CN111748286A - A kind of metal cobalt polishing liquid and its application - Google Patents
A kind of metal cobalt polishing liquid and its application Download PDFInfo
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- 238000005498 polishing Methods 0.000 title claims abstract description 112
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 29
- 239000010941 cobalt Substances 0.000 title claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 10
- 239000002184 metal Substances 0.000 title claims abstract description 9
- 239000007788 liquid Substances 0.000 title abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000007791 liquid phase Substances 0.000 claims abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000012286 potassium permanganate Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 abstract description 30
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 abstract description 28
- 229960003180 glutathione Drugs 0.000 abstract description 14
- 108010024636 Glutathione Proteins 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 239000008139 complexing agent Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000003746 surface roughness Effects 0.000 abstract description 5
- 229910017816 Cu—Co Inorganic materials 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 abstract 1
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 abstract 1
- 229960005261 aspartic acid Drugs 0.000 abstract 1
- 235000003704 aspartic acid Nutrition 0.000 description 18
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 14
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 12
- 239000010949 copper Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000004475 Arginine Substances 0.000 description 6
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 6
- 235000019260 propionic acid Nutrition 0.000 description 6
- 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 6
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 5
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 5
- 235000009582 asparagine Nutrition 0.000 description 5
- 229960001230 asparagine Drugs 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- -1 KMnO 4 Chemical compound 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001803 electron scattering Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- NSRBDSZKIKAZHT-UHFFFAOYSA-N tellurium zinc Chemical compound [Zn].[Te] NSRBDSZKIKAZHT-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
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
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
本发明涉及一种金属钴抛光液及其应用，按重量百分比，包括如下组分：液相载体50‑80％；磨料0.1‑10％；氧化剂≤10％；L‑天冬氨酸0.005‑10％；谷胱甘肽0.005‑10％。本发明通过调配氧化剂和络合剂的比例以及添加谷胱甘肽，得到的抛光液可以抑制金属钴的化学腐蚀，同时提高抛光速率以及降低表面粗糙度，同时降低Cu‑Co之间的电偶腐蚀，具有良好的应用前景。
The invention relates to a metal cobalt polishing liquid and an application thereof, comprising the following components in percentage by weight: liquid phase carrier 50-80%; abrasive 0.1-10%; oxidizing agent≤10%; L-aspartic acid 0.005-10% %; Glutathione 0.005‑10%. By adjusting the ratio of oxidant and complexing agent and adding glutathione, the obtained polishing liquid can inhibit the chemical corrosion of metal cobalt, improve the polishing rate and reduce the surface roughness, and reduce the galvanic coupling between Cu-Co at the same time. Corrosion, has good application prospects.
Description
技术领域technical field
本发明属于抛光液领域，特别涉及一种金属钴抛光液及其应用。The invention belongs to the field of polishing liquid, in particular to a metal cobalt polishing liquid and its application.
背景技术Background technique
随着特征尺寸进一步发展到14nm以下，由于在侧壁和晶界处电子散射的增加，Cu线电阻率不断提高，通过减少粘附层/阻挡层厚度去完善。钴(Co)由于其优异的性能已被选为IC铜互连的最有希望的阻挡金属之一。Co具有低电阻率，出色的台阶覆盖率，良好的热稳定性以及与铜的可靠附着力，可以有效地防止铜扩散。但是随着特征尺寸进一步缩小到7nm以下时，粘附层/阻挡层厚度不能无限减少，所以必须寻求新的互连线材料。作为替代金属的候选，Co不存在此问题，并且还提供了无空隙的无缝填充，并为金属和阻挡层厚度缩放提供了更多空间。由于这些优点，Co被认为是一种新型的导电互连材料，可在中部和前部金属化层替代钨(W)和铜。As feature sizes further develop below 14 nm, Cu wire resistivity continues to increase due to increased electron scattering at sidewalls and grain boundaries, which is refined by reducing adhesion/barrier thicknesses. Cobalt (Co) has been selected as one of the most promising barrier metals for IC copper interconnects due to its excellent properties. Co has low resistivity, excellent step coverage, good thermal stability, and reliable adhesion to copper, which can effectively prevent copper diffusion. However, as the feature size is further reduced below 7nm, the adhesion layer/barrier layer thickness cannot be reduced indefinitely, so new interconnect materials must be sought. As a candidate for metal replacement, Co does not suffer from this problem and also provides seamless filling without voids and more room for metal and barrier thickness scaling. Due to these advantages, Co is considered as a new type of conductive interconnect material that can replace tungsten (W) and copper in the middle and front metallization layers.
Co的抛光研究主要集中在弱酸弱碱性环境中的抛光。在酸性条件下，很容易对金属Co有化学腐蚀。碱性环境下Co表面会产生Co(OH)2和Co3O4。这些难溶于碱性溶液的氧化物或氢氧化物会抑制Co的抛光速率，导致Co的抛光速率很低。国内外对Co的CMP过程进行了诸多探索，但是还未找到满意的同时兼容抛光速率和抑制Co本身的化学腐蚀。因此本发明提出了一种能够提高Co的抛光速率，同时降低Cu-Co之间的电偶腐蚀的抛光液。The polishing research of Co mainly focuses on the polishing in weak acid and weak alkaline environment. Under acidic conditions, it is easy to chemically corrode the metal Co. Co(OH) 2 and Co 3 O 4 are generated on the surface of Co in an alkaline environment. These oxides or hydroxides that are poorly soluble in alkaline solution will inhibit the polishing rate of Co, resulting in a very low polishing rate of Co. Many explorations have been carried out on the CMP process of Co at home and abroad, but a satisfactory one that is compatible with the polishing rate and inhibits the chemical corrosion of Co itself has not yet been found. Therefore, the present invention provides a polishing solution which can improve the polishing rate of Co and reduce the galvanic corrosion between Cu-Co at the same time.
发明内容SUMMARY OF THE INVENTION
本发明所要解决的技术问题是提供一种金属钴抛光液及其应用，通过调配球形二氧化硅颗粒粒径以及氧化剂和络合剂的比例，得到的抛光液可以抑制金属钴的化学腐蚀，同时提高抛光速率以及降低表面粗糙度，同时降低Cu-Co之间的电偶腐蚀，具有良好的应用前景。The technical problem to be solved by the present invention is to provide a metallic cobalt polishing liquid and its application. By adjusting the particle size of spherical silica particles and the ratio of oxidant and complexing agent, the obtained polishing liquid can inhibit the chemical corrosion of metallic cobalt, and simultaneously It has good application prospects to improve the polishing rate and reduce the surface roughness, while reducing the galvanic corrosion between Cu-Co.
本发明提供了一种金属钴抛光液，按重量百分比，包括如下组分：The invention provides a kind of metallic cobalt polishing liquid, by weight percentage, comprises the following components:
优选的，所述液相载体为去离子水。Preferably, the liquid carrier is deionized water.
所述磨料为二氧化硅颗粒、氧化铈颗粒或氧化铝颗粒。The abrasives are silica particles, cerium oxide particles or alumina particles.
优选的，所述二氧化硅颗粒的粒径为5-100nm。Preferably, the particle size of the silica particles is 5-100 nm.
优选的，所述二氧化硅颗粒的粒径为单一粒径。所述单一粒径通常指所使用的二氧化硅颗粒的粒径保持一致。Preferably, the particle size of the silica particles is a single particle size. The single particle size generally means that the particle size of the silica particles used remains the same.
优选的，所述二氧化硅颗粒优选为球形二氧化硅颗粒或者非球形二氧化硅颗粒。Preferably, the silica particles are preferably spherical silica particles or non-spherical silica particles.
优选的，所述氧化剂为NaClO、KMnO4、K2Cr2O7、双氧水中的一种或几种。Preferably, the oxidant is one or more of NaClO, KMnO 4 , K 2 Cr 2 O 7 , and hydrogen peroxide.
优选的，所述抛光液为化学机械抛光(CMP)液。Preferably, the polishing liquid is a chemical mechanical polishing (CMP) liquid.
优选的，酸碱性的调节主要通过高浓度的氢氧化钾以及稀硝酸进行调节，pH范围选在7.00-12.00。Preferably, the adjustment of acidity and alkalinity is mainly carried out by high-concentration potassium hydroxide and dilute nitric acid, and the pH is selected in the range of 7.00-12.00.
有益效果beneficial effect
本发明通过调配氧化剂和络合剂的比例以及添加谷胱甘肽，得到的抛光液可以抑制金属钴的化学腐蚀，同时提高抛光速率以及降低表面粗糙度，同时降低Cu-Co之间的电偶腐蚀，具有良好的应用前景。By adjusting the ratio of oxidizing agent and complexing agent and adding glutathione in the present invention, the obtained polishing liquid can inhibit the chemical corrosion of metal cobalt, improve the polishing rate, reduce the surface roughness, and reduce the galvanic coupling between Cu-Co at the same time. Corrosion, has good application prospects.
附图说明Description of drawings
图1为抛光用的Co片的照片。Fig. 1 is a photograph of a Co sheet for polishing.
具体实施方式Detailed ways
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
取粒径80nm、固含量为5％的钠型球形二氧化硅磨料1000mL，一份不添加任何添加剂；其他份分别加入天冬氨酸、天冬酰胺、丙酸、1,2,3,4-丁烷四羧酸、精氨酸搅拌均匀。Take 1000mL of sodium-type spherical silica abrasive with a particle size of 80nm and a solid content of 5%, one part without any additives; the other parts are respectively added with aspartic acid, asparagine, propionic acid, 1,2,3,4 -Butanetetracarboxylic acid and arginine stir well.
抛光实验：本抛光实验使用CP-4机台，将2英寸的钴圆片通过蜡粘在抛光头上。抛光参数设置如下：抛光垫用Politex；抛光压力为3psi；抛光垫转速为90rpm；抛光片转速为90rpm；抛光液流速为125mL/min；抛光时间为10min。每次抛光结束后，清水清洗抛光垫5分钟，抛光后的片在清洗液中超声清洗10分钟后用氮气吹干。结果列于表1。Polishing experiment: In this polishing experiment, a CP-4 machine was used, and a 2-inch cobalt disc was adhered to the polishing head through wax. The polishing parameters were set as follows: Politex was used for polishing pad; polishing pressure was 3 psi; polishing pad rotation speed was 90 rpm; polishing pad rotation speed was 90 rpm; polishing liquid flow rate was 125 mL/min; polishing time was 10 min. After each polishing, the polishing pad was cleaned with clean water for 5 minutes, and the polished wafer was ultrasonically cleaned in the cleaning solution for 10 minutes and then blown dry with nitrogen gas. The results are listed in Table 1.
表1Table 1
由表1结果可知，在抛光液中加入不同的但等量的络合剂时，明显看出加入天冬氨酸提高钴的抛光速率效果最好，将钴的抛光速率提高三倍。其次是丙酸，抛光速率提高2倍。精氨酸提高钴抛光速率不明显。It can be seen from the results in Table 1 that when different but equal amounts of complexing agents are added to the polishing liquid, it is obvious that adding aspartic acid has the best effect on improving the polishing rate of cobalt, and the polishing rate of cobalt is increased by three times. Followed by propionic acid, the polishing rate increased by 2 times. Arginine did not significantly improve the cobalt polishing rate.
实施例2Example 2
取粒径80nm、固含量为5％的钠型球形二氧化硅磨料1000mL，每份均添加0.1％H2O2，一份不添加任何添加剂；其他份分别加入天冬氨酸、天冬酰胺、丙酸、1,2,3,4-丁烷四羧酸、精氨酸搅拌均匀。Take 1000mL of sodium-type spherical silica abrasive with a particle size of 80nm and a solid content of 5%, add 0.1% H 2 O 2 to each part, and add no additives to one part; add aspartic acid and asparagine to the other parts respectively , propionic acid, 1,2,3,4-butanetetracarboxylic acid and arginine, and stir well.
抛光实验：本抛光实验使用CP-4机台，将2英寸的钴圆片通过蜡粘在抛光头上。抛光参数设置如下：抛光垫用Politex；抛光压力为3psi；抛光垫转速为90rpm；抛光片转速为90rpm；抛光液流速为125mL/min；抛光时间为10min。每次抛光结束后，清水清洗抛光垫5分钟，抛光后的片在清洗液中超声清洗10分钟后用氮气吹干。结果列于表2。Polishing experiment: In this polishing experiment, a CP-4 machine was used, and a 2-inch cobalt disc was adhered to the polishing head through wax. The polishing parameters were set as follows: Politex was used for polishing pad; polishing pressure was 3 psi; polishing pad rotation speed was 90 rpm; polishing pad rotation speed was 90 rpm; polishing liquid flow rate was 125 mL/min; polishing time was 10 min. After each polishing, the polishing pad was cleaned with clean water for 5 minutes, and the polished wafer was ultrasonically cleaned in the cleaning solution for 10 minutes and then blown dry with nitrogen gas. The results are listed in Table 2.
表2Table 2
由表2结果可知，在加入0.1％的双氧水时加入不同的络合剂，明显看出加入天冬氨酸的抛光速率最高并且将抛光速率提高七倍。其次是丙酸，1,2,3,4-丁烷四羧酸，天冬酰胺，最后是精氨酸。It can be seen from the results in Table 2 that different complexing agents are added when 0.1% hydrogen peroxide is added, and it is obvious that adding aspartic acid has the highest polishing rate and increases the polishing rate by seven times. This is followed by propionic acid, 1,2,3,4-butanetetracarboxylic acid, asparagine, and finally arginine.
实施例3Example 3
取粒径80nm、固含量为5％的钠型球形二氧化硅磨料1000mL，一份不添加任何添加剂；其他份分别加入不同浓度的天冬氨酸。Take 1000 mL of sodium-type spherical silica abrasive with a particle size of 80 nm and a solid content of 5%, one part without adding any additives; the other parts are respectively added with different concentrations of aspartic acid.
抛光实验：本抛光实验使用CP-4机台，将2英寸的钴圆片通过蜡粘在抛光头上。抛光参数设置如下：抛光垫用Politex；抛光压力为3psi；抛光垫转速为90rpm；抛光片转速为90rpm；抛光液流速为125mL/min；抛光时间为10min。每次抛光结束后，清水清洗抛光垫5分钟，抛光后的片在清洗液中超声清洗10分钟后用氮气吹干。结果列于表3。Polishing experiment: In this polishing experiment, a CP-4 machine was used, and a 2-inch cobalt disc was adhered to the polishing head through wax. The polishing parameters were set as follows: Politex was used for polishing pad; polishing pressure was 3 psi; polishing pad rotation speed was 90 rpm; polishing pad rotation speed was 90 rpm; polishing liquid flow rate was 125 mL/min; polishing time was 10 min. After each polishing, the polishing pad was cleaned with clean water for 5 minutes, and the polished wafer was ultrasonically cleaned in the cleaning solution for 10 minutes and then blown dry with nitrogen gas. The results are listed in Table 3.
表3table 3
由表3结果可知，增加天冬氨酸的浓度有利于提高钴的抛光速率。It can be seen from the results in Table 3 that increasing the concentration of aspartic acid is beneficial to improve the polishing rate of cobalt.
接下来将以0.5％天冬氨酸去研究其他添加剂。Next, other additives will be investigated with 0.5% aspartic acid.
实施例4Example 4
取粒径80nm，固含量为5％的钠型球形二氧化硅磨料1000mL，每份均添加0.5％天冬氨酸；其他份分别加入不同浓度的双氧水。Take 1000 mL of sodium-type spherical silica abrasive with a particle size of 80 nm and a solid content of 5%, add 0.5% aspartic acid to each part, and add hydrogen peroxide of different concentrations to the other parts.
抛光实验：本抛光实验使用CP-4机台，将2英寸的钴圆片通过蜡粘在抛光头上。抛光参数设置如下：抛光垫用Politex；抛光压力为3psi；抛光垫转速为90rpm；抛光片转速为90rpm；抛光液流速为125mL/min；抛光时间为10min。每次抛光结束后，清水清洗抛光垫5分钟，抛光后的片在清洗液中超声清洗10分钟后用氮气吹干。结果列于表4。Polishing experiment: In this polishing experiment, a CP-4 machine was used, and a 2-inch cobalt disc was adhered to the polishing head through wax. The polishing parameters were set as follows: Politex was used for polishing pad; polishing pressure was 3 psi; polishing pad rotation speed was 90 rpm; polishing pad rotation speed was 90 rpm; polishing liquid flow rate was 125 mL/min; polishing time was 10 min. After each polishing, the polishing pad was cleaned with clean water for 5 minutes, and the polished wafer was ultrasonically cleaned in the cleaning solution for 10 minutes and then blown dry with nitrogen gas. The results are listed in Table 4.
表4Table 4
由表4结果可知，在加入等量的天冬氨酸时，加入不同的双氧水对钴的抛光速率起到不一样的影响。随着双氧水浓度增大时，钴的抛光速率在逐渐提高。当加入1.0％H2O2，抛光速率反而出现了降低。抛光后钴的表面粗糙度也是出现了先减少后增大的现象。考虑到抛光速率超过100nm/min以及表面质量良好，所以选择0.1％H2O2进行后续实验探索。It can be seen from the results in Table 4 that when adding the same amount of aspartic acid, adding different hydrogen peroxide has different effects on the polishing rate of cobalt. As the concentration of hydrogen peroxide increases, the polishing rate of cobalt increases gradually. When 1.0% H 2 O 2 was added, the polishing rate decreased instead. The surface roughness of cobalt after polishing also decreases first and then increases. Considering that the polishing rate exceeds 100 nm/min and the surface quality is good, 0.1% H 2 O 2 is selected for subsequent experimental exploration.
实施例5Example 5
取粒径80nm，固含量为5％的钠型球形二氧化硅磨料1000mL，每份均添加天冬氨酸(L-Asp)和H2O2的基础上，添加一定量的谷胱甘肽(GSH)进行抛光实验。Take 1000 mL of sodium-type spherical silica abrasive with a particle size of 80 nm and a solid content of 5%, and add a certain amount of glutathione on the basis of adding aspartic acid (L-Asp) and H 2 O 2 to each portion. (GSH) for polishing experiments.
抛光实验：本抛光实验使用CP-4机台，将2英寸的钴圆片通过蜡粘在抛光头上。抛光参数设置如下：抛光垫用Politex；抛光压力为3psi；抛光垫转速为90rpm；抛光片转速为90rpm；抛光液流速为125mL/min；抛光时间为10min。每次抛光结束后，清水清洗抛光垫5分钟，抛光后的片在清洗液中超声清洗10分钟后用氮气吹干。结果列于表5。Polishing experiment: In this polishing experiment, a CP-4 machine was used, and a 2-inch cobalt disc was adhered to the polishing head through wax. The polishing parameters were set as follows: Politex was used for polishing pad; polishing pressure was 3 psi; polishing pad rotation speed was 90 rpm; polishing pad rotation speed was 90 rpm; polishing liquid flow rate was 125 mL/min; polishing time was 10 min. After each polishing, the polishing pad was cleaned with clean water for 5 minutes, and the polished wafer was ultrasonically cleaned in the cleaning solution for 10 minutes and then blown dry with nitrogen gas. The results are listed in Table 5.
表5table 5
由表5结果可知，在溶液中加入0.15％天冬氨酸的基础上，加入0.15％谷胱甘肽能将钴的抛光速率提高一倍。接着在溶液中加入0.5％天冬氨酸的基础上，加入0.15％谷胱甘肽能将钴的抛光速率提高25％。说明谷胱甘肽的加入有利于提高钴的抛光速率。It can be seen from the results in Table 5 that on the basis of adding 0.15% aspartic acid to the solution, adding 0.15% glutathione can double the polishing rate of cobalt. Then adding 0.15% glutathione to the solution can increase the polishing rate of cobalt by 25% on the basis of adding 0.5% aspartic acid to the solution. It shows that the addition of glutathione is beneficial to improve the polishing rate of cobalt.
实施例6Example 6
制备500mL溶液，每份均添加相同质量的天冬氨酸和H2O2的基础上，添加一定量的谷胱甘肽对铜和钴进行电化学测试。A 500 mL solution was prepared, and on the basis of adding the same mass of aspartic acid and H 2 O 2 to each portion, a certain amount of glutathione was added to conduct electrochemical tests on copper and cobalt.
电化学实验：本实验中所采用的参比电极是银/氯化银电极，对电极是面积为10×10cm2的Pt电极，工作电极是铜片/钴片，样品与溶液接触的工作面积是1cm2。电化学测试实验所用溶液是不含有硅溶胶的溶液，与静态刻蚀的溶液相同。动电位极化测试中的扫描速率为0.5mV/s，电位范围为-0.6～0.6V。Electrochemical experiment: The reference electrode used in this experiment is a silver/silver chloride electrode, the counter electrode is a Pt electrode with an area of 10 × 10 cm 2 , the working electrode is a copper sheet/cobalt sheet, and the working area of the sample in contact with the solution is 1cm 2 . The solution used in the electrochemical test experiment is a solution without silica sol, which is the same as the solution for static etching. The scan rate in the potentiodynamic polarization test was 0.5 mV/s, and the potential range was -0.6 to 0.6 V.
表6Table 6
由表6结果可知，在溶液中只加天冬氨酸和H2O2时，铜-钴之间的电位差是370mV。在溶液中加入0.1％谷胱甘肽时，铜-钴之间的电位差降低为341mV。说明谷胱甘肽有利于降低铜-钴之间的电偶腐蚀。It can be seen from the results in Table 6 that when only aspartic acid and H 2 O 2 are added to the solution, the potential difference between copper and cobalt is 370mV. When 0.1% glutathione was added to the solution, the potential difference between copper-cobalt was reduced to 341mV. It shows that glutathione is beneficial to reduce the galvanic corrosion between copper and cobalt.
当实施例给出数值范围时，应理解，除非本发明另有说明，每个数值范围的两个端点以及两个端点之间任何一个数值均可选用。除非另外定义，本发明中使用的所有技术和科学术语与本技术领域技术人员通常理解的意义相同。除实施例中使用的具体方法、设备、材料外，根据本技术领域的技术人员对现有技术的掌握及本发明的记载，还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。When numerical ranges are given in the examples, it is to be understood that, unless otherwise indicated herein, both endpoints of each numerical range and any number between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, equipment and materials used in the embodiments, according to the mastery of the prior art by those skilled in the art and the description of the present invention, the methods, equipment and materials described in the embodiments of the present invention can also be used Any methods, devices and materials similar or equivalent to those of the prior art can be used to implement the present invention.
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| CN100394555C (en) * | 2003-10-22 | 2008-06-11 | Cmp罗姆和哈斯电子材料控股公司 | Polishing method and polishing fluid using polishing pad and polishing fluid |
| CN101297015A (en) * | 2005-10-24 | 2008-10-29 | 3M创新有限公司 | Polishing fluids and methods for CMP |
| CN104830235A (en) * | 2015-04-29 | 2015-08-12 | 清华大学 | Polishing solution for chemically and mechanically polishing cobalt barrier layer structure and applications thereof |
| CN105295737A (en) * | 2014-07-25 | 2016-02-03 | 气体产品与化学公司 | Chemical mechanical polishing (CMP) of cobalt-containing substrate |
| CN109563375A (en) * | 2016-08-05 | 2019-04-02 | 凯斯科技股份有限公司 | Tungsten barrier polishing slurry composition |
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| CN100394555C (en) * | 2003-10-22 | 2008-06-11 | Cmp罗姆和哈斯电子材料控股公司 | Polishing method and polishing fluid using polishing pad and polishing fluid |
| CN101297015A (en) * | 2005-10-24 | 2008-10-29 | 3M创新有限公司 | Polishing fluids and methods for CMP |
| CN105295737A (en) * | 2014-07-25 | 2016-02-03 | 气体产品与化学公司 | Chemical mechanical polishing (CMP) of cobalt-containing substrate |
| CN104830235A (en) * | 2015-04-29 | 2015-08-12 | 清华大学 | Polishing solution for chemically and mechanically polishing cobalt barrier layer structure and applications thereof |
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