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WO2011069345A1 - Pâte de polissage mécano-chimique et son utilisation - Google Patents

Pâte de polissage mécano-chimique et son utilisation Download PDF

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Publication number
WO2011069345A1
WO2011069345A1 PCT/CN2010/002034 CN2010002034W WO2011069345A1 WO 2011069345 A1 WO2011069345 A1 WO 2011069345A1 CN 2010002034 W CN2010002034 W CN 2010002034W WO 2011069345 A1 WO2011069345 A1 WO 2011069345A1
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WO
WIPO (PCT)
Prior art keywords
acid
star
polishing slurry
group
slurry according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2010/002034
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English (en)
Chinese (zh)
Inventor
荆建芬
蔡鑫元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anji Microelectronics Shanghai Co Ltd
Original Assignee
Anji Microelectronics Shanghai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anji Microelectronics Shanghai Co Ltd filed Critical Anji Microelectronics Shanghai Co Ltd
Publication of WO2011069345A1 publication Critical patent/WO2011069345A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23F—NON-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
    • C23F3/00—Brightening metals by chemical means
    • C23F3/04—Heavy metals
    • H10P52/403—

Definitions

  • the invention relates to a chemical mechanical polishing liquid and an application thereof.
  • 5,527,423 discloses a A chemical mechanical polishing slurry of a metal layer
  • US Pat. No. 6,821,897 discloses a method of copper CMP using a polymer complexing agent
  • Patent No. CN 02114147.9 discloses a copper chemical-mechanical polishing process polishing liquid
  • No. CN 01818940.7 discloses a slurry for chemical mechanical polishing of copper
  • Patent No. CN 98120987.4 discloses a CMP slurry manufacturing process for copper and for integrated electricity The manufacturing method of the road.
  • the technical problem to be solved by the present invention is to provide a chemical mechanical polishing slurry capable of reducing the static etching rate of copper, improving the dishing recess of the polished copper wire, and its use in polishing copper.
  • the polishing slurry contains at least one star-structured polymer surfactant having a pigment affinity group, abrasive particles, a complexing agent, a corrosion inhibitor, and an oxidizing agent.
  • the pigment-affinity group in the star-structured polymer surfactant having a pigment-affinity group is one or more of a hydroxyl group, an amino group and a carboxyl group.
  • the polymerizable monomer forming the star-shaped polymer containing the pigment-affinity group includes one or more of the following: an acrylic monomer, an acrylate monomer, an acrylamide monomer, and an epoxy acetamidine. .
  • the acrylic monomer is acrylic acid and/or methacrylic acid; the acrylate monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, A One or more of propyl acrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate; the acrylamide monomer is acrylamide and/or methyl Acrylamide.
  • the monomer forming the star polymer containing the pigment-affinity group also includes other vinyl monomers.
  • the other vinyl monomer is ethylene, propylene, styrene or p-methylstyrene.
  • the star-shaped polymer containing the pigment affinity group is a polyacrylic acid star homopolymer, styrene and Binary star copolymer of hydroxyethyl acrylate, binary star copolymer of p-methylstyrene and epoxy oxime, binary star copolymer of styrene and ethylene oxide, methyl methacrylate a binary star copolymer with epoxy oxime, a binary star copolymer of methyl acrylate and hydroxyethyl acrylate, a binary star copolymer of acrylic acid and hydroxyethyl acrylate, and acrylic acid, butyl acrylate and One or more of the ternary star copolymers of acrylamide.
  • the star polymer containing the pigment-affinity group has a number average molecular weight of 800 to 50,000.
  • the content of the star-type polymer containing the pigment-affinity group is 0.0001 to 5% by mass.
  • the abrasive particles are one or more of silica, alumina, aluminum-doped silica, aluminum-coated silica, ceria, titania, and polymer abrasive particles.
  • the content of the abrasive particles is 0.1 to 20% by mass.
  • the abrasive particles have a particle diameter of 20 to 150 nm.
  • the complexing agent is an amino acid and a salt thereof, an organic carboxylic acid and a salt thereof, an organic phosphonic acid and a salt thereof.
  • One or more of the organic carboxylic acids are acetic acid, oxalic acid, citric acid, tartaric acid, maleic acid, malonic acid, succinic acid, malic acid, lactic acid, gallic acid, and sulfosalicylic acid.
  • One or more of the organic phosphonic acids are 2-phosphonic acid butyl phosphonium-1, 2, 4-tricarboxylic acid, aminotrimethylidene phosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediamine tetramethylidene
  • the corrosion inhibitor is one of azole, imidazole, thiazole, pyridine and pyrimidine Or a variety.
  • the azole compound is selected from one or more of the group consisting of benzotriazole, 5-methyl-1,2,3-benzotriazole, 5-carboxybenzotriazole, 1-hydroxyl Tribenzotriazole, 1,2,4-triazole, 3-amino-1, 2,4-triazole, 4-amino-1, 2,4-triazole, 3, 5-di Amino-1, 2, 4-triazole, 5-carboxy-3-amino-1, 2,4-triazole, 3-amino-5-mercapto-1, 2,4-triazole, 5- Acetic acid-1H-tetrazole, 5-methyltetrazole, 5-phenyltetrazolium, 5-amino-1H-tetrazole and 1-phenyl-5-mercapto-tetrazolium;
  • the imidazole compound is benzimidazole and/or 2-mercaptobenzimidazole;
  • the thiazole compound is selected from one or more of the following: 2-indolyl-
  • the content of the corrosion inhibitor is 0.005 to 5% by mass.
  • the oxidizing agent is hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, persulfate, percarbonate, periodic acid, perchloric acid, perboric acid, potassium permanganate and ferric nitrate. One or more.
  • the content of the oxidizing agent is 0.05 to 10% by mass.
  • the polishing solution has a pH of from 3 to 11, preferably from 4 to 8.
  • the polishing liquid of the present invention may further contain other conventional additives in the art such as a pH adjuster, a viscosity modifier, an antifoaming agent, a bactericide, and the like.
  • the polishing liquid of the present invention can prepare a concentrated sample which is diluted with deionized water and added with an oxidizing agent before use.
  • the positive progressive effect of the present invention is that the polishing liquid of the present invention can significantly improve the degree of dishing of the copper block after polishing while maintaining a high polishing rate, and the surface of the polished chip is non-corrosive, and the copper is significantly lowered at room temperature. And static corrosion rate at polishing temperature to improve the dish shape of the polished copper wire (dishing) a depression.
  • FIG. 1 is a view showing the surface corrosion observed by SEM after polishing and immersing a patterned copper wafer with the polishing liquid of Example 51. Summary of the 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. Examples 1 to 49
  • Mn 15000 methyl acrylate, hydroxyethyl acrylate
  • Mn 20000 diethylene methacrylic acid
  • Mn 10000 propyl acrylate
  • Mn 5000 Si0 2 2 -hydroxyethyl hydroxyethyl acrylate
  • Mn 8000 methyl acrylate, ethylenediamine hydroxyethyl acrylate
  • Mn 3000 diethylene butyl acrylate
  • Mn 30000 ethyl acrylate, polystyrene methacrylate
  • Mn 5000 propyl methacrylate and methacryl
  • Triazole is 0.0001
  • Mn 10000 methyl methacrylate and ethylene oxide
  • Table 2 shows the comparative polishing liquids 1 to 3 and the polishing liquids 50 to 52 of the present invention. According to the formulation given in the table, the components other than the oxidizing agent are uniformly mixed, and the mass percentage is made up to 100% with water, using KOH or HN0 3 is adjusted to the desired pH. Add oxidizing agent before use and mix well.
  • the star polymers were added in Examples 50 to 52, and the star polymer was more effective in suppressing the removal rate of copper under low pressure. It is beneficial to reduce the depression on the patterned copper wafer, and maintain a high copper removal rate under high pressure without affecting the production capacity.
  • the star polymer can effectively inhibit the static corrosion rate of copper at normal temperature and polishing temperature (such as 50 Q C), which is beneficial to reduce defects and butterfly depression after polishing.
  • the patterned copper wafer is polished using the comparative polishing liquid 2 and the polishing liquid 51 of the present invention.
  • the polished trap values of the 80um*80um copper block on the patterned copper wafer after polishing were measured by XE-300P atomic force microscope.
  • Polishing conditions 3 psi under pressure, polished patterned copper wafer to residual copper of approximately 2000 A, and then the residual copper was removed and oversprayed for 30 seconds at 1 psi.
  • Polishing disc and polishing head speed 70/80rpm, polishing pad PPG MX710, polishing liquid flow rate 100ml/min, polishing machine is Logitech PM5 Polisher.
  • Example 51 added a star polymer which can effectively reduce the butterfly shape on the patterned copper wafer. Depression. Effect Example 3
  • the patterned copper wafer is polished and immersed using the polishing liquid 51 of the present invention.
  • Polishing process conditions polishing disc and polishing head speed 70/80rpm, polishing pad PPG MX710, polishing liquid flow rate 100ml/min, polishing machine for Logitech PM5 Polishes down 3psi, polishing patterned copper wafer to residual copper about 2000A, then The remaining copper was removed by lpsi and left for 30 seconds. After immersing the polished copper wafer in the polishing solution for 30 minutes, it is taken out and cleaned and then scanned. A submicroscope (SEM) was used to observe the corrosion of the wafer surface.
  • SEM submicroscope
  • the surface As shown in Fig. 1, on the patterned copper wafer polished and immersed by the polishing liquid of the present invention, the surface has no scratches and the like, and the surface and edge of the copper wire are smooth and free from corrosion.

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

Abstract

L'invention concerne une pâte de polissage mécano-chimique et son utilisation. La pâte de polissage est utilisée pour le polissage mécano-chimique du cuivre. La pâte de polissage comprend un tensioactif polymère en étoile contenant des groupes d'affinité pour un pigment, et également des particules abrasives, un agent complexant, un inhibiteur de corrosion et un oxydant. En appliquant la pâte de polissage, le taux de corrosion statique du cuivre peut être réduit, et les cavités d'un fil en cuivre poli peuvent être améliorées.
PCT/CN2010/002034 2009-12-11 2010-12-13 Pâte de polissage mécano-chimique et son utilisation Ceased WO2011069345A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200910200319.8A CN102093818A (zh) 2009-12-11 2009-12-11 一种化学机械抛光浆料及其应用
CN200910200319.8 2009-12-11

Publications (1)

Publication Number Publication Date
WO2011069345A1 true WO2011069345A1 (fr) 2011-06-16

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Application Number Title Priority Date Filing Date
PCT/CN2010/002034 Ceased WO2011069345A1 (fr) 2009-12-11 2010-12-13 Pâte de polissage mécano-chimique et son utilisation

Country Status (2)

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CN (1) CN102093818A (fr)
WO (1) WO2011069345A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104745085B (zh) * 2013-12-25 2018-08-21 安集微电子（上海）有限公司 一种用于钴阻挡层抛光的化学机械抛光液
CN104449398B (zh) * 2014-11-25 2017-06-23 河北工业大学 一种适用于钴阻挡层的碱性化学机械抛光液
KR101943702B1 (ko) * 2016-05-12 2019-01-29 삼성에스디아이 주식회사 구리 연마용 cmp 슬러리 조성물 및 이를 이용한 연마 방법
KR101943704B1 (ko) * 2016-06-27 2019-01-29 삼성에스디아이 주식회사 금속막용 cmp 슬러리 조성물 및 연마 방법
CN108251845A (zh) * 2016-12-28 2018-07-06 安集微电子科技（上海）股份有限公司 一种化学机械抛光液及其应用
CN109971356B (zh) 2017-12-27 2025-10-28 安集微电子（上海）有限公司 一种化学机械抛光液
CN109971357B (zh) * 2017-12-27 2021-12-07 安集微电子（上海）有限公司 一种化学机械抛光液
CN108997941A (zh) * 2018-06-21 2018-12-14 大连理工大学 一种铜片化学机械抛光液
CN114686888A (zh) * 2020-12-30 2022-07-01 安集微电子科技（上海）股份有限公司 一种化学机械抛光液及其应用
CN114686115A (zh) * 2020-12-30 2022-07-01 安集微电子科技（上海）股份有限公司 一种化学机械抛光液及其使用方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040060613A (ko) * 2002-12-30 2004-07-06 제일모직주식회사 구리배선 연마용 슬러리 조성물
CN1644640A (zh) * 2003-12-19 2005-07-27 Cmp罗姆和哈斯电子材料控股公司 用于铜的受控抛光的组合物和方法
CN1699444A (zh) * 2004-02-23 2005-11-23 Cmp罗姆和哈斯电子材料控股公司 用于控制半导体晶片中金属互连去除速率的抛光组合物
CN101747844A (zh) * 2008-12-19 2010-06-23 安集微电子（上海）有限公司 一种化学机械抛光液及其应用
WO2010069149A1 (fr) * 2008-12-19 2010-06-24 安集微电子（上海）有限公司 Liquide de polissage chimique-mécanique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040060613A (ko) * 2002-12-30 2004-07-06 제일모직주식회사 구리배선 연마용 슬러리 조성물
CN1644640A (zh) * 2003-12-19 2005-07-27 Cmp罗姆和哈斯电子材料控股公司 用于铜的受控抛光的组合物和方法
CN1699444A (zh) * 2004-02-23 2005-11-23 Cmp罗姆和哈斯电子材料控股公司 用于控制半导体晶片中金属互连去除速率的抛光组合物
CN101747844A (zh) * 2008-12-19 2010-06-23 安集微电子（上海）有限公司 一种化学机械抛光液及其应用
WO2010069149A1 (fr) * 2008-12-19 2010-06-24 安集微电子（上海）有限公司 Liquide de polissage chimique-mécanique

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