WO2017114301A1 - Suspension de polissage chimico-mécanique pour métal - Google Patents

Suspension de polissage chimico-mécanique pour métal Download PDF

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Publication number
WO2017114301A1
WO2017114301A1 PCT/CN2016/111684 CN2016111684W WO2017114301A1 WO 2017114301 A1 WO2017114301 A1 WO 2017114301A1 CN 2016111684 W CN2016111684 W CN 2016111684W WO 2017114301 A1 WO2017114301 A1 WO 2017114301A1
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WIPO (PCT)
Prior art keywords
acid
mechanical polishing
chemical mechanical
polishing slurry
metal chemical
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PCT/CN2016/111684
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English (en)
Chinese (zh)
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张建
荆建芬
宋凯
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安集微电子科技(上海)有限公司
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Publication of WO2017114301A1 publication Critical patent/WO2017114301A1/fr

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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00Brightening metals by chemical means
    • C23F3/04Heavy metals
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00Brightening metals by chemical means
    • C23F3/04Heavy metals
    • C23F3/06Heavy metals with acidic solutions

Definitions

  • the present invention relates to a chemical mechanical polishing slurry and its use, and more particularly to a chemical mechanical polishing slurry for copper and its use.
  • the copper interconnect can only be fabricated by a damascene process, that is, : forming a trench in the first layer, filling the trench with a copper barrier layer and copper, forming a metal wire and covering the dielectric layer.
  • the excess copper/copper barrier on the dielectric layer is then removed by chemical mechanical polishing leaving a single interconnect in the trench.
  • the chemical mechanical polishing process of copper is generally divided into three steps. The first step is to remove a large amount of copper on the surface of the substrate with a high and low pressure at a high and low removal rate. The second step is to approach the barrier layer. When the downforce is lowered, the removal rate is reduced to polish the remaining metal copper and stopped in the barrier layer.
  • the barrier layer polishing solution is used to remove the barrier layer and part of the dielectric layer and the metal copper to achieve planarization.
  • copper polishing should remove excess copper on the barrier layer as soon as possible.
  • the butterfly depression of the polished copper wire should be minimized.
  • the metal layer Prior to copper polishing, the metal layer is partially recessed above the copper wire.
  • polishing The copper on the dielectric material is easily removed at higher bulk pressures, while the copper at the depressions is subjected to a lower polishing pressure than the bulk pressure and a lower copper removal rate. As the polishing progresses, the height difference of the copper is gradually reduced to achieve flattening.
  • the passivation film of copper is easily removed even at a lower pressure (such as a copper line depression), resulting in planarization efficiency. Reduced, the polished butterfly depression increases.
  • TSV Through-silicon via
  • the current TSV process combines a conventional IC process to form copper vias through a silicon substrate, that is, copper is filled in the TSV opening to achieve conduction, and excess copper after filling needs to be removed by chemical mechanical polishing to achieve planarization.
  • the excess copper in the surface after filling is usually several to several tens of micrometers thick due to the deep through-silicon via. In order to quickly remove these extra copper. It is usually required to have a high copper removal rate while the surface roughness after polishing is good. In order to make copper better in semiconductor technology, people are constantly trying to improve the new polishing solution.
  • Chinese patent CN1256765C provides a polishing liquid containing citric acid, potassium citrate and a chelate organic acid buffer system.
  • CN1195896C employs a polishing liquid containing an oxidizing agent, a carboxylate such as ammonium citrate, an abrasive slurry, an optional triazole or triazole derivative.
  • CN1459480A provides a copper chemical mechanical polishing liquid comprising a film forming agent and a film forming aid: the film forming agent is composed of a buffer solution composed of a mixture of a strong base and acetic acid, and the film forming aid is potassium nitrate (sodium) salt. .
  • 5,552,742 provides a metal chemical mechanical polishing slurry comprising a surfactant comprising aramid silicone, an alkane polysiloxane, a polyoxyalkylene ether and copolymers thereof.
  • US6821897B2 provides a use of poly A copper chemical mechanical polishing method for a polishing agent of a complexing agent, which employs a negatively charged polymer including sulfuric acid and salts thereof, sulfates, phosphoric acid, phosphates, phosphates and the like.
  • the US5527423 metal chemical mechanical polishing slurry comprises one or more of a surfactant: aramid siloxane, polysiloxane, polyoxyalkylene ether and copolymers thereof.
  • the technology in the above patents strives to reduce pitting and corrosion of the copper layer during the polishing process of copper, control the static etching rate, thereby better removing the copper layer, improving the polishing rate of copper, and obtaining good copper mutuality. Even flat.
  • the above patent overcomes the problems encountered by the above copper in the polishing process to a certain extent, but the effect is not obvious. After use, there are defects on the copper surface, the flatness is low, and the polished copper wire has a dish-shaped depression and a large The problem of narrow window throwing; the polishing rate is not high enough to be applied to processes requiring higher removal rates.
  • the invention provides a metal chemical mechanical polishing slurry, wherein a surfactant containing phosphate as a main component is added to the polishing slurry, which can maintain a high polishing rate of copper and reduce the dishing of the copper after polishing. It improves the flatness of the surface, strengthens the polishing effect, and has fewer defects on the copper surface after polishing, and has no defects such as corrosion.
  • a metal chemical mechanical polishing slurry comprising abrasive particles, a complexing agent, a corrosion inhibitor, an oxidizing agent and a phosphate surfactant, wherein the phosphate surfactant is a phosphate monoester compound and a phosphoric acid ester
  • the mass percentage of the phosphate monoester compound and the phosphodiester compound is 70:30-30:70.
  • the structural formula of the phosphoric acid monoester compound is as shown in 1, and the structural formula of the phosphodiester compound is as shown in 2:
  • X RO, RO-(CH 2 CH 2 O) n , RCOO-(CH 2 CH 2 O) n ;
  • R is a glyceryl group or a C8-C22 alkyl group, an alkylbenzene group, etc.;
  • the phosphate surfactant is polyoxyethylene ether phosphate or a salt thereof, preferably dodecyl polyoxyethylene ether phosphate, dodecane Polyoxyethylene ether phosphate potassium salt, octadecyl polyoxyethylene ether phosphate, octadecyl polyoxyethylene ether phosphate potassium salt.
  • the surfactant is an alkylphenol ethoxylate phosphate or a salt thereof, preferably octylphenol ethoxylate phosphate, nonylphenol ethoxylate phosphate, octadecane Sodium phenol polyoxyethylene ether phosphate sodium salt.
  • the metal chemical mechanical polishing slurry of the present invention wherein the abrasive particles are one of silica, alumina, doped aluminum or aluminum-coated silica, ceria, titania, and polymer abrasive particles or A variety.
  • the metal chemical mechanical polishing slurry of the present invention wherein the abrasive particles are contained in an amount of 0.1 to 20% by mass.
  • the metal chemical mechanical polishing slurry of the present invention wherein the complexing agent is one of an amino acid and a salt thereof, an aminocarboxylic acid compound and a salt thereof, an organic carboxylic acid and a salt thereof, an organic phosphonic acid and a salt thereof, and an organic amine Or several.
  • the amino acid is glycine, alanine, valine, leucine, valine, phenylalanine, tyrosine, tryptophan, lysine, arginine, histidine, serine , aspartic acid, threonine, glutamic acid, asparagine, glutamine;
  • the aminocarboxylate compound and its salt are ammonia triacetic acid, ethylenediaminetetraacetic acid, cyclohexanediaminetetraacetic acid, ethylene One or more of amine disuccinic acid, diethylene triamine penta acetic acid and triethylene tetraamine hexaacetic acid;
  • the organic carboxylic acid is acetic acid, oxalic acid, citric acid, tartaric acid, malonic acid, succinic acid, apple One or more of acid, lactic acid, gallic acid and sulfosalicylic acid;
  • the organic phosphoric acid is 2-phosphonic acid butane
  • the mass percentage is 0.1-5%
  • the metal chemical mechanical polishing slurry of the present invention wherein the oxidizing agent is hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, persulfate, percarbonate, periodic acid, perchloric acid, One or more of high boronic acid, potassium permanganate, and ferric nitrate.
  • the content of the oxidizing agent is 0.05-10% by mass.
  • the metal chemical mechanical polishing slurry of the present invention wherein the corrosion inhibitor is one or more of a azole, an imidazole, a thiazole, a pyridine, and a pyrimidine compound.
  • the azole compound is benzotriazole, 5-methylbenzotriazole, 5-carboxybenzotriazole, 1-hydroxy-benzotriazole, 1,2,4-triazo Oxazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 5-carboxyl -3-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 5-acetic acid-1H-tetrazole, 5-methyltetrazolium One or more of 5-phenyltetrazolium, 5-amino-1H-tetrazole and 1-phenyl-5-mercapto-tetrazole; the azo
  • the thiazole compound is one or more of 2-mercapto-benzothiazole, 2-mercaptothiadiazole and 5-amino-2-mercapto-1,3,4-thiadiazole;
  • the pyridine It is one or more of 2,3-diaminopyridine, 2-aminopyridine and 2-picolinic acid;
  • the pyrimidine is a 2-aminopyrimidine.
  • the metal chemical mechanical polishing slurry of the present invention has a pH of from 3 to 11, preferably from 4 to 8.
  • the above metal chemical mechanical polishing slurry further includes a conventional additive in the field such as a pH adjuster, a viscosity modifier, an antifoaming agent, and a bactericide.
  • a conventional additive in the field such as a pH adjuster, a viscosity modifier, an antifoaming agent, and a bactericide.
  • the above metal chemical mechanical polishing slurry is prepared, other components other than the oxidizing agent can be prepared.
  • the sample is concentrated and diluted with deionized water to the concentration range of the present invention before use and an oxidizing agent is added.
  • metal chemical mechanical polishing slurry of the present invention in chemical mechanical polishing of a substrate containing copper.
  • advantages of using the metal chemical mechanical polishing slurry of the present invention are as follows:
  • the polishing slurry of the present invention has a reduced copper removal rate at a low pressure, and still has a high copper removal rate under high pressure, thereby increasing the productivity.
  • the metal chemical mechanical polishing slurry of the present invention enhances the polishing effect of copper, reduces the butterfly depression of the polished copper wire, and improves the over-throwing window.
  • 1A and 1B are scanning electron micrographs of a copper wafer surface polished by the polishing slurry of the present invention.
  • 2A and 2B are scanning electron micrographs of the surface of a copper wafer polished and immersed by the polishing slurry of the present invention.
  • Table 1 shows Examples 1 to 49 of the chemical mechanical polishing liquid of the present invention. According to the formulation given in the table, the components other than the oxidizing agent were uniformly mixed, and the mass percentage was made up to 100% with water. Adjust to the desired pH with KOH or HNO 3 . Add oxidizing agent before use and mix well.
  • Table 2 shows Examples 50 to 71 and Comparative Examples 1 to 9 of the chemical mechanical polishing liquid of the present invention, according to the formulation given in the table, the components other than the oxidizing agent were uniformly mixed, and the mass percentage was made up to 100 by water. %. Adjust to the desired pH with KOH or HNO 3 . Add oxidizing agent before use and mix well.
  • the copper (Cu) wafer and the patterned copper wafer are polished using the comparative polishing liquids 1 to 8 and the polishing liquids 50 to 65 of the present invention.
  • the removal rate of the obtained copper is shown in Table 3.
  • the polishing conditions of the pattern wafer and the butterfly dishing value and copper residue of the copper block are shown in Table 4.
  • Empty copper wafer polishing conditions downforce 1 to 3 psi; polishing disc and polishing head rotation speed 93/87 rpm, polishing pad IC1010, polishing liquid flow rate 150 ml/min, polishing machine 8" Mirra.
  • Patterned copper wafer polishing process conditions polishing disc and polishing head rotation speed 93/87 rpm, polishing pad IC1010, polishing liquid flow rate 150 ml/min, polishing machine table 8" Mirra. Polished on the polishing disc 1 with corresponding downforce The patterned copper wafer was left to residual copper of about 3000 A, and then the residual copper was removed and polished for 20 seconds on the polishing disk 2 with a corresponding downforce. The patterned copper wafer was measured by XE-300P atomic force microscope at 80 um*80 um. Butterfly trap value of copper block, observe the patterned copper after polishing The residual copper on the wafer is shown in Table 4.
  • Table 4 Butterfly depressions at 80um*80um copper block and copper residue after polishing under different polishing conditions of patterned copper wafers
  • Example 57 The patterned wafer polished in Example 57 was immersed in the polishing solution for 30 minutes, and the surface condition of the copper wire before the immersion (after polishing) and after immersion was observed by a scanning electron microscope, see FIGS. 1A, 1B, 2A, 2B. It can be seen from the figure that the surface of the wafer polished by the polishing liquid has no corrosion and no defects. After immersing in the polishing solution for 30 minutes, the copper wire still has no obvious corrosion and defects, indicating that the polishing liquid of the present invention has a strong ability to inhibit metal corrosion.
  • the copper (Cu) wafer, the empty silicon dioxide wafer, the empty wafer wafer, and the patterned copper wafer are polished using the comparative polishing liquid 9 and the polishing liquids 66 to 71 of the present invention. Polished rate And the butterfly depression value of the copper block is shown in Table 5.
  • Patterned copper wafer polishing process conditions polishing disk and polishing head rotation speed 93/87 rpm, polishing pad IC1010, polishing liquid flow rate 150ml/min, polishing machine table 8" Mirra. Polished on the polishing plate 1 with 3psi under pressure The patterned copper wafer was left to about 5000 A of residual copper, and then the residual copper was removed by a 2 psi downforce on the polishing pad 2. The patterned copper wafer was measured on a patterned copper wafer by XE-300P atomic force microscope (copper wire/dioxide) Butterfly trap value at the copper wire of silicon).
  • Table 5 Blank removal rate of polishing solution and polishing condition of patterned copper wafer and butterfly depression value after polishing
  • the metal chemical mechanical polishing slurry 66-68 of the present invention can achieve a smoother polished surface while maintaining a higher removal rate than the comparative polishing liquid 9, by Example 69.
  • the polishing solution can also provide a higher removal rate of silicon dioxide and germanium while the copper removal rate is adjustable.
  • the polishing solution can meet different application needs.
  • wt% of the present invention refers to the mass percentage.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

La présente invention concerne une suspension de polissage chimico-mécanique pour le cuivre, et des applications associées. Ladite suspension comprend : (a) des particules abrasives, (b) un agent complexant, (c) un agent oxydant, (d) un inhibiteur de corrosion et (e) un agent tensio-actif phosphate. À l'aide de la suspension de la présente invention, une vitesse élevée d'élimination du cuivre peut être maintenue, les évidements concaves, les fenêtres de surpolissage et d'autres défauts d'un fil de cuivre poli sont réduits, il y a moins de salissures sur une surface de cuivre poli, et aucune corrosion ne se produit.
PCT/CN2016/111684 2015-12-31 2016-12-23 Suspension de polissage chimico-mécanique pour métal WO2017114301A1 (fr)

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CN201511029138.5 2015-12-31
CN201511029138.5A CN106929858A (zh) 2015-12-31 2015-12-31 金属化学机械抛光浆料

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CN113789519A (zh) * 2021-08-12 2021-12-14 上海新阳半导体材料股份有限公司 一种化学机械抛光后清洗液的应用
CN114000155A (zh) * 2021-09-26 2022-02-01 西北大学 一种通用型铝及其合金环保除灰剂
CN115260912A (zh) * 2022-07-29 2022-11-01 江苏山水半导体科技有限公司 用于降低硅片表面腐蚀的抛光液及其制备和使用方法
CN115785824A (zh) * 2022-12-21 2023-03-14 北京天科合达半导体股份有限公司 一种化学机械抛光液、其制备方法及应用
EP4127088A4 (fr) * 2020-03-31 2023-11-08 FUJIFILM Electronic Materials U.S.A, Inc. Compositions de polissage et leurs procédés d'utilisation

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CN108250234A (zh) * 2016-12-28 2018-07-06 安集微电子(上海)有限公司 一种磷酸酯表面活性剂的合成工艺及其应用
US11401441B2 (en) * 2017-08-17 2022-08-02 Versum Materials Us, Llc Chemical mechanical planarization (CMP) composition and methods therefore for copper and through silica via (TSV) applications
CN107629449A (zh) * 2017-08-24 2018-01-26 金寨宏伟新材料有限公司 一种pa6一级回料制备母粒的方法
CN111356747A (zh) * 2017-11-22 2020-06-30 巴斯夫欧洲公司 化学机械抛光组合物
CN109393673B (zh) * 2018-10-31 2021-09-03 深圳市指尖坊黄金珠宝首饰有限公司 镜面黄金表面抗花处理工艺
CN111378367A (zh) * 2018-12-27 2020-07-07 安集微电子(上海)有限公司 一种化学机械抛光液
CN111378376A (zh) * 2018-12-29 2020-07-07 安集微电子(上海)有限公司 一种化学机械抛光液及其应用
CN110434680A (zh) * 2019-07-19 2019-11-12 大连理工大学 一种螺旋桨的化学机械抛光液及抛光方法
CN113122142B (zh) * 2019-12-31 2024-04-12 安集微电子科技(上海)股份有限公司 一种化学机械抛光液
CN116288362A (zh) * 2023-02-17 2023-06-23 厦门金波贵金属制品有限公司 一种纯铜化学抛光酸洗液及其制作工艺、纯铜的表面抛光处理工艺

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CN103160207A (zh) * 2011-12-16 2013-06-19 安集微电子(上海)有限公司 一种金属化学机械抛光浆料及其应用
CN103865400A (zh) * 2012-12-10 2014-06-18 安集微电子(上海)有限公司 一种磷酸酯表面活性剂在自停止抛光中的应用
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4127088A4 (fr) * 2020-03-31 2023-11-08 FUJIFILM Electronic Materials U.S.A, Inc. Compositions de polissage et leurs procédés d'utilisation
CN113789519A (zh) * 2021-08-12 2021-12-14 上海新阳半导体材料股份有限公司 一种化学机械抛光后清洗液的应用
CN113789519B (zh) * 2021-08-12 2024-02-02 上海新阳半导体材料股份有限公司 一种化学机械抛光后清洗液的应用
CN114000155A (zh) * 2021-09-26 2022-02-01 西北大学 一种通用型铝及其合金环保除灰剂
CN114000155B (zh) * 2021-09-26 2023-09-12 西北大学 一种通用型铝及其合金环保除灰剂
CN115260912A (zh) * 2022-07-29 2022-11-01 江苏山水半导体科技有限公司 用于降低硅片表面腐蚀的抛光液及其制备和使用方法
CN115260912B (zh) * 2022-07-29 2024-03-26 江苏山水半导体科技有限公司 用于降低硅片表面腐蚀的抛光液及其制备和使用方法
CN115785824A (zh) * 2022-12-21 2023-03-14 北京天科合达半导体股份有限公司 一种化学机械抛光液、其制备方法及应用
CN115785824B (zh) * 2022-12-21 2024-04-09 北京天科合达半导体股份有限公司 一种化学机械抛光液、其制备方法及应用

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