CN102101977A - 一种化学机械抛光液 - Google Patents
一种化学机械抛光液 Download PDFInfo
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- CN102101977A CN102101977A CN2009102013819A CN200910201381A CN102101977A CN 102101977 A CN102101977 A CN 102101977A CN 2009102013819 A CN2009102013819 A CN 2009102013819A CN 200910201381 A CN200910201381 A CN 200910201381A CN 102101977 A CN102101977 A CN 102101977A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
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- -1 acrylic ester Chemical class 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
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- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
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- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic 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-QWKBTXIPSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229960000448 lactic acid Drugs 0.000 claims description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
本发明揭示了一种新的用于金属抛光的化学机械抛光液。这种抛光液可以通过下列物质组合在一起而形成：研磨颗粒、络合剂及腐蚀抑制剂。使用本发明的浆料的可以降低金属的去除速率，防止金属材料的整体和局部腐蚀，使缺陷明显下降，提高表面质量。
Description
技术领域
本发明涉及一种化学机械抛光液。
背景技术
随着微电子技术的发展，甚大规模集成电路芯片集成度已高达几十亿个元器件，特征尺寸已进入纳米级，这就要求微电子工艺中的近百道工艺，尤其是多层布线、衬底、介质必须进行化学机械全局平整化，而化学机械抛光(CMP)已被证明是最好的平整化方法。
在化学机械抛光方法中，将基底的被抛光表面直接与旋转抛光垫接触，同时在基底背面施加压力。在抛光期间，抛光垫随操作台旋转，同时在基底背面保持向下的力，将磨料和化学活性溶液组成的液体(通常称为化学机械抛光液)涂布于抛光垫片上，该化学机械抛光液与正在抛光的薄膜发生化学反应和机械作用开始进行抛光过程。化学机械抛光液在CMP中是一种重要的因素，而可根据制程的需要来选取合适的化学机械抛光液的来改变抛光性能。
在典型的金属化学机械抛光中，缺陷水平通常较高，尤其是存在点蚀、边蚀、腐蚀等问题。而且，抛光速率也很高，对金属表面的损伤程度较大，易产生如划伤、表面粗糙等问题。如美国专利US5,209,816揭示了一种用于铝的抛光液，其含有研磨颗粒、磷酸和双氧水，铝的去除速率较高。
发明内容
本发明的目的是提供一种降低金属的去除速率，防止金属材料在酸性条件下的整体和局部腐蚀，减少缺陷，提高表面质量的化学机械抛光液。
本发明揭示了一新的用于抛光金属层的化学机械抛光液。这种抛光液可以通过下列物质组合在一起而形成：研磨颗粒、络合剂及腐蚀抑制剂。使用本发明的浆料的可以降低金属的去除速率，防止金属材料的整体和局部腐蚀，使缺陷明显下降，提高表面质量。
详细说来，本发明的具体方法是向抛光液中添加了腐蚀抑制剂。
该腐蚀抑制剂是一种具有星型结构的聚合物表面活性剂
所述的化学机械抛光液，其特征在于：所述的颜料亲和基团为羟基、氨基和羧基中的一种或多种。
形成所述的含颜料亲和基团的星型聚合物的聚合单体包括下列中的一种或多种：丙烯酸类单体、丙烯酸酯类单体、丙烯酰胺类单体和环氧乙烷。
所述的丙烯酸类单体为丙烯酸和/或甲基丙烯酸；所述的丙烯酸酯类单体为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸羟乙酯和甲基丙烯酸羟乙酯中的一种或多种；所述的丙烯酰胺类单体为丙烯酰胺和/或甲基丙烯酰胺。
形成所述的含颜料亲和基团的星型聚合物的单体还包括其他乙烯基类单体。
所述的其他乙烯基类单体为乙烯、丙烯、苯乙烯或对甲基苯乙烯。
所述的含颜料亲和基团的星型聚合物为聚丙烯酸星型均聚物，苯乙烯与丙烯酸羟乙酯的二元星型共聚物，对甲基苯乙烯与环氧乙烷的二元星型共聚物，苯乙烯与环氧乙烷的二元星型共聚物，甲基丙烯酸甲酯与环氧乙烷的二元星型共聚物，丙烯酸甲酯与丙烯酸羟乙酯的二元星型共聚物，丙烯酸与丙烯酸羟乙酯的二元星型共聚物，以及丙烯酸、丙烯酸丁酯和丙烯酰胺的三元星型共聚物中的一种或多种。
所述的含颜料亲和基团的星型聚合物的数均分子量为800-50000。
所述的含颜料亲和基团的星型聚合物的含量为质量百分比0.0001～5％。
所述的研磨颗粒为二氧化硅、三氧化二铝、掺杂铝的二氧化硅、覆盖铝的二氧化硅、二氧化铈、二氧化钛和高分子研磨颗粒中的一种或多种。所述的研磨颗粒的含量为质量百分比0.1～20％。所述的研磨颗粒的粒径为20～150nm。
所述络合剂为有机酸及其盐、有机膦酸及其盐。
所述的有机酸为醋酸、草酸、柠檬酸、酒石酸、丙二酸、丁二酸、马来酸、苹果酸、乳酸、丹宁酸、没食子酸和磺基水杨酸、乙二胺四乙酸、环己烷四乙酸、乙二胺二琥珀酸、二乙烯三胺五乙酸和三乙烯四胺六乙酸中的一种或多种；所述的有机膦酸为2-膦酸丁烷-1，2，4-三羧酸、氨基三甲叉膦酸、羟基乙叉二膦酸、乙二胺四甲叉膦酸、二乙烯三胺五甲叉膦酸、多元醇膦酸酯、2-羟基膦酸基乙酸、乙二胺四甲叉膦酸和多氨基多醚基甲叉膦酸中的一种或多种。所述的盐为铵盐、钾盐和钠盐等。所述络合剂的含量为质量百分比0.01～10％。
本发明的化学机械抛光液还可以包含氧化剂。该氧化剂可为现有技术中的任何氧化剂，较佳地为过氧化氢、硝酸铁、有机过氧化物和/或无机过氧化物。
本发明的化学机械抛光液还可以包括表面活性剂、粘度调节剂、pH调节剂等。
本发明的另一目的是提供本发明的化学机械抛光液在抛光金属中的用途，所述的金属为铝、铜、钽、氮化钽、钛、氮化钛、银或金，优选抛光铝。
本发明的积极进步效果在于：本发明的化学机械抛光液可以明显降低缺陷率，提高金属表面平坦化水平，显著地降低金属的抛光速率。
具体实施方式
下面用实施例来进一步说明本发明，但本发明并不受其限制。
实施例1～30
表1给出了本发明的化学机械抛光液的实施例1～30，按表中所给配方，将所有组分混合均匀，用水补足质量百分比至100％。用KOH或HNO3调节到所需要的pH值。
表1实施例1～30
效果实施例
表2给出了对比抛光液1和本发明的抛光液，按表中所给配方，用水补足质量百分比至100％，用KOH或HNO3调节到所需要的pH值。混合均匀即可。
表2对比抛光液1和抛光液
采用对比抛光液1和本发明的抛光液31～36对空片铝晶片进行抛光，去除速率见表3。将铝晶片在抛光液中浸泡30分钟，测得铝的静态腐蚀速率见表3
抛光材料：空片铝晶片；抛光条件：下压力3Psi，抛光盘及抛光头转速70/80rpm，抛光垫PPG MX710，抛光液流速100ml/min，抛光机台为LogitechPM5Polisher。
表3对比抛光液1和抛光液31～36对金属铝的去除速率和铝的静态腐蚀速率
| 抛光液 | 铝的去除速率(A/min) | 铝的静态腐蚀速率(A/min) |
| 对比1 | 1242 | 3.76 |
| 31 | 549 | 1.65 |
| 32 | 151 | 0.68 |
| 33 | 67 | 0 |
| 34 | 780 | 1.97 |
| 35 | 413 | 1.20 |
| 36 | 249 | 0.73 |
由表可见，使用本发明的抛光液，可大大降低铝的去除速率，同时铝的静态腐蚀速率也降低，能有效的抑制腐蚀。
Claims (16)
1.一种化学机械抛光液，其包含：研磨颗粒、络合剂及腐蚀抑制剂。
2.如权利要求1所述抛光液，其特征在于，所述腐蚀抑制剂为含颜料亲和基团的星型聚合物。
3.如权利要求2所述抛光液，其特征在于，所述含颜料亲和基团的星型聚合物为选自羟基、氨基和羧基中的一种或多种。
4.如权利要求3所述抛光液，其特征在于，形成所述的含颜料亲和基团的星型聚合物的聚合单体包括下列中的一种或多种：丙烯酸类单体、丙烯酸酯类单体、丙烯酰胺类单体和环氧乙烷。
5.如权利要求4所述抛光液，其特征在于，所述的丙烯酸类单体为丙烯酸和/或甲基丙烯酸；所述的丙烯酸酯类单体为选自丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸羟乙酯和甲基丙烯酸羟乙酯中的一种或多种；所述的丙烯酰胺类单体为丙烯酰胺和/或甲基丙烯酰胺。
6.如权利要求4所述抛光液，其特征在于，形成所述的含颜料亲和基团的星型聚合物的单体还包括其他乙烯基类单体。
7.如权利要求6所述抛光液，其特征在于，所述其他乙烯基类单体为选自乙烯、丙烯、苯乙烯和对甲基苯乙烯中的一种或多种。
8.如权利要求2所述抛光液，其特征在于，所述含颜料亲和基团的星型聚合物为选自聚丙烯酸星型均聚物，苯乙烯与丙烯酸羟乙酯的二元星型共聚物，对甲基苯乙烯与环氧乙烷的二元星型共聚物，苯乙烯与环氧乙烷的二元星型共聚物，甲基丙烯酸甲酯与环氧乙烷的二元星型共聚物，丙烯酸甲酯与丙烯酸羟乙酯的二元星型共聚物，丙烯酸与丙烯酸羟乙酯的二元星型共聚物，以及丙烯酸、丙烯酸丁酯和丙烯酰胺的三元星型共聚物中的一种或多种。
9.如权利要求2所述抛光液，其特征在于，所述含颜料亲和基团的星型聚合物的数均分子量为800-50000。
10.如权利要求2所述抛光液，其特征在于，所述含颜料亲和基团的星型聚合物的含量为质量百分比0.0001～5％。
11.如权利要求1所述抛光液，其特征在于，所述研磨颗粒为选自二氧化硅、三氧化二铝、掺杂铝的二氧化硅、覆盖铝的二氧化硅、二氧化铈、二氧化钛和高分子研磨颗粒中的一种或多种。
12.如权利要求1所述抛光液，其特征在于，所述研磨颗粒的含量为质量百分比0.1～20％。
13.如权利要求1所述抛光液，其特征在于，所述研磨颗粒的粒径为20～150nm。
14.如权利要求1所述的抛光液，其特征在于，所述络合剂为有机酸及其盐、有机膦酸及其盐。
15.如权利要求14所述的抛光液，其特征在于，所述有机酸为选自醋酸、草酸、柠檬酸、酒石酸、丙二酸、丁二酸、马来酸、苹果酸、乳酸、丹宁酸、没食子酸、磺基水杨酸、乙二胺四乙酸、环己烷四乙酸、乙二胺二琥珀酸、二乙烯三胺五乙酸和三乙烯四胺六乙酸中的一种或多种；所述有机膦酸为选自2-膦酸丁烷-1，2，4-三羧酸、氨基三甲叉膦酸、羟基乙叉二膦酸、乙二胺四甲叉膦酸、二乙烯三胺五甲叉膦酸、多元醇膦酸酯、2-羟基膦酸基乙酸、乙二胺四甲叉膦酸和多氨基多醚基甲叉膦酸中的一种或多种。所述的盐为铵盐、钾盐和/或钠盐。
16.如权利要求1所述的抛光液，其特征在于，所述络合剂的含量为质量百分比0.01～10％。
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| CN102757732A (zh) * | 2012-06-28 | 2012-10-31 | 上海新安纳电子科技有限公司 | Al衬底用化学机械抛光液 |
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