CN103146306A - 一种tsv阻挡层抛光液 - Google Patents
一种tsv阻挡层抛光液 Download PDFInfo
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- 238000005498 polishing Methods 0.000 title claims abstract description 61
- 230000004888 barrier function Effects 0.000 title claims abstract description 10
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 20
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
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- 239000003795 chemical substances by application Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011814 protection agent Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 4
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
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- -1 methylene-bis naphthene sulfonic acid disodium salt Chemical class 0.000 claims description 3
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- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
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- 239000010703 silicon Substances 0.000 abstract description 8
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- 230000002950 deficient Effects 0.000 description 6
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- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 description 1
- SRDOTWUOTQTGAK-UHFFFAOYSA-N C=O.C1(=CC=CC2=CC=CC=C12)S(=O)(=O)OCC1=CC=CC=C1 Chemical compound C=O.C1(=CC=CC2=CC=CC=C12)S(=O)(=O)OCC1=CC=CC=C1 SRDOTWUOTQTGAK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- WQHQCQSAAOGHQP-UHFFFAOYSA-N formaldehyde;2-methylnaphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WQHQCQSAAOGHQP-UHFFFAOYSA-N 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- 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
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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
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- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
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Abstract
本发明揭示了一种适用于硅通孔(TSV)阻挡层的化学机械抛光液，至少含有一种磨料，一种复合金属铜腐蚀抑制剂，一种络合剂，一种氮化硅调节剂，该抛光液具有较高的二氧化硅去除速率，和较低的氮化硅去除速率，能够对阻挡层进行高效的平坦化，并停止在氮化硅层，形成硅通孔，同时不产生金属腐蚀，具有较高的缺陷校正能力和较低的表面污染物指标。
Description
技术领域
本发明涉及一种抛光液，尤其涉及一种用于抛光TSV阻挡层的化学机械抛光液。
背景技术
参见图5-7，为了提高IC的性能、进一步缩小尺寸、降低功耗和成本，小尺寸3D TSV(TSV，Through-Silicon-Via硅通孔)封装技术也由此应运而生。3D TSV是通过在芯片和芯片之间、晶圆和晶圆之间制作垂直导通，实现芯片之间互连的最新技术。与以往IC封装键合和使用凸点的叠加技术不同，TSV能够使芯片在三维方向堆叠的密度最大，外形尺寸最小，大大改善芯片速度和低功耗的性能。其主要优势表现为：具有最小的尺寸和重量，将不同种类的技术集成到单个封装中，用短的垂直互连代替长的2D互连，降低寄生效应和功耗等。
TSV制程的集成方式非常多，但都面临一个共同的难题，即TSV制作都需要打通不同材料层，包括硅材料、IC中各种绝缘或导电的薄膜层。例如金属铜，阻挡层金属钽，二氧化硅绝缘层以及氮化硅停止层等，各种膜层的厚度也比较高，这就需要在CMP过程中具有较高的去除速率和合适的抛光选择比，才能实现对前程缺陷的最大矫正，并停止在氮化硅层，同时不能产生金属的腐蚀和缺陷，表面颗粒物控制在工艺要求的范围。这对硅通孔阻挡层的CMP提出了更高的要求。目前还没有商业化的TSV阻挡层抛光液的报道。
发明内容
本发明的目的是解决上述现有技术中存在的问题，提供一种具有较高的二氧化硅介质材料去除速率和较高的对氮化硅的抛光选择比，对前程的缺陷具有较高的校正能力，不产生金属腐蚀和缺陷，稳定性较好的化学机械抛光液。
本发明的技术方案如下：
一种TSV阻挡层抛光液，其特征在于，包含以下组分：磨料、组合金属保护剂、络合剂、氧化剂、氮化硅抑制剂和pH调节剂。
其中，所述磨料是二氧化硅溶胶或气相法二氧化硅。所述磨料的粒径为20-200nm，较佳的为40-120nm。所述磨料含量为10-50％，较佳的为20-30％。
其中，组合金属保护剂包括一种唑类化合物和一种水溶性聚合物。
其中，所述的唑类化合物为苯并三氮唑及其衍生物；所述水溶性聚合物为聚丙烯酸及其共聚物。
其中，所述唑类化合物的浓度为0.01-0.5％；所述水溶性聚合物的浓度为0.005-0.1％。优选的，所述唑类化合物的浓度为0.05-0.2％；所述水溶性聚合物的浓度为0.01-0.05％。
其中，所述的络合剂选自有机磷酸，PBTCA，HPAA，HEDP，EDTMP和ATMP中的一种或多种。所述络合剂的浓度为0.05％-1％，优选0.1-0.5％。
其中，所述氮化硅抑制剂为一种萘磺酸盐的甲醛缩聚物，具有以下通式：
其中：
所述氮化硅抑制剂的浓度从50ppm到0.1％。
其中，所述氮化硅抑制剂为亚甲基双萘磺酸二钠盐，甲基萘磺酸甲醛缩聚物和/或苄基萘磺酸甲醛缩聚物。
其中，所述pH调节剂为一种有机羧酸。
其中，所述有机羧酸选自草酸，丙二酸，丁二酸，柠檬酸和酒石酸中的一种或多种。
其中，所述氧化剂为过氧化物或过硫化物。所述氧化剂选自过氧化氢，过氧化钠，过氧化钾，过氧化苯甲酰，过硫酸钠，过硫酸钾和过硫酸铵中的一种或多种。
其中，抛光液还包括：杀菌防霉变剂。所述杀菌防霉变剂为季铵盐活性剂。
其中，所述抛光液的pH值为2-5，优选3-4。
本发明具备的有益效果是：
具有更高的Ta和SiO2的去除速率，氮化硅的去除速率小于100A/min，选择比达到15-20。能够较好地停止在氮化硅层，络合剂以及组合金属保护剂的共同作用下，很好的保护金属铜，未发现金属腐蚀，且金属的去除速率碎双氧水呈温和的线性变化。抛光后表面的细线区域清晰锐利，无颗粒物和有机物质残留等污染物。此外，对前程同抛光后的缺陷具有较大幅度的校正，具有较好的平坦化效率。浸泡后，具有较好的抗腐蚀性能。
附图说明
图1、2为抛光后图形片的表面形貌；
图3、4为在抛光液中浸泡过的表面图片；
图5-7为TSV硅通孔阻挡层抛光前后的抛面示意图，其中：
图5为硅通孔(TSV)抛光前抛面示意图
图6为硅通孔(TSV)铜抛光后抛面示意图
图7为硅通孔(TSV)阻挡层抛光后抛面示意图
具体实施方式
下面通过具体实施方式来进一步阐述本发明的优势。
抛光条件：
抛光垫：IC pad
抛光条件：70/90rpm
抛光液流量：100ml/min
静态腐蚀速率：将新鲜抛光的铜片放入浆液中浸渍15min，测量前后的膜层厚度。
蝶形凹陷：采用Semitech 854图形晶圆测量80um金属块的蝶形凹陷。
切片内的抛光均一性：为一个管芯内不同线宽的蝶形凹陷。
空白晶片：PETEOS，Ta，Cu，Si3N4
表1、实施例1-7与对比抛光液的配方
BTA：苯并三氮唑，PAA：聚丙烯酸，PBTCA：2-膦酸-1，2，4-三羧酸丁烷。DIS N1，亚甲基双萘磺酸二钠盐，DISN2：甲基萘磺酸盐甲醛缩合物，DISN3：苄基萘磺酸盐甲醛缩合物。HPAA：2-羟基膦酰基乙酸，HEDP：羟基乙叉二膦酸。参比抛光液为市售的阻挡层抛光液。
表2、效果数据
从图1-4中可以看出，本抛光液和对比抛光液相比，具有更高的Ta和SiO2的去除速率，添加氮化硅抑制剂后，使得氮化硅的去除速率小于100A/min，选择比达到15-20。能够较好地停止在氮化硅层，络合剂以及组合金属保护剂的共同作用下，很好的保护金属铜，未发现金属腐蚀，且金属的去除速率碎双氧水呈温和的线性变化。抛光后表面的细线区域清晰锐利，无颗粒物和有机物质残留等污染物。此外，对前程同抛光后的缺陷具有较大幅度的校正，具有较好的平坦化效率。浸泡后，图形片表面无明显变化，显示了较好的抗腐蚀性能。
Claims (24)
1.一种TSV阻挡层抛光液，其特征在于，包含以下组分：磨料、组合金属保护剂、络合剂、氧化剂、氮化硅抑制剂和pH调节剂。
2.如权利要求1所述的抛光液，其特征在于，所述磨料是二氧化硅溶胶或气相法二氧化硅。
3.如权利要求1或2所述的抛光液，其特征在于，所述磨料的粒径为20-200nm。
4.如权利要求3所述的抛光液，其特征在于，所述磨料的粒径为40-120nm。
5.如权利要求1或2所述的抛光液，其特征在于，所述磨料含量为10-50％。
6.如权利要求5所述的抛光液，其特征在于，所述磨料含量为20-30％。
7.如权利要求1所述的抛光液，其特征在于，所述组合金属保护剂包括一种唑类化合物和一种水溶性聚合物。
8.如权利要求7所述的抛光液，其特征在于，所述的唑类化合物为苯并三氮唑及其衍生物；所述水溶性聚合物为聚丙烯酸及其共聚物。
9.如权利要求7所述的抛光液，其特征在于，所述唑类化合物的浓度为0.01-0.5％；所述水溶性聚合物的浓度为0.005-0.1％。
10.如权利要求9所述的抛光液，其特征在于，所述唑类化合物的浓度为0.05-0.2％；所述水溶性聚合物的浓度为0.01-0.05％。
11.如权利要求1所述的抛光液，其特征在于，所述的络合剂选自有机磷酸，PBTCA，HPAA，HEDP，EDTMP和ATMP中的一种或多种。
12.如权利要求1所述的抛光液，其特征在于，所述络合剂的浓度为0.05％-1％。
13.如权利要求12所述的抛光液，其特征在于，所述络合剂的浓度为0.1-0.5％。
14.如权利要求1所述的抛光液，其特征在于，所述氮化硅抑制剂为一种萘磺酸盐的甲醛缩聚物，具有以下通式：
其中：
15.如权利要求14所述的抛光液，其特征在于，所述氮化硅抑制剂为亚甲基双萘磺酸二钠盐，甲基萘磺酸甲醛缩聚物和/或苄基萘磺酸甲醛缩聚物。
16.如权利要求1所述的抛光液，其特征在于，所述pH调节剂为一种有机羧酸。
17.如权利要求16所述的抛光液，其特征在于，所述有机羧酸选自草酸，丙二酸，丁二酸，柠檬酸和酒石酸中的一种或多种。
18.如权利要求1所述的抛光液，其特征在于，所述氧化剂为过氧化物或过硫化物。
19.如权利要求18所述的抛光液，其特征在于，所述氧化剂选自过氧化氢，过氧化钠，过氧化钾，过氧化苯甲酰，过硫酸钠，过硫酸钾和过硫酸铵中的一种或多种。(此处氧化剂需要每一种都出现在实施例中至少一次)
20.如权利要求1所述的抛光液，其特征在于，所述抛光液还包括：杀菌防霉变剂。
21.如权利要求20所述的抛光液，其特征在于，所述杀菌防霉变剂为季铵盐活性剂。
22.如权利要求1所述的抛光液，其特征在于，所述抛光液的pH值为2-5。
23.如权利要求22所述的抛光液，其特征在于，所述抛光液的pH值为3-4。
24.如权利要求1所述的抛光液，其特征在于，所述氮化硅抑制剂的浓度从50ppm到0.1％。
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| PCT/CN2012/001016 WO2013082863A1 (zh) | 2011-12-07 | 2012-07-30 | 一种tsv阻挡层抛光液 |
| KR1020147015534A KR20140100953A (ko) | 2011-12-07 | 2012-07-30 | Tsv 장벽층용 연마 슬러리 |
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| CN111378375A (zh) * | 2018-12-28 | 2020-07-07 | 安集微电子科技（上海）股份有限公司 | 一种化学机械抛光液 |
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| TWI534221B (zh) | 2016-05-21 |
| SG11201402831SA (en) | 2014-08-28 |
| CN103146306B (zh) | 2016-12-28 |
| TW201323547A (zh) | 2013-06-16 |
| KR20140100953A (ko) | 2014-08-18 |
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