CN1927975B - 可除去聚合物阻挡层的抛光浆液 - Google Patents
可除去聚合物阻挡层的抛光浆液 Download PDFInfo
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- CN1927975B CN1927975B CN2006101517966A CN200610151796A CN1927975B CN 1927975 B CN1927975 B CN 1927975B CN 2006101517966 A CN2006101517966 A CN 2006101517966A CN 200610151796 A CN200610151796 A CN 200610151796A CN 1927975 B CN1927975 B CN 1927975B
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- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
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- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
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- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 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
- 125000004437 phosphorous atom Chemical group 0.000 description 1
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- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 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
- 150000005846 sugar alcohols Polymers 0.000 description 1
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical compound S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 description 1
- 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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- 229920002258 tannic acid Polymers 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 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
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-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
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- 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
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H01L21/3105—After-treatment
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- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
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- 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
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Abstract
一种用来对具有铜互连的半导体基片进行化学机械抛光的水性浆液。所述水性浆液包含0.01-25重量％的氧化剂、0.1-50重量％的磨粒、0.001-3重量％的聚乙烯吡咯烷酮、0.01-10重量％的用来减少对铜互连的静态蚀刻的抑制剂、0.001-5重量％的用来增大铜互连的去除速率的含磷化合物、0.001-10重量％的在抛光过程中形成的络合剂和余量的水；所述水性浆液的pH值至少等于8。
Description
技术领域
本发明涉及可除去聚合物阻挡层的抛光浆液。
背景技术
随着超大规模集成电路(ULSI)技术向着更小线宽方向的发展，对常规的化学机械抛光(CMP)法使用提出了新的挑战。另外，随着低k和超低k介电膜的引入，由于这些膜机械强度低，而且与相邻的层的粘着性很差，因此需要使用更加温和的CMP法。另外，越来越严格的缺陷率标准对用于低k膜的抛光浆液提出了另外的要求。
将各种低k膜用于USLI中还会需要大量另外的步骤，以及使用一些新技术，例如超临界清洁、介电罩和金属罩、阻挡层和铜的保形沉积、在低的向下作用力和使用无磨料浆液的条件下进行的化学机械平面化。除了这些可能要用的技术以外，ULSI制造者还必须考虑和解决工艺复杂性相对于产率、可靠性、机械强度和性能(即由于阻容(RC)延迟造成的功率耗散)的关系。
关于使用低k材料的复杂性给阻挡层CMP法带来了更大的挑战，这要求该方法必须具有控制复杂的输入变量的能力，而且能够达到恒定的高产率。通过调节过程变量可以减少低k膜上的抛光差异。但是最需要的阻挡层CMP浆液要含有具有工艺可调的形成调节性的低k介电特征表面活化剂。例如，Ye等人在美国专利第6916742号中揭示了一种浆液，该浆液通过调节聚乙烯吡咯烷酮的量来控制氮化钽和掺杂碳的氧化物(CDO)的去除速率。通过调节聚乙烯吡咯烷酮和二氧化硅的量，可以控制浆液去除氮化钽(阻挡层)和去除CDO(超低k电介质)的速率之比。不幸的是，对于一些应用，这些浆液对铜的去除速率尚显不足。
人们需要一种浆液，该浆液能够可控地除去阻挡层和超低k电介质，而且提高对铜的去除速率。另外，人们还需要一种浆液，该浆液能够在除去阻挡层的同时，对电介质的侵蚀和使铜产生的凹陷都受到控制。
发明内容
在本发明一个方面，本发明包括可用来对具有铜互连(copper interconnect)的半导体基片进行化学机械抛光的水性浆液，所述浆液包含0.01-25重量％的氧化剂、0.1-50重量％的磨粒、0.001-3重量％的聚乙烯吡咯烷酮、0.01-10重量％的用来减少对铜互连的静态蚀刻的抑制剂、0.001-5重量％的用来增大铜互连的去除速率的含磷化合物、0.001-10重量％的在抛光过程中形成的络合剂和余量的水；所述水性浆液的pH值至少等于8。
在本发明另一个方面，本发明包括可用来对具有铜互连的半导体基片进行化学机械抛光的水性浆液，所述浆液包含0.05-15重量％的氧化剂、0.1-40重量％的二氧化硅磨粒、0.002-2重量％的聚乙烯吡咯烷酮、0.02-5重量％的用来减少对铜互连的静态蚀刻的吡咯抑制剂、0.01-3重量％的用来增大铜互连的去除速率的含磷化合物、0.01-5重量％的在抛光过程中形成的有机酸络合剂和余量的水；所述水性浆液的pH值为8-12。
在本发明另一个方面，本发明包括可用来对具有铜互连的半导体基片进行化学机械抛光的水性浆液，所述浆液包含0.1-10重量％的氧化剂、0.25-35重量％的二氧化硅磨粒、0.01-1.5重量％的聚乙烯吡咯烷酮、0.05-2重量％的用来减少对铜互连的静态蚀刻的苯并三唑抑制剂、0.02-2重量％的用来增大铜互连的去除速率的含磷化合物、0.01-5重量％的在抛光过程中形成的有机酸络合剂和余量的水；所述水性浆液的pH值为9-11.5。
具体实施方式
已发现将包含磷酸盐的化合物加入包含聚乙烯吡咯烷酮的浆料可以提高铜的去除速率，同时不会对阻挡层、低k和超低k半导体基片的去除速率造成负面影响。出于本说明书的目的，半导体基片包括其上具有金属导体互连和介电材料的晶片，这些互连和介电材料被绝缘层以一定的方式分离，从而能够产生电信号。另外，这些浆液出人意料地改进了晶片的表面糙度。最后，这些浆料在CMP法后提供了稳定的膜，因此有利于用侵蚀性的清洁剂进行清洁而不会对晶片的表面糙度造成负面影响。
所述浆液还包含0.001-3重量％的用来除去阻挡层的聚乙烯吡咯烷酮，所述聚乙烯吡咯烷酮对低k介电膜具有选择性去除速率。除非另外说明，说明书中所有的浓度均为重量百分数。较佳的是，该浆液包含0.002-2重量％的聚乙烯吡咯烷酮。最佳的是，所述浆液包含0.01-1.5重量％的聚乙烯吡咯烷酮。对于要求在适当的低k介电膜去除速率下去除阻挡层的应用，该浆液的聚乙烯吡咯烷酮含量优选小于0.4重量％。对于要求在低的低k介电膜去除速率下去除阻挡层的应用，该浆液优选包含至少0.4重量％的聚乙烯吡咯烷酮。这种非离子型聚合物促进了对低k和超低k介电膜(通常是疏水的)以及硬掩蔽覆盖膜的抛光。
所述聚乙烯吡咯烷酮的重均分子量优选为1000-1000000。出于本说明书的目的，重均分子量表示由凝胶渗透色谱法测得的分子量。更优选浆液的分子量为1000-500000，最优选分子量为2500-50000。例如，已证明分子量为12000-15000的聚乙烯吡咯烷酮是特别有效的。
该浆液包含0.001-5重量％的含磷化合物。出于本说明书的目的，“含磷”化合物是任何包含磷原子的化合物。较佳的是，所述浆液包含0.01-3重量％的含磷化合物。最佳的是，该浆液包含0.02-2重量％的含磷化合物。例如，含磷化合物包括磷酸盐/酯、焦磷酸盐/酯、多磷酸盐/酯、膦酸盐/酯、氧膦、硫膦、phosphorinane、膦酸盐/酯、亚磷酸盐/酯和次膦酸盐/酯，包括它们的酸、盐、混合酸盐、酯、偏酯、混合酯、及其混合物，例如磷酸。具体来说，所述抛光浆液可包含以下的具体含磷化合物：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、混合酸盐、酯、偏酯、混合酯、及其混合物。
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。过量的游离铵会侵蚀铜，形成粗糙的金属表面。加入磷酸，与钾之类的游离碱金属原位反应生成磷酸钾盐和磷酸氢二钾盐，这是特别有效的。
钾化合物的另一个优点在于其还可形成保护膜，在侵蚀性的CMP后清洁液中起到保护铜的作用。例如，CMP后的晶片的膜具有足够的完整性，足以在包含侵蚀性铜络合剂(例如氢氧化四甲基铵、乙醇胺和抗坏血酸)的pH值为12的溶液中保护晶片。
含量为0.01-25重量％的氧化剂也可促进对钽、氮化钽、钛和氮化钛之类的阻挡层的去除。较佳的是，该浆液包含0.05-15重量％的氧化剂。最佳的是，该浆液包含0.1-10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、过乙酸和其他过酸、过硫酸、溴酸、高碘酸盐、硝酸盐、铁盐、铈盐、三价锰盐、四价锰盐和六价锰盐、银盐、铜盐、铬盐、钴盐、卤素、高氯酸盐或包含至少一种上述氧化剂的混合物。优选的氧化剂是过氧化氢。应当注意氧化剂通常在临使用之前加入抛光组合物中，在这些情况下，氧化剂置于独立的包装中，在使用的位置混合。这对于过氧化氢之类的不稳定的氧化剂特别有效。
通过调节过氧化物之类的氧化剂的量也可控制金属互连去除速率。例如，增大过氧化物的浓度可以提高铜的去除速率。但是氧化剂的过度增加会对抛光速率造成负面影响。
阻挡层金属抛光组合物包含用来“机械”地除去阻挡层材料的磨料。所述磨料优选为胶体磨料。示例性的磨料包括以下物质：无机氧化物、金属硼化物、金属碳化物、金属氢氧化物、金属氮化物或包含至少一种上述磨料的混合物。合适的无机氧化物包括例如二氧化硅(SiO2)、氧化铝(Al2O3)、氧化铈(CeO2)、氧化锰(MnO2)及其混合物。氧化铝可以为许多形式，例如α-氧化铝、γ-氧化铝、δ-氧化铝和无定形(非晶态)氧化铝。氧化铝的其他合适的例子为勃姆石颗粒及其混合物。如果需要的话，也可使用这些无机氧化物的改性形式，例如用聚合物涂敷的无机氧化物颗粒。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、以及包含至少一种上述金属碳化物、硼化物和氮化物的混合物。如果需要，也可将金刚石用作磨料。其它磨料还包括聚合物颗粒和涂布的聚合物颗粒。优选的磨料是二氧化硅。
所述抛光组合物水相中的磨料浓度为0.1-50重量％。对于不含磨料的溶液，固定的研磨垫有助于除去阻挡层。较佳的是，磨料浓度为0.1-40重量％。最佳的是，磨料浓度为0.25-35重量％。通常增大磨料浓度可以提高介电材料的去除速率；尤其会增大碳掺杂氧化物之类的低k介电材料的去除速率。例如，如果半导体制造商需要提高低k电介质的去除速率，则可以通过增大磨料浓度，将电介质去除速率提高到所需的程度。
为了防止发生过度的金属凹陷和电介质腐蚀，所述磨料的平均粒度优选小于250纳米。出于本说明书的目的，粒度表示胶体二氧化硅的平均粒度。最佳的是，二氧化硅的平均粒度小于150纳米，以进一步减少金属凹陷和电介质侵蚀。具体来说，磨料平均粒度小于75纳米的情况下，可以以可接受的速率除去阻挡层材料，而且不会过分地除去介电材料。例如，当胶体二氧化硅的平均粒度为20-75纳米时，所产生的电介质腐蚀和金属凹陷最少。减小胶体二氧化硅的尺寸可以提高溶液的选择性；但是也容易减小阻挡层的去除速率。另外，优选的胶体二氧化硅可包含分散剂之类的添加剂，以提高二氧化硅在酸性pH范围内的稳定性。一种这样的磨料是购自法国，Puteaux的AZ Electronic MaterialsFrance S.A.S.的胶体二氧化硅。
除了抑制剂以外，还使用0.001-10重量％的络合剂来防止非铁金属沉淀。最佳的是，该浆液包含0.01-5重量％的络合剂。较佳的是，所述络合剂是有机酸。示例性的络合剂包括以下化合物：乙酸、柠檬酸、乙酰乙酸乙酯、乙醇酸、乳酸、马来酸、草酸、铜锌灵、琥珀酸、酒石酸、亚硫基二乙酸、甘氨酸、丙氨酸、天冬氨酸、乙二胺、三甲基二胺、丙二酸、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、连苯三酚、丹宁酸及其盐。较佳的是，所述络合剂选自乙酸、柠檬酸、乙酰乙酸乙酯、乙醇酸、乳酸、马来酸、草酸。最佳的是，所述络合剂是柠檬酸。
加入占总重量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，防止其发生静态蚀刻。出于本实施方式的目的，铜互连表示由包含少量附带的杂质的铜或铜基合金形成的互连。通过调节抑制剂的浓度，可以保护金属使其免于发生静态蚀刻，从而调节铜互连的去除速率。较佳的是，该浆液包含0.02-5重量％的抑制剂。最佳的是，所述溶液包含0.05-2重量％的抑制剂。所述抑制剂可以由抑制剂的混合物组成。吡咯抑制剂对于铜互连是特别有效的。通常的吡咯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对于铜互连是特别有效的抑制剂，咪唑可提高铜的去除速率。
所述抛光组合物的pH值至少为8，还包含余量的水。较佳的是，pH值为8-12，最优选为9-11.5。另外，该溶液最优选依靠余量的去离子水来限制偶然夹杂的杂质。可使用氨、氢氧化钠或氢氧化钾之类的氢氧根离子源将pH值调节到碱性范围内。最佳的是，氢氧根离子源是氢氧化钾。
所述浆液可任选地包含氯化物(具体来说为氯化铵)之类的流平剂、缓冲剂、分散剂和表面活性剂。例如，该浆液任选地包含0.0001-0.1重量％的氯化铵。氯化铵可以改进表面外观，还可通过提高铜的去除速率来促进铜的去除。
所述抛光组合物还可任选地包含缓冲剂，例如pKa在大于8-12的pH值范围内的各种有机和无机碱或其盐。该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、醇、乙氧基化物、硅化合物、氟化合物、醚、苷及其衍生物等。消泡剂还可以是两性表面活性剂。抛光组合物可任选地包含生物杀伤剂，例如KordekTM MLK(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)或包含以下活性组分的KathonTMICPIII：2-甲基-4-异噻唑啉-3-酮和5-氯-2-甲基-4-异噻唑啉-3-酮，这两种生物杀伤剂均由罗门哈斯公司生产(Kathon和Kordek是罗门哈斯公司的商标)。
较佳的是，通过对半导体基片施加浆液，并且在抛光垫上施加等于或小于21千帕的向下作用力，用浆液抛光半导体基片。向下作用力表示抛光垫对半导体基片的作用力。抛光垫可以是圆形、带形或网状结构的。向下作用力可以特别有效地对半导体基片进行平整化，从半导体基片上除去阻挡层材料。最佳的是，在进行抛光时的向下作用力小于15千帕。
实施例
下表1显示了一系列的混有余量为去离子水的三种比较例浆液(A至C)和三种实施例浆液(1至3)。
表1
| 浆液 | NH<sub>4</sub>Cl(重量％) | CA(重量％) | PVP(重量％) | 咪唑(重量％) | BTA(重量％) | 生物杀伤剂(重量％) | H<sub>3</sub>PO<sub>4</sub>(重量％) | pH(重量％) | 二氧化硅(重量％) | H<sub>2</sub>O<sub>2</sub>(重量％) |
| A | 0.01 | 0.3 | 0.4 | 0.8 | 0.05 | 0.005 | 10.50 | 14 | 0.8 | |
| B | 0.01 | 0.3 | 0.4 | 0.03 | 0.005 | 9.50 | 16 | 0.4 | ||
| C | 0.01 | 0.3 | 0.7 | 0.03 | 0.005 | 9.50 | 18 | 0.4 | ||
| 1 | 0.01 | 0.3 | 0.4 | 0.02 | 0.005 | 0.1 | 10.50 | 14 | 0.4 | |
| 2 | 0.01 | 0.3 | 0.4 | 0.05 | 0.005 | 0.1 | 10.50 | 14 | 0.8 | |
| 3 | 0.01 | 0.3 | 0.4 | 0.05 | 0.005 | 0.2 | 10.50 | 14 | 0.8 |
CA＝柠檬酸，PVP＝聚乙烯吡咯烷酮，BTA＝苯并三唑，生物杀伤剂＝罗门哈斯公司生产的KordekTM MLK(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)，二氧化硅＝1501-50，一种购自法国Puteaux的AZ Electronic Materials France S.A.S.的50纳米的二氧化硅。
实施例1
抛光试验使用购自Novellus Systems，Inc.的200毫米的CoralTM碳掺杂氧化物晶片、TEOS电介质、氮化钽和电镀铜。使用购自Rohm and Haas ElectronicMaterials CMP Technologies的IC1010TM和压纹的PolitexTM抛光垫抛光晶片，获得形貌数据。
使用MIRRATM旋转型抛光台抛光晶片。
在第一步对铜进行抛光的时候，使用Eternal浆液EPL2360、IC1010TM抛光垫在抛光台1和2上进行抛光，使用Kinik AD3CG-181060隔栅金刚石修整盘。抛光台1的抛光条件是：台板转速93rpm，支架转速21rpm，向下作用力为4psi(27.6千帕)，抛光台2的台板转速为33rpm，支架转速为61rpm，向下作用力为3psi(20.7千帕)。抛光台3的抛光条件为：向下作用力1.5psi(10.3千帕)、台板转速93rpm、支架转速87rpm，浆液流速200毫升/分钟，使用Hi压纹的PolitexTM抛光垫。
使用抛光之前和抛光之后的膜厚度计算去除速率。所有光学透明的膜都使用Tencor SM300椭圆偏光测量仪测量，对于铜在170×10-6Ω测量，对于氮化钽在28000×10-6Ω测量。使用Dektak Veeco V200SL针尖轮廓曲线仪测量晶片的形貌数据。所有的去除速率的单位均为
分钟。
表2
表2说明咪唑和磷酸可以促进铜的去除速率的提高，对TEOS的去除速率有一定的提高。但是试验中用的pH值，磷酸与钾结合生成磷酸钾和磷酸氢二钾。将表2中的浆液2与浆液C相比较，可见所有被抛光物质的去除速率都由于较高的磨料含量而增加了，例外的是CDO去除速率，这是由于浆液C中的聚乙烯吡咯烷酮增加造成的。将浆液B(不含铜促进剂)与浆液A(咪唑促进剂)和表2中的浆液1、2和3(磷酸盐促进剂)相比；发现这些促进剂使得铜的去除速率加快。
下表3包括用ATMI提供的ESC784清洁之后测得的AFM表面糙度。
表3
| 浆液 | P.V.(纳米) | RMS(纳米) | RA(纳米) |
| A | 23.15 | 0.459 | 0.215 |
| B | 3.32 | 0.312 | 0.243 |
| C | 3.16 | 0.226 | 0.175 |
| 1 | 8.80 | 0.311 | 0.229 |
| 2 | 3.49 | 0.245 | 0.188 |
| 3 | 4.14 | 0.246 | 0.190 |
表3的数据说明，相对于使用包含咪唑的浆液抛光的晶片，使用钾化合物抛光的晶片表面糙度获得提高。将表3中的浆液B(不含促进剂)的RMS表面糙度与浆液A(咪唑促进剂)相比；制剂A在CMP后清洁中(在此实施例中是使用ATMI提供的ESC784进行清洁)会制得更为粗糙的表面。将浆液B(不含促进剂)与浆液1、2和3(磷酸盐促进剂)相比；发现通过使用这种促进剂可以在CMP后清洁处理中减小表面糙度。
Claims (10)
1.一种用来对具有铜互连的半导体基片进行化学机械抛光，以从所述半导体基片除去阻挡层材料的水性浆液，所述浆液包含0.01-25重量％的氧化剂、0.1-50重量％的磨粒、0.001-3重量％的聚乙烯吡咯烷酮、0.01-10重量％的用来减少对铜互连的静态蚀刻的抑制剂、0.001-5重量％的用来增大铜互连的去除速率的选自磷酸铵、磷酸钾和磷酸氢二钾中的至少一种的磷酸盐化合物、0.0001-0.1重量％的用来增大铜互连的去除速率的氯化铵、0.001-10重量％的络合剂和余量的水；所述水性浆液的pH值至少等于8。
2.如权利要求1所述的水性浆液，其特征在于，所述聚乙烯吡咯烷酮的重均分子量为1000-1000000。
3.如权利要求1所述的水性浆液，其特征在于，所述浆液包含二氧化硅磨粒。
4.一种用来对具有铜互连的半导体基片进行化学机械抛光，以从所述半导体基片除去阻挡层材料的水性浆液，所述浆液包含0.05-15重量％的氧化剂、0.1-40重量％的二氧化硅磨粒、0.002-2重量％的聚乙烯吡咯烷酮、0.01-5重量％的用来减少对铜互连的静态蚀刻的吡咯抑制剂、0.01-3重量％的用来增大铜互连的去除速率的选自磷酸铵、磷酸钾和磷酸氢二钾中的至少一种的磷酸盐化合物、0.0001-0.1重量％的用来增大铜互连的去除速率的氯化铵、0.01-5重量％的有机酸络合剂和余量的水；所述水性浆液的pH值为8-12。
5.如权利要求4所述的水性浆液，其特征在于，所述聚乙烯吡咯烷酮的重均分子量为1000-500000。
6.如权利要求4所述的水性浆液，其特征在于，所述浆液包含平均粒度小于100纳米的二氧化硅磨粒。
7.如权利要求4所述的水性浆液，其特征在于，所述磷酸盐化合物是磷酸氢二钾。
8.一种用来对具有铜互连的半导体基片进行化学机械抛光，以从所述半导体基片除去阻挡层材料的水性浆液，所述浆液包含0.1-10重量％的氧化剂、0.25-35重量％的二氧化硅磨粒、0.01-1.5重量％的聚乙烯吡咯烷酮、0.01-2重量％的用来减少对铜互连的静态蚀刻的苯并三唑抑制剂、0.02-2重量％的用来增大铜互连的去除速率的选自磷酸铵、磷酸钾和磷酸氢二钾中至少一种的磷酸盐化合物、0.0001-0.1重量％的用来增大铜互连的去除速率的氯化铵、0.01-5重量％的有机酸络合剂和余量的水；所述水性浆液的pH值为9-11.5。
9.如权利要求8所述的水性浆液，其特征在于，所述铜络合剂是柠檬酸。
10.如权利要求8所述的水性浆液，其特征在于，所述磷酸盐化合物是磷酸氢二钾。
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| CN1927975A (zh) | 2007-03-14 |
| TWI385226B (zh) | 2013-02-11 |
| FR2890393A1 (fr) | 2007-03-09 |
| KR101257115B1 (ko) | 2013-04-22 |
| KR20070029079A (ko) | 2007-03-13 |
| DE102006041805B4 (de) | 2017-05-11 |
| US20070051917A1 (en) | 2007-03-08 |
| JP2007116105A (ja) | 2007-05-10 |
| FR2890393B1 (fr) | 2011-06-03 |
| JP5161448B2 (ja) | 2013-03-13 |
| DE102006041805A1 (de) | 2007-03-15 |
| US7785487B2 (en) | 2010-08-31 |
| TW200718763A (en) | 2007-05-16 |
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