选分子量为2,500-50,000。例如,分子量为12000-15000的聚乙烯吡咯烷酮已被证明是特别有效的。
所述浆液任选包含0-5重量%的含磷化合物。对于本发明来说,″含磷”化合物是任意含有磷原子的化合物。任选地,所述浆液包含0-3重量%的含磷化合物。例如,所述浆液任选包含0.01-2的含磷化合物。例如,含磷化合物包括磷酸类,焦磷酸类,多磷酸类,膦酸类,氧化膦,硫化膦,正膦(phosphorinane),膦酸类,亚磷酸类和次膦酸类,包括它们的酸、盐、混酸盐、酯、偏酯、混合酯、以及它们的混合物,例如磷酸。具体来说,所述抛光浆液可包含以下具体的含磷化合物:磷酸锌、焦磷酸锌、多磷酸锌、膦酸锌、磷酸铵、焦磷酸铵、多磷酸铵、膦酸铵、磷酸氢二铵、焦磷酸氢二铵、多磷酸氢二铵、膦酸氢二铵、磷酸钾、磷酸氢二钾、磷酸胍、焦磷酸胍、多磷酸胍、膦酸胍、磷酸铁、焦磷酸铁、多磷酸铁、膦酸铁、磷酸铈、焦磷酸铈、多磷酸铈、膦酸铈、磷酸乙二胺、磷酸哌嗪、焦磷酸哌嗪、膦酸哌嗪、磷酸三聚氰胺、磷酸氢二(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、焦磷酸蜜白胺、多磷酸蜜白胺、膦酸蜜白胺、磷酸蜜勒胺、焦磷酸蜜勒胺、多磷酸蜜勒胺、膦酸蜜勒胺、磷酸二氰基二酰胺、磷酸脲,包括它们的酸、盐、混酸盐、酯、偏酯、混合酯、以及它们的混合物。
优选的含磷化合物包括磷酸铵和磷酸。但是过量的磷酸铵会在溶液中引入过量的游离铵。过量的游离铵会腐蚀铜,产生粗糙的金属表面。加入磷酸与游离碱金属(例如钾)原位反应以形成磷酸钾盐和磷酸氢二钾盐是特别有效的。
所述钾化合物也能提供以下优点:形成保护膜,在侵蚀性的CMP处理后的清洁溶液中保护铜。例如,CMP处理后的晶片膜具有足够的完整性,足以在包含侵蚀性铜配位剂如氢氧化四甲铵、乙醇胺和抗坏血酸的pH=12的溶液中保护晶片。
任选的钽阻挡层去除剂可以是乙脒,乙脒盐,乙脒衍生物,精氨酸,精氨酸盐,精氨酸衍生物,甲脒,甲脒盐,甲脒衍生物,胍,胍衍生物,胍盐和它们的混合物。例如,所述溶液任选依赖于至少一种选自以下的钽阻挡层去除剂来提高阻挡层去除速率:甲脒,甲脒盐,甲脒衍生物,胍,胍衍生物,胍盐和它们的混合物。具体的例子包括以下的至少一种:胍、盐酸胍、硫酸胍、盐酸氨基胍,乙酸胍,碳酸胍,硝酸胍,甲脒,亚磺酸甲脒,乙酸甲脒以及它们的混合物。任选地,所述溶液包含0-12重量%的阻挡层去除剂。在另一种可供选择的配方中,所述溶液任选包含0-10重量%的阻挡层去除剂;对于一些配方,任选的阻挡层去除剂浓度为0.1-5重量%、或者0.1-3重量%可以提高阻挡层去除速率。这些阻挡层去除剂对于具有较低固体浓度的配方具有较大的影响。另外,根据pH值范围,增加过氧化氢之类的氧化剂的加入可以进一步增大对阻挡层去除速率的影响。例如,在酸性pH值范围,增大过氧化氢的浓度可以提高甲脒和胍之类的阻挡层去除剂的效果。
任选的含量为0-25重量%的氧化剂可有助于除去阻挡层,例如钽、氮化钽、钛和氮化钛。任选地,所述浆液包含0-20重量%的氧化剂。最佳的是,所述浆液包含0.05-10重量%的氧化剂。合适的氧化剂包括例如过氧化氢、单过硫酸盐、碘酸盐、过邻苯二甲酸镁、过乙酸和其它过酸、过硫酸盐、溴酸盐、高碘酸盐、硝酸盐、铁盐、铈盐、锰(Mn)(III)盐、Mn(IV)盐和Mn(VI)盐、银盐、铜盐、铬盐、钴盐、卤素、次氯酸盐、或者包含上述氧化剂中的至少一种的组合。优选的氧化剂是过氧化氢。注意所述氧化剂通常正好在使用之前加入抛光组合物中,在这些情况下,所述氧化剂包含在独立的包装内,在使用之处混合。对于不稳定的氧化剂(例如过氧化氢)来说,这是特别有用的。
还可通过调节氧化剂(例如过氧化物)的量来控制金属互连的去除速率。例如,增大过氧化物的浓度可以加快铜去除速率。但是,过分增加氧化剂会对抛光速率造成不利的影响。
所述阻挡层金属抛光组合物包含用来“机械”去除阻挡层材料的磨料。所述磨料优选是胶体磨料。示例性的磨料包括以下这些:无机氧化物、金属硼化物、金属碳化物、金属氢氧化物、金属氮化物、或者包含上述磨料中至少一种的组合。合适的无机氧化物包括例如二氧化硅(SiO2),氧化铝(Al2O3),氧化锆(ZrO2),氧化铈(CeO2),氧化锰(MnO2),以及它们的混合物。氧化铝可以许多形式得到,例如α-氧化铝、γ-氧化铝、δ-氧化铝以及无定形(非晶态)氧化铝。氧化铝的其它合适的例子是勃姆石(AlO(OH))颗粒以及它们的混合物。如果需要,也可使用这些无机氧化物的改良形式,例如聚合物涂覆的无机氧化物颗粒。合适的金属碳化物、硼化物和氮化物包括例如碳化硅、氮化硅、碳氮化硅(SiCN)、碳化硼、碳化钨、碳化锆、硼化铝、碳化钽、碳化钛、以及包含上述金属碳化物、硼化物和氮化物中的至少一种的混合物。如果需要,还可使用金刚石作为磨料。另外的磨料还可包括聚合物颗粒和涂覆的聚合物颗粒。最佳的是,所述磨料选自氧化铝、氧化铈、二氧化硅、以及它们的混合物。因为胶体二氧化硅以较低速率腐蚀低k电介质,因此胶体二氧化硅是优选的磨料。
在所述抛光组合物的水相中磨料的浓度为1-50重量%。对于无磨料的溶液,固定的研磨垫有助于阻挡层的去除。较佳的是,所述磨料浓度为5-50重量%。最佳的是,所述磨料浓度为5-40重量%。通常,增大磨料的浓度可以加快阻挡层材料的去除速率;特别能够提高含钽阻挡层,例如碳化钽、氮化钽、碳氮化钽的去除速率。例如,如果半导体制造商需要增大的阻挡层去除速率,则通过增大磨料含量可将电介质去除速率增大到所需的水平。例如,20-40重量%的磨料浓度可以制得具有高阻挡层去除速率的选择性抛光溶液。
所述磨料的平均粒度优选小于250nm,以防过度的金属凹陷和电介质腐蚀。对于本说明书来说,粒度表示胶体二氧化硅的平均粒度。最佳的是,所述二氧化硅的平均粒度小于150nm,以进一步减小金属凹陷和电介质腐蚀。具体来说,小于75纳米的平均磨料粒度可以以可接受的速率除去所述阻挡层金属,同时不会过多除去电介质材料。例如,使用平均粒度为20-75纳米的胶体二氧化硅使电介质腐蚀和金属凹陷最少。减小胶体二氧化硅粒度能够改进溶液的选择性;但是也往往会减小阻挡层去除速率。另外,优选的胶体二氧化硅可包含分散剂之类的添加剂以改进二氧化硅在酸性pH值范围内的稳定性。一种这样的磨料是购自法国普提乌斯(Puteaux,France)的AZ电子材料法国S.A.S公司(AZ Electronic Materials France S.A.S.)的胶体二氧化硅。
任选地,用0-10重量%的铜配位剂防止有色金属沉淀。例如,所述浆液包含0.01-5重量%的铜配位剂。较佳的是,所述铜配位剂是有机酸。示例性的铜配位剂包括以下这些:乙酸、柠檬酸、乙酰乙酸乙酯、羟基乙酸、乳酸、苹果酸、草酸、水杨酸、二乙基二硫代氨基甲酸钠、琥珀酸、酒石酸、巯基乙酸、甘氨酸、丙氨酸、天冬氨酸、乙二胺、三甲基二胺、丙二酸、戊二酸(gluteric acid)、3-羟基丁酸、丙酸、邻苯二甲酸、间苯二甲酸、3-羟基水杨酸、3,5-二羟基水杨酸、五倍子酸、葡糖酸、邻苯二酚、邻苯三酚、丹宁酸、以及它们的盐。较佳的是,所述铜配位剂选自乙酸、柠檬酸、乙酰乙酸乙酯、羟基乙酸、乳酸、苹果酸、草酸。最佳的是,所述铜配位剂是柠檬酸。
加入总计0.01-10重量%的抑制剂可以减小铜互连的去除速率并保护铜免于静态蚀刻。对于本申请来说,铜互连表示用包含附带的杂质的铜或铜基合金形成的互连。调节抑制剂的浓度可以通过保护金属免于静态蚀刻而调节铜互连的去除速率。较佳的是,所述浆液包含0.005-10重量%的抑制剂。最优选的是,所述溶液包含0.01-2重量%的抑制剂。所述抑制剂可以由抑制剂的混合物组成。唑类抑制剂对于铜互连是特别有效的。常规的唑类抑制剂包括苯并三唑(BTA),巯基苯并噻唑(MBT),甲苯基三唑和咪唑。BTA是特别有效的用于铜互连的抑制剂,咪唑能够增加铜去除速率。
所述抛光组合物可以在酸性和碱性pH的范围操作。较佳的是,其pH值至少为8,包含余量的水。较佳的是,所述pH值为8-12,最优选为9-11.5。另外,溶液最优选依赖于余量的去离子水来限制附带的杂质。氨、氢氧化钠或氢氧化钾之类的氢氧根离子源能够将pH值调节在碱性范围内。最优选,所述氢氧根离子源是氢氧化钾。
任选地,所述浆液可包含流平剂(例如氯化物,或者具体来说氯化铵),缓冲剂,分散剂和表面活性剂。例如,所述浆液任选包含0.0001-0.1重量%的氯化铵。氯化铵提供了表面外观的改进,还可通过提高铜去除速率来促进铜的去除。具体来说,加入0.01-0.1重量%的氯化铵可以加快铜去除速率。
所述抛光组合物还可任选地包含缓冲剂,例如各种有机和无机碱或其盐,其pKa在大于8至12的pH范围内。所述抛光组合物还可任选地包含消泡剂,例如非离子型表面活性剂,其包括酯、环氧乙烷类、醇、乙氧基化物、硅化合物、氟化合物、醚、苷和它们的衍生物。所述消泡剂还可以是两性表面活性剂。所述抛光组合物可以任选地包含杀生物剂,例如考德克(Kordex)TM MLX(9.5-9.9%甲基-4-异噻唑啉-3-酮,89.1-89.5%水和≤1.0%的相关的反应产物)或卡森(Kathon)TM ICP III,其包含以下活性成分:2-甲基-4-异噻唑啉-3-酮和5-氯-2-甲基-4-异噻唑啉-3-酮,它们各自由罗门哈斯公司生产(考德克和卡森是罗门哈斯公司的商标)。
较佳的是,通过将所述浆液施加于半导体基片,在抛光垫上施加等于或小于21千帕的向下作用力,从而对半导体基片进行抛光。所述向下作用力表示抛光垫对半导体基片的作用力。所述抛光垫可以是圆形、带形或织网构型。这种低的向下作用力对于从半导体基片除去阻挡层材料、从而使半导体基片平面化是特别有效的。最佳的是,所述抛光在小于15千帕的向下作用力下进行。
以埃/分钟为单位测量的所述溶液提供的去除氮化钽的速率大于去除碳掺杂氧化物的速率,或者氮化钽∶碳掺杂氧化物选择性至少为1∶1,上述结果是在微孔聚氨酯抛光垫对晶片施加垂直压力的测量值小于20.7千帕的条件下测得的。用来测定选择性的具体抛光垫是Hi压纹PolitexTM微孔聚氨酯抛光垫。较佳的是,在微孔聚氨酯抛光垫对晶片施加垂直压力的测量值小于20.7千帕的条件下,所述溶液提供的氮化钽/碳掺杂的氧化物的选择性至少为1.5∶1,最优选,此范围至少为2∶1。
实施例
如下表1所示,将一系列比较浆液(A-G)和实施例浆液(1-11)与余量的去离子水混合。
表1
浆液 | BTA(重量%) | 二氧化硅(重量%) | H3PO4(重量%) | PVP(10K)(重量%) | 盐酸胍 | CA(重量%) | NH4Cl(重量%) | 聚(甲基乙烯基醚-苹果酸)交替共聚物(重量%) | 聚(甲基乙烯基醚)(重量%) |
A | 0.2 | 14 | 0.3 | 0.3 | 0.01 | ||||
B | 0.08 | 14 | 0.3 | 0.2 | 0.3 | 0.01 | 0.03 | ||
C | 0.08 | 14 | 0.3 | 0.2 | 0.3 | 0.01 | 0.010 | ||
D | 0.08 | 14 | 0.3 | 0.2 | 0.3 | 0.01 | 0.30 | ||
E | 0.08 | 14 | 0.3 | 0.2 | 0.3 | 0.01 | 0.90 | ||
F | 0.02 | 14 | 0.1 | 0.4 | 0.3 | 0.01 | |||
G | 0.02 | 14 | 0.1 | 0.4 | 0.5 | 0.3 | 0.01 |
浆液 | BTA(重量%) | 二氧化硅(重量%) | H3PO4(重量%) | PVP(10K)(重量%) | 盐酸胍 | CA(重量%) | NH4Cl(重量%) | 聚(甲基乙烯基醚-苹果酸)交替共聚物(重量%) | 聚(甲基乙烯基醚)(重量%) |
1 | 0.08 | 14 | 0 | 0.3 | 0.01 | 0.005 | |||
2 | 0.08 | 14 | 0.3 | 0.3 | 0.01 | 0.010 | |||
3 | 0.08 | 14 | 0.3 | 0.3 | 0.01 | 0.005 | |||
4 | 0.2 | 14 | 0.3 | 0.3 | 0.01 | 0.005 | |||
5 | 0.02 | 30 | 0.01 | ||||||
6 | 0.02 | 30 | 0.1 | 0.01 | |||||
7 | 0.02 | 30 | 0.3 | 0.01 | |||||
8 | 0.02 | 30 | 0.5 | 0.01 | |||||
9 | 0.02 | 30 | 1 | 0.01 | |||||
10 | 0.02 | 30 | 0.005 | ||||||
11 | 0.02 | 30 | 0.003 |
所有的样品包含0.4重量%的H2O2,0.005重量%的生物杀灭剂,pH为10.5,CA=柠檬酸,BTA=苯并三唑,生物杀灭剂=罗门哈斯公司生产的KordekTM MLX(9.5-9.9%甲基-4-异噻唑啉-3-酮,89.1-89.5%的水和≤1.0%的相关反应产物),PVP=聚乙烯基吡咯烷酮,二氧化硅=1501-50,购自法国普泰克斯的AZ电子材料法国S.A.S.公司(AZ Electronic Materials FranceS.A.S.,of Puteaux,France)的平均直径50纳米的胶体二氧化硅颗粒,希格玛-艾尔德瑞奇公司(Sigma-Aldrich Co.)提供聚(甲基乙烯基-苹果酸)交替共聚物和聚(甲基乙烯醚)。
实施例1
抛光测试使用来自诺威勒斯系统有限公司(Novellus Systems,Inc.)的克罗尔(Coral)TM碳掺杂氧化物(CDO)、TEOS电介质、氮化钽和电镀铜的200毫米片状晶片。使用来自罗门哈斯电子材料CMP技术公司(Rohm and HaasElectronic Materials CMP Technologies)的IC1010TM和压纹泊莱特克斯(Politex)TM抛光垫对片状晶片进行抛光而获得形貌(topographical)数据。
米拉(MIRRA)TM旋转式抛光平台抛光所述片状晶片。在台板1和2上,使用IC1010TM抛光垫和Eternal浆液EPL2360进行第一步铜抛光。抛光垫调整器是Kinik AD3CG-181060格子金刚石调整盘。平台1的抛光条件为:台板转速93rpm,支架转速21rpm,向下作用力4psi(27.6千帕),台板2的条件为:台板转速33rpm,支架转速61rpm,向下作用力3psi(20.7kPa)。台板3的抛光条件为:向下作用力1.5psi(10.3kPa),台板转速93rpm,支架转速87rpm,浆液流速200毫升/分钟,使用Hi压纹PolitexTM抛光垫。
由抛光之前和之后的膜厚度计算除去速率。所有光学透明的膜都使用Tencor SM300椭圆偏振光测量装置进行测量,对于铜设置在170×10-6Ω,对于氮化钽设置在28,000×10-6Ω。使用德克塔克维科(DektakVeeco)V200SL触针表面光度仪收集晶片形貌数据。本说明书所有报道的去除速率的单位都是埃/分钟。
表2
表2的数据显示,聚(甲基乙烯基醚-苹果酸)交替共聚物对碳掺杂的氧化物的去除速率具有中等的影响。一般来说,其可以减小碳掺杂的氧化物的去除速率,同时显著加快铜去除速率。铜去除速率的增大造成配制物效用显著降低。
表3.
通过表1和表3,显然可以看出,加入50ppm的聚(甲基乙醚)可以将碳掺杂的氧化物去除速率从1985减小到201/min(浆液A,1),而Cu和TaN的去除速率几乎不变。这种速率减小是在14重量%的二氧化硅的存在下发生的,在此二氧化硅浓度下,通常会导致低k电介质过高的腐蚀。
表4
浆液 | 平均TEOS(RR) | 平均Cu(RR) | 平均TaN(RR) | 平均CDO(RR) | 聚(甲基乙烯基醚)(重量%) | 盐酸胍(重量%) | 二氧化硅(重量%) |
F | 679 | 499 | 604 | 14 | |||
5 | 1332 | 816 | 1381 | 325 | 0.01 | 30 | |
6 | 1288 | 751 | 1393 | 448 | 0.01 | 0.1 | 30 |
7 | 1229 | 656 | 1383 | 547 | 0.01 | 0.3 | 30 |
8 | 1154 | 509 | 1335 | 622 | 0.01 | 0.5 | 30 |
9 | 1008 | 184 | 1289 | 546 | 0.01 | 1 | 30 |
10 | 1268 | 788 | 1370 | 795 | 0.005 | 30 | |
11 | 1282 | 790 | 1370 | 1179 | 0.003 | 30 | |
G | 670 | 705 | 834 | 689 | 0.5 | 14 |
以上实施例说明,对于快速的TaN去除速率以及可以接受的铜去除速率和碳掺杂的氧化物的去除速率,所述抛光浆液可以在高二氧化硅浓度下操作。特别是,浆液5-11可以在30重量%的二氧化硅的存在下有效地减小碳掺杂的氧化物的去除速率,此二氧化硅浓度已经远远超过了通常会以无法接受的速率腐蚀低k电介质的浓度。
Claims (10)
2.如权利要求1所述的水性浆液,其特征在于,所述浆液包含0.01-5重量%的选自以下的至少一种组分:甲脒、甲脒衍生物、甲脒盐、胍、胍衍生物、胍盐、以及它们的混合物。
3.如权利要求1所述的水性浆液,其特征在于,所述浆液包含5-50重量%的胶体二氧化硅磨粒。
4.一种可用来对包括铜互连的半导体基片进行化学机械抛光的水性浆液,其包含0-20重量%的氧化剂,5-50重量%的磨粒,0.005-10重量%的用来减少铜互连的静态蚀刻的抑制剂,0.005-5重量%的具有以下结构式的聚(甲基乙烯基醚):
所述聚(甲基乙烯基醚)是水溶性的,n的数值至少为10,0-10重量%的在抛光过程中形成的铜配位剂,以及余量的水;所述水性浆液的pH值至少为8。
5.如权利要求4所述的水性浆液,其特征在于,所述浆液包含0.01-3重量%的选自以下的至少一种组分:甲脒、甲脒衍生物、甲脒盐、胍、胍衍生物、胍盐、以及它们的混合物。
6.如权利要求4所述的水性浆液,其特征在于,所述浆液包含20-40重量%的二氧化硅磨粒。
7.如权利要求4所述的水性浆液,其特征在于,所述浆液包含0.0001-1重量%的氯化铵。
8.如权利要求4所述的水性浆液,其特征在于,所述浆液包含0.01-5重量%的铜配位剂。
9.一种对半导体基片进行抛光的方法,所述半导体基片包括阻挡层、TEOS层和低k电介质层,所述方法包括以下步骤:
在抛光垫上施加抛光浆液,所述抛光浆液具有以下组成:0-25重量%的氧化剂,1-50重量%的磨粒,0.001-10重量%的用来减少铜互连的静态蚀刻的抑制剂,0.001-5重量%的具有以下结构式的聚(甲基乙烯基醚):
所述聚(甲基乙烯基醚)是水溶性的,n的数值至少为5,0-10重量%的在抛光过程中形成的铜配位剂,以及余量的水;
将所述半导体基片压靠在抛光垫上;以及
在抛光垫和半导体基片之间产生运动,以便以阻挡层/碳掺杂氧化物层去除速率之比至少为1∶1的选择性除去阻挡层,所述去除速率以埃/分钟为单位测量。
10.如权利要求9所述的方法,其特征在于,所述方法去除含钽或含钛的阻挡层的速率大于去除碳掺杂的低k电介质层的速率,所述速率以为单位测量。
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CN104745086A (zh) * | 2013-12-25 | 2015-07-01 | 安集微电子(上海)有限公司 | 一种用于阻挡层平坦化的化学机械抛光液及其使用方法 |
CN105313001A (zh) * | 2014-07-28 | 2016-02-10 | 罗门哈斯电子材料Cmp控股股份有限公司 | 用于化学机械抛光含有钌和铜的衬底的方法 |
TWI573848B (zh) * | 2014-07-28 | 2017-03-11 | 羅門哈斯電子材料Cmp控股公司 | 含有釕及銅之基板之化學機械硏磨方法 |
CN105313001B (zh) * | 2014-07-28 | 2018-12-07 | 罗门哈斯电子材料Cmp控股股份有限公司 | 用于化学机械抛光含有钌和铜的衬底的方法 |
CN104400624A (zh) * | 2014-10-20 | 2015-03-11 | 南京航空航天大学 | 固结磨料化学机械抛光铜的加工方法 |
CN104400624B (zh) * | 2014-10-20 | 2016-11-23 | 南京航空航天大学 | 固结磨料化学机械抛光铜的加工方法 |
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EP2199353A1 (en) | 2010-06-23 |
TW201028461A (en) | 2010-08-01 |
US20100159807A1 (en) | 2010-06-24 |
KR20100074012A (ko) | 2010-07-01 |
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