CN111378366B - Chemical mechanical polishing solution and application thereof - Google Patents
Chemical mechanical polishing solution and application thereof Download PDFInfo
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- CN111378366B CN111378366B CN201811613972.2A CN201811613972A CN111378366B CN 111378366 B CN111378366 B CN 111378366B CN 201811613972 A CN201811613972 A CN 201811613972A CN 111378366 B CN111378366 B CN 111378366B
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- chemical mechanical
- mechanical polishing
- polishing solution
- polishing
- silicon dioxide
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- 238000005498 polishing Methods 0.000 title claims abstract description 73
- 239000000126 substance Substances 0.000 title claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 22
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000007046 ethoxylation reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 239000002736 nonionic surfactant Substances 0.000 abstract description 7
- 230000003746 surface roughness Effects 0.000 abstract description 7
- 239000003989 dielectric material Substances 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 10
- 238000007517 polishing process Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000005380 borophosphosilicate glass Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
- H01L21/31055—Planarisation of the insulating layers involving a dielectric removal step the removal being a chemical etching step, e.g. dry etching
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention provides a chemical mechanical polishing solution comprising abrasive particles and an ethoxylated butoxylated alkyl alcohol. The chemical mechanical polishing solution of the invention, by adding the nonionic surfactant with a specific molecular structure, greatly improves the surface roughness of the silicon dioxide (TEOS) after polishing while obtaining high silicon dioxide (TEOS) removal rate, effectively reduces the residue of surface pollutants, ensures that better wafer surface smoothness and flatness are obtained after polishing, and can meet the requirements on the surface of a dielectric material under various process conditions.
Description
Technical Field
The invention relates to the technical field of polishing solution, in particular to chemical mechanical polishing solution for flattening a silicon dioxide substrate in the field of integrated circuit manufacturing and application thereof.
Background
In the fabrication of integrated circuits, thousands of structural units are often built on a silicon wafer substrate, and these structural units are interconnected by multiple layers of metal to further form functional circuits and devices. In the multilevel metal interconnection structure, silicon dioxide or silicon dioxide doped with other elements is filled between metal wires to be used as an interlayer Dielectric (ILD). With the development of integrated circuit metal interconnection technology and the increase of the number of wiring layers, chemical Mechanical Polishing (CMP) has been widely used for surface planarization in the chip manufacturing process. These planarized chip surfaces facilitate the production of multi-layer integrated circuits and prevent distortions caused by the application of dielectric layers on uneven surfaces.
The CMP process is the polishing of the surface of the integrated circuit using an abrasive-containing mixture and a polishing pad. In a typical chemical mechanical polishing process, a substrate is brought into direct contact with a rotating polishing pad, and a carrier is used to apply pressure to the backside of the substrate. During polishing, the pad and platen are rotated while maintaining a downward force on the back surface of the substrate, and an abrasive and chemically reactive solution (commonly referred to as a slurry or slurry) are applied to the pad, which reacts chemically with the film being polished to begin the polishing process.
Silicon dioxide, a commonly used dielectric material in integrated circuits, involves the removal of the silicon dioxide dielectric layer in many polishing processes. For example, in the polishing process of the oxide interlayer dielectric, the polishing slurry is mainly used for removing the oxide dielectric layer and flattening; when the shallow trench isolation layer is polished, the polishing solution is mainly used for removing and flattening the oxide dielectric layer and stopping on the silicon nitride; in barrier layer polishing, the polishing solution needs to remove silicon dioxide, copper and a copper barrier layer; in a Through Silicon Via (TSV) process, the formation of the Via also requires the removal of excess Silicon dioxide with a polishing solution. In these polishing processes, a higher removal rate of the oxide dielectric layer is required to ensure the productivity.
Oxide dielectric materials include thin film thermal oxide silicon dioxide (thin thermal oxide), high density plasma oxide (high density plasma oxide), borophosphosilicate glass (borophosphosilicate glass), tetraethoxy silicon dioxide (PETEOS), and carbon doped silicon dioxide (carbon doped oxide). Polishing abrasives used in the silica dielectric material polishing slurry are mainly ceria and silica, but the ceria abrasive easily scratches the surface during polishing. Silica generates less surface defects during polishing, so silica is used in a large amount as abrasive grains. However, to achieve higher oxide material removal rates, it is common to increase the amount of abrasive particles used, which increases the surface roughness of the wafer.
The chemical mechanical polishing solution disclosed in chinese patent CN104449396A adopts sulfonic acid compounds to improve the surface defect degree of polished silica, and comprises water, colloidal silica abrasive, sulfonic acid additives, a clathrate, and an oxidizing agent, and the pH value is greater than or equal to 10. The chemical mechanical polishing solution has a silicon oxide removal rate of not less than 1000Per minute, and promotes post-polishing dimensions>The SP1 defect count of 0.16 micron is less than or equal to 70, and the SP1 scratch number is less than or equal to 25. A number of patents also disclose the use of nonionic surfactants in polishing solutions. Chinese patent CN1688665A discloses the use of an amphiphilic nonionic surfactant in the chemical mechanical polishing process of copper, which reduces dishing and dielectric erosion by adding the surfactant, but does not address the effect of the surfactant on the silica surface. Chinese patent CN101280158A discloses a chemical mechanical polishing solution for polysilicon, which uses a polyol-type nonionic surfactant to inhibit the removal rate of polysilicon, so as to obtain the polysilicon/silicon dioxide removal rate selectivity ratio required by the process. But the effect of the nonionic surfactant on the silica surface is not mentioned.
In order to overcome the problems of large surface roughness and more residual pollutants of silicon dioxide (TEOS) in the polishing process of the conventional chemical polishing solution, a new chemical mechanical polishing solution is urgently needed.
Disclosure of Invention
In order to solve the problems, the invention provides a chemical mechanical polishing solution, which improves the problems of surface flatness and much pollutant residue of a polished wafer through a nonionic surfactant with a specific molecular structure.
In order to achieve the above purpose, the invention is realized by the following technical scheme: a chemical mechanical polishing slurry is provided comprising abrasive particles and an ethoxylated butoxylated alkyl alcohol.
Preferably, the ethoxy butoxylated alkyl alcohol has 5 to 20 ethoxy groups x, 5 to 20 butoxy groups y, and an alkyl group of 11 to 15 carbon atoms which is straight or branched.
Preferably, the concentration of the ethoxylated butoxylated alkyl alcohol is 0.0005 to 1% by mass
Preferably, the concentration of the ethoxylated butoxylated alkyl alcohol is 0.001% -0.5% by mass.
Preferably, the abrasive particles are selected from one or more of silicon dioxide, aluminum oxide, cerium oxide, aluminum-doped silicon dioxide, and polymer particles.
Preferably, the content of the abrasive particles is 5-30% by mass. .
Preferably, the content of the grinding particles is 10-25% by mass.
Preferably, the abrasive particles have a particle size of 30 to 200nm.
Preferably, the abrasive particles have a particle size of 50 to 180nm.
Preferably, the pH value of the chemical mechanical polishing solution is 8-12.
Preferably, the pH value of the chemical mechanical polishing solution is 9-12.
The chemical mechanical polishing solution can also comprise a metal corrosion inhibitor, a complexing agent, an oxidizing agent and the like which are used for polishing silicon dioxide and metal at the same time.
The chemical mechanical polishing solution of the present invention may further comprise other additives commonly used in the art, such as pH regulator, bactericide, etc
In another aspect, the present invention provides a use of the chemical mechanical polishing liquid described above in polishing silicon dioxide.
The chemical mechanical polishing solution can be prepared by the following method: mixing the above components at a certain proportion, and adjusting to desired pH value with pH regulator (such as KOH or HNO 3).
Compared with the prior art, the chemical mechanical polishing solution has the following beneficial effects: the chemical mechanical polishing solution greatly improves the surface roughness of silicon dioxide (TEOS) after polishing by the nonionic surfactant with a specific molecular structure, effectively reduces the residue of surface pollutants, obtains high silicon dioxide (TEOS) removal rate, ensures better wafer surface smoothness and flatness after polishing, and can meet the requirements on the surface of a dielectric material under various process conditions.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
The reagents and starting materials used in the present invention are commercially available.
The wt% of the invention refers to mass percentage.
Preparation examples:
table 1 shows the components and contents of the polishing solutions of examples 1 to 11 of the present invention and comparative examples 1 to 3. And preparing polishing solutions of examples and comparative examples according to the table, uniformly mixing the components, supplementing the mass percent to 100% with water, and adjusting the pH to a corresponding value by using a pH regulator to obtain the polishing solutions of the examples and the comparative examples.
TABLE 1 polishing slurry compositions of inventive examples 1-11 and comparative examples 1-3
Effect embodiment:
silica (TEOS) was polished using comparative polishing solutions 1 to 3 and polishing solutions of examples 1 to 11 under the following polishing conditions: the polishing machine is a 12-Reflexion LK machine, the polishing pad is IC1010pad, the downward pressure is 4.0psi, the rotating speed is that the polishing disk/polishing head =93/87rpm, the flow rate of the polishing solution is 300ml/min, and the polishing time is 1min. The results of the removal rate, the surface roughness of the polished silicon dioxide wafer measured by atomic force microscope AFM, and the number of contaminant particles on the surface of the polished silicon dioxide wafer measured by defect scanner SP2 are shown in table 2.
TABLE 2 removal Rate, surface roughness, surface contaminant particle count for TEOS for comparative polishing solutions 1-3 and polishing solutions of examples 1-11
The results are shown in table 2: the addition of the ethoxy butoxyl alkyl alcohol greatly improves the surface roughness of TEOS after polishing and effectively reduces the residue of surface pollutants, so that the polishing solution of the invention can obtain high silicon dioxide removal rate, simultaneously ensure better wafer surface smoothness and flatness after polishing, and can meet the requirements on the surface of a dielectric material under various process conditions.
It should be noted that the embodiments of the present invention have been described in a preferred embodiment and not limited to the embodiments, and those skilled in the art may modify and modify the above-disclosed embodiments to equivalent embodiments without departing from the scope of the present invention.
Claims (9)
1. A chemical mechanical polishing solution comprising abrasive particles and an ethoxylated butoxylated alkyl alcohol;
in the ethoxylated butoxylated alkyl alcohol, the number x of ethoxylation groups is 5-20, the number y of butoxylation groups is 5-20, and alkyl is a straight chain or branched chain with 11-15 carbon atoms;
the mass percentage concentration of the ethoxylated butoxylated alkyl alcohol is 0.0005 to 1 percent;
the pH value of the chemical mechanical polishing solution is 8-12.
2. The chemical mechanical polishing solution of claim 1, wherein the ethoxylated butoxylated alkyl alcohol is present in a concentration of 0.001% to 0.5% by weight.
3. The chemical mechanical polishing solution of claim 1 wherein the abrasive particles are selected from one or more of silicon dioxide, aluminum oxide, cerium oxide, aluminum-doped silicon dioxide, and polymer particles.
4. The chemical mechanical polishing solution of claim 1, wherein the abrasive particles are present in an amount of 5 to 30% by mass.
5. The chemical mechanical polishing solution of claim 4, wherein the content of the abrasive particles is 10-25% by mass.
6. The chemical mechanical polishing solution of claim 1, wherein the abrasive particles have a particle size of 30 to 200nm.
7. The chemical mechanical polishing solution of claim 6, wherein the abrasive particles have a particle size of 50 to 180nm.
8. The chemical mechanical polishing solution according to claim 1, wherein the pH of the chemical mechanical polishing solution is 9 to 12.
9. Use of a chemical mechanical polishing liquid according to any one of claims 1 to 8 for polishing silica.
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CN201811613972.2A CN111378366B (en) | 2018-12-27 | 2018-12-27 | Chemical mechanical polishing solution and application thereof |
TW108148032A TWI826624B (en) | 2018-12-27 | 2019-12-27 | Chemical-mechanical polishing slurry and its using method |
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CN201811613972.2A CN111378366B (en) | 2018-12-27 | 2018-12-27 | Chemical mechanical polishing solution and application thereof |
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CN111378366B true CN111378366B (en) | 2022-11-18 |
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CN113122143B (en) * | 2019-12-31 | 2024-03-08 | 安集微电子(上海)有限公司 | Chemical mechanical polishing solution and application thereof in copper polishing |
Citations (6)
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CN1902291A (en) * | 2003-11-14 | 2007-01-24 | 昭和电工株式会社 | Polishing composition and polishing method |
CN101638557A (en) * | 2008-08-01 | 2010-02-03 | 安集微电子(上海)有限公司 | Chemi-mechanical polishing liquid |
CN102585649A (en) * | 2012-03-06 | 2012-07-18 | 淮海工学院 | Silicone-acrylic-resin-based self-polishing marine antifouling coating |
CN103361028A (en) * | 2012-04-10 | 2013-10-23 | 盟智科技股份有限公司 | Polishing slurry composition |
CN104046246A (en) * | 2013-03-12 | 2014-09-17 | 气体产品与化学公司 | Chemical Mechanical Planarization for Tungsten-Containing Substrates |
CN108250973A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子科技(上海)股份有限公司 | A kind of chemical mechanical polishing liquid for barrier layer planarization |
Family Cites Families (2)
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US7335788B2 (en) * | 2000-02-16 | 2008-02-26 | Lubrizol Advanced Materials, Inc. | S-(α, α′-disubstituted-α″-acetic acid) substituted dithiocarbonate derivatives for controlled radical polymerizations, process and polymers made therefrom |
US9281210B2 (en) * | 2013-10-10 | 2016-03-08 | Cabot Microelectronics Corporation | Wet-process ceria compositions for polishing substrates, and methods related thereto |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1902291A (en) * | 2003-11-14 | 2007-01-24 | 昭和电工株式会社 | Polishing composition and polishing method |
CN101638557A (en) * | 2008-08-01 | 2010-02-03 | 安集微电子(上海)有限公司 | Chemi-mechanical polishing liquid |
CN102585649A (en) * | 2012-03-06 | 2012-07-18 | 淮海工学院 | Silicone-acrylic-resin-based self-polishing marine antifouling coating |
CN103361028A (en) * | 2012-04-10 | 2013-10-23 | 盟智科技股份有限公司 | Polishing slurry composition |
CN104046246A (en) * | 2013-03-12 | 2014-09-17 | 气体产品与化学公司 | Chemical Mechanical Planarization for Tungsten-Containing Substrates |
CN108250973A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子科技(上海)股份有限公司 | A kind of chemical mechanical polishing liquid for barrier layer planarization |
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TWI826624B (en) | 2023-12-21 |
TW202024292A (en) | 2020-07-01 |
CN111378366A (en) | 2020-07-07 |
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