WO2005035688A1 - Abrasif pour le polissage chimique mecanique et procede de production associe - Google Patents

Abrasif pour le polissage chimique mecanique et procede de production associe Download PDF

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Publication number
WO2005035688A1
WO2005035688A1 PCT/KR2004/002584 KR2004002584W WO2005035688A1 WO 2005035688 A1 WO2005035688 A1 WO 2005035688A1 KR 2004002584 W KR2004002584 W KR 2004002584W WO 2005035688 A1 WO2005035688 A1 WO 2005035688A1
Authority
WO
WIPO (PCT)
Prior art keywords
abrasive
shell
ceria
silica
mechanical polishing
Prior art date
Application number
PCT/KR2004/002584
Other languages
English (en)
Inventor
Su-Chul Chung
Seung-Ho Lee
Hyung-Mi Lim
Dae-Sun Ryu
Gyong-Beum Ko
Jong-Dai Park
Original Assignee
Korea Institute Of Ceramic Engineering & Technology
Dongjin Semichem 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 Korea Institute Of Ceramic Engineering & Technology, Dongjin Semichem Co.,Ltd. filed Critical Korea Institute Of Ceramic Engineering & Technology
Publication of WO2005035688A1 publication Critical patent/WO2005035688A1/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09GPOLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00Polishing compositions
    • C09G1/02Polishing compositions containing abrasives or grinding agents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives
    • C09K3/1409Abrasive particles per se
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives
    • C09K3/1436Composite particles, e.g. coated particles
    • C09K3/1445Composite particles, e.g. coated particles the coating consisting exclusively of metals
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives
    • C09K3/1454Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463Aqueous liquid suspensions

Definitions

  • This invention relates to an abrasive for chemical mechanical polishing (CMP) and a method for producing the same. More particularly, this invention relates to an abrasive for CMP which is produced by hydrothermally treating a ceria particle coated silica.
  • the abrasive includes a silica core, the first shell for coating the silica core, and the second shell for coating the first shell, wherein the first shell is made of ceria particles and the second shell is made of silica.
  • One of the effective and widely used global planarization techniques is a chemical mechanical polishing (CMP) process, which performs the chemical polishing and the mechanical polishing simultaneously.
  • CMP chemical mechanical polishing
  • the CMP process is relatively simple, and the planarizing area of the CMP process is greater than that of other planarization techniques by 100 to 1,000 times.
  • the slurry useful for the CMP process includes metallic oxide abrasive, oxidizer, deionized water and various additives.
  • Exemplary metallic oxide abrasive includes silica (SiO ), aluminum oxide (Al O ), ceria (CeO ), 2 2 3 2 zirconia (ZO ), or so on.
  • the silica is widely used as the metallic oxide abrasive 2 because it is commercially available and inexpensive.
  • the silica in case of using the silica, serious contamination of semiconductor can be avoided since the material for forming an insulating layer of a semiconductor is SiO . Ifcwever, in case of using the 2 silica, the removal (polishing) rate is not satisfactory, and the selectivity of SiO layer 2 and Si N layer is not satisfactory, for example, in shallow trench isolation (STI) 3 4 process.
  • STI shallow trench isolation
  • Ceria abrasive has been used in polishing a glass lens, and the slurry including the ceria abrasive has the removal rate which is 3 to 4 times faster than the slurry including the silica abrasive, and also shows high removal rate in neutral solution.
  • H)wever the ceria abrasive is expensive, has irregular shapes and sizes, and is liable to be aggregated.
  • the slurry including the ceria abrasive has drawbacks in that the wafer can be scratched in the polishing process, and degree of the planarization of the wafer decreases.
  • the Haymaker constant which represents the attractive force between particles, of the ceria abrasive is 27.7, which is greater than that of silica (5.99) and aluminum oxide (15.4). Therefore, when the size of the ceria particles increases, the repulsive power between particles and the dispersibility of the ceria particles decrease, which results in the high possibility of abrasive aggregation and precipitation.
  • U.S. patent publication No. 2002-95873 titled Aqueous dispersions, process for their production, and their use, discloses alkaline treated silica abrasive having average particle size of less than lOOnm
  • U.S. patent No. 6,328,944 titled Doped, pyrogenically prepared oxides, discloses oxides of metals and/or non-metals which are doped with one or more doping components such as a metal, a non-metal, or an oxide and/or a salt of a metal and/or a non-metal.
  • 10-2003-0017352 titled Polishing composition comprising silica-coated ceria powder, discloses a ceria abrasive having improved stability.
  • the abrasive is also not uniform in their particle sizes and shapes. Therefore, the abrasive and the slurry flow irregularly in polishing process, and the contacts between an abrasive pad, a wafer and an abrasive are also irregular, which may result in the irregular polishing of a wafer.
  • the present inventors have prepared an abrasive for CMP by coating ceria particles on colloidal silica sol in solution state.
  • the abrasive has uniform sizes and shapes, and the slurry including the same has better removal rate and the scratch formation is suppressed.
  • the slurry including such abrasive is unstable, and liable to be aggregated and precipitated in neutral solvent, especially when pH is more than 4.
  • particle aggregation also occurs when heating amorphous ceria hydroxide to produce crystalline ceria particles coated on the silica sol.
  • an object of the present invention to provide an abrasive for CMP having improved polishing rate and stability at wide pH range, and suitable for long- term storage. It is other object of the present invention to provide an abrasive for CMP having regular particle sizes and shapes and capable of being uniformly dispersed in a solvent without aggregation. It is another object of the present invention to provide an abrasive for CMP capable of improving the degree of planarization of wafer, and for producing a polished surface having fewer defects and scratches. It is yet another object of the present invention to provide an abrasive for CMP which is inexpensive. It is yet another object of the present invention to provide a method for producing an abrasive for CMP which can be mass-produced by relatively simple processes.
  • the present invention provides an abrasive for CMP comprising a silica core, the first shell for coating the silica core, and the second shell for coating the first shell, wherein the first shell is made of ceria particles and the second shell is made of silica particles.
  • the second shell is produced by hydrothermally treating the ceria particle coated silica core.
  • the present invention also provides a method for producing an abrasive for CMP which comprises the steps of: (a) preparing ceria particle suspension by mixing aqueous ammonia and aqueous cerous nitrate solution and stirring the solution; (b) preparing core/shell particles by adding colloidal silica slurry into the prepared ceria particle suspension and stirring the suspension; (c) washing the suspension; and (d) hydrothermally treating the washed suspension.
  • FIG. 1 is a diagram for illustrating a method for producing an abrasive for CMP according to an embodiment of the present invention
  • FIG. 2 is a diagram for illustrating a method for producing an abrasive for CMP according to other embodiment of the present invention
  • FIG. 3 shows TEM photographs before and after hydrothermally treating core/shell particles
  • Fig. 4 is a graph showing Zeta potential changes of the slurry including core/shell particle with respect to pH variation before and after the hydrothermal treatment.
  • Fig. 5 shows XRD graphs of the core/shell particle before and after the hydrothermal treatment.
  • the abrasive for CMP according to the present invention comprises a silica core, the first shell for coating the silica core, and the second shell for coating the first shell.
  • the first shell is made of ceria particles.
  • 5 to 30 weight parts of ceria particles is uniformly coated on the 100 weight parts of the silica core.
  • the preferable amount of ceria particles is about 30 weight parts based on 100 weight parts of the silica core.
  • the preferable amount of ceria particles is about 5 weight parts based on 100 weight parts of the silica core.
  • the silica core useful in this invention is uniform colloidal silica having a spherical shape and a diameter of preferably 20 to 400 nm, and more preferably 100 to 400nm.
  • the ceria particles coated on the silica core preferably have crystalline structure and sizes of 5 to 20nm.
  • the ceria particles are uniformly coated on the silica core without aggregation to form uniform abrasive particles.
  • the ceria particles coated silica core is called as core/shell particle.
  • the core/shell particle is hydrothermally treated to form the second shell on the surface of the core/shell particle.
  • the second shell is made of silica particles and has the thickness of less than 2nm, preferably 0.01 to 2nm, and more preferably 0.1 to 2nm. When the thickness of the second shells is less than 1 nm, the removal rate increase, but when the thickness of the second shells is more than 2 nm, the removal rate decrease.
  • the size of the abrasive for CMP according to the present invention is preferably about 50 to 500nm, and more preferably about 100 to 300 nm. When the size of the abrasive is less than 50nm, the stability of the abrasive increases but the removal rate decrease. On the contrary, when the size of the abrasive is more than 500nm, the stability of the abrasive decrease.
  • FIG. 1 is a diagram for illustrating a method for producing an abrasive for CMP according to an embodiment of the present invention. As shown in Fig.
  • the method for producing an abrasive for CMP includes the steps of: (a) preparing ceria particle suspension by mixing aqueous ammonia and aqueous cerous nitrate solution and stirring the solution; (b) preparing core/shell particles by adding colloidal silica slurry into the prepared ceria particle suspension and stirring the suspension; (c) washing the suspension preferably before or after centrifuging and/or filtering the stined suspension to remove excess salt in the suspension; and (d) hydrothermally treating the washed suspension.
  • 300m£ of 0.2M aqueous ammonia is added into 200 mil of 0.2M aqueous cerous nitrate solution, and the solution is stined at the temperature of 80 to 100°C to prepare suspension including ceria particles having the sizes of 5 to 20nm.
  • colloidal silica slurry is added into the prepared ceria particle suspension.
  • the colloidal silica slurry includes spherical silica particles of uniform size, and the preferable amount of the solid particles is 5g.
  • the suspension is stined for about 2 hours to produce core/shell particles, which comprise silica core and ceria particles uniformly coated on the silica core.
  • the washed suspension is hydrothermally treated in an auto-clave at the temperature of 100 to 350°C for more than 30 minutes, and preferably 30 minutes to 2 hours to produce silica coated core/shell particles.
  • the preferable pH of the washed suspension is 3.0 to 4.0, and more preferably 3.5 to 3.9. When the pH is less than 3.0, or the pH is more than 4.0, the suspension is liable to be unstable.
  • the Zeta potential change before the hydrothermal treatment is similar with that of the ceria particle, but the Zeta potential change after the hydrothermal treatment is similar with that of the silica sol, and the IEP (Isoelectric Point) was about 2. Therefore, it is confirmed that silica layer was formed on the surface of the core/shell particle by the hydrothermal treatment.
  • the XRD peak of the solid particles before and after the hydrothermal treatment are set forth in upper part of Fig. 5. After the hydrothermal treatment, the full width at half maximum decreases, which means that the crystalline size of particle increases.
  • Fig. 2 is a diagram for illustrating a method for producing an abrasive for CMP according to other embodiment of the present invention.
  • the method for producing an abrasive for CMP includes the steps of: (a) preparing a suspension including silica on which ceria particles are electrostatically coated by mixing silica sol and ceria sol; and (b) hydrothermally treating the suspension.
  • the ceria sol includes ceria particles having the sizes of 5 to 20nm.
  • the hydrothermally treated slurry is centrifuged and/or filtered to remove the silica particle not coated with ceria particles.
  • the Zeta potentials of the slurry before and after the hydrothermal treatment were measured as previously described, and the results were similar as shown in Fig. 4.
  • the X-ray diffractions of the solid particles before and after the hydrothermal treatment are also set forth in lower part of Fig. 5, which confirms the crystalline size of the particle increases after the hydrothermal treatment.
  • the first shell namely the ceria particles
  • the first shell can also be coated on the silica core by a chemical vapor deposition (CVD), but the preferable coating method is the previously described solution phase reaction.
  • the pH of the slurry including the abrasive of the present invention is important for abrasive dispersion, and the preferable pH of the slurry is 2 to 10, and more preferably 4 to 9.
  • the surface of the abrasive is electrically charged, and the magnitude and type (positive or negative) of the charge depend on the pH of the slurry.
  • the Zeta potential of the abrasive of the present invention decreases as the pH increases, and has (-) value when the pH of the slurry is more than 2.
  • the silica abrasive when the pH is more than 2, the silica abrasive can be uniformed dispersed due to the electrostatic repulsion.
  • the pH when the pH is more than 10, the silica coated on the ceria and the silica core can be dissolved to form silicate, and the ceria particles can be separated from the silica, which may decrease the polishing efficiency of the slurry.
  • the washed slurry was hydrothermally treated in an auto-clave at the temperature of 150 °C for 1 hour.
  • the obtained slurry was dispersed in water with supersonic wave to produce polishing slurry of pH 6.0 and having the abrasive concentration of 1 weight%.

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

Abstract

L'invention concerne un abrasif pour le polissage chimique mécanique, cet abrasif étant obtenu par traitement hydrothermal de silice enrobée de particules d'oxyde cérique. Cet abrasif pour le polissage chimique mécanique comprend un noyau de silice, une première enveloppe enrobant le noyau de silice, une deuxième enveloppe enrobant la première enveloppe, la première enveloppe étant composée de particules d'oxyde cérique et la deuxième enveloppe de particules de silice. La présente invention porte également sur un procédé pour produire un abrasif pour le polissage chimique mécanique, ce procédé comprenant les opérations suivantes: (a) préparer une suspension de particules d'oxyde cérique en mélangeant de l'ammoniac aqueux et une solution aqueuse de nitrate céreux et agiter cette solution; (b) préparer des particules de noyau/d'enveloppe en additionnant de la boue de silice colloïdale à la suspension de particules d'oxyde cérique préparée et agiter la suspension; (c) nettoyer la suspension; (d) traiter de manière hydrothermale la suspension nettoyée.
PCT/KR2004/002584 2003-10-10 2004-10-09 Abrasif pour le polissage chimique mecanique et procede de production associe WO2005035688A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020030070684A KR100574225B1 (ko) 2003-10-10 2003-10-10 실리카에 세리아/실리카가 코팅된 화학적 기계적 연마용연마재 및 그 제조방법
KR10-2003-0070684 2003-10-10

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Publication Number Publication Date
WO2005035688A1 true WO2005035688A1 (fr) 2005-04-21

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TW (1) TWI265193B (fr)
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Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010139603A1 (fr) 2009-06-05 2010-12-09 Basf Se Nanostructures d'oxyde de métal de type framboise enrobées avec des nanoparticules de ceo2 pour la planarisation chimique-mécanique (cmp)
EP2428541A1 (fr) 2010-09-08 2012-03-14 Basf Se Composition aqueuse de polissage et procédé de polissage mécanique chimique de substrats contenant des films diélectriques en oxyde de silicium et polysilicone
WO2012032466A1 (fr) 2010-09-08 2012-03-15 Basf Se Compositions de polissage aqueuses contenant des dioxydes de diazénium n-substitués et/ou des sels d'oxyde de n'-hydroxy-diazénium
WO2012032469A1 (fr) 2010-09-08 2012-03-15 Basf Se Composition aqueuse de polissage et procédé de polissage chimico-mécanique de matériaux de substrat pour dispositifs optiques, mécaniques et électriques
CN102653633A (zh) * 2011-03-03 2012-09-05 台湾永光化学工业股份有限公司 蓝色、红色及黄色染料化合物及所组成的黑色墨水组合物
WO2014038536A1 (fr) * 2012-09-05 2014-03-13 コニカミノルタ株式会社 Procédé de production de particules de matériau de polissage
WO2014045939A1 (fr) * 2012-09-19 2014-03-27 コニカミノルタ株式会社 Procédé de production de particules de matière de polissage
CN103814102A (zh) * 2011-09-20 2014-05-21 堺化学工业株式会社 玻璃研磨用复合颗粒
WO2014122976A1 (fr) * 2013-02-05 2014-08-14 コニカミノルタ株式会社 Suspension de matériau de polissage
WO2014122992A1 (fr) * 2013-02-05 2014-08-14 コニカミノルタ株式会社 Particules inorganiques de type cœur/coquille
WO2014122982A1 (fr) * 2013-02-05 2014-08-14 コニカミノルタ株式会社 Suspension de polissage
WO2014122978A1 (fr) * 2013-02-05 2014-08-14 コニカミノルタ株式会社 Procédé pour la production d'abrasif
EP2826827A1 (fr) 2013-07-18 2015-01-21 Basf Se Composition CMP comprenant des particules abrasives à cérium
WO2016069244A1 (fr) * 2014-10-30 2016-05-06 Applied Materials, Inc. Nanoparticule à base de boues d'oxyde de cérium
JP2016127139A (ja) * 2014-12-26 2016-07-11 花王株式会社 酸化珪素膜研磨用研磨粒子
US9524874B2 (en) 2010-12-10 2016-12-20 Basf Se Aqueous polishing composition and process for chemically mechanically polishing substrates containing silicon oxide dielectric and polysilicon films
JP2017200999A (ja) * 2016-04-22 2017-11-09 日揮触媒化成株式会社 シリカ系複合微粒子を含む研磨用砥粒分散液
JP2017206411A (ja) * 2016-05-18 2017-11-24 日揮触媒化成株式会社 シリカ系複合微粒子分散液、その製造方法及びシリカ系複合微粒子分散液を含む研磨用スラリー
JP2017214271A (ja) * 2016-04-22 2017-12-07 日揮触媒化成株式会社 シリカ系複合微粒子分散液、その製造方法及びシリカ系複合微粒子分散液を含む研磨用砥粒分散液
JPWO2016159167A1 (ja) * 2015-03-31 2018-03-29 日揮触媒化成株式会社 シリカ系複合微粒子分散液、その製造方法及びシリカ系複合微粒子分散液を含む研磨用スラリー
JP2018101693A (ja) * 2016-12-20 2018-06-28 花王株式会社 研磨液組成物
JP2018168063A (ja) * 2018-07-12 2018-11-01 日揮触媒化成株式会社 シリカ系複合粒子分散液の製造方法
CN109155246A (zh) * 2016-04-22 2019-01-04 日挥触媒化成株式会社 二氧化硅系复合微粒分散液及其制造方法
EP3476910A1 (fr) 2017-10-27 2019-05-01 Versum Materials US, LLC Particules composites, procédé de raffinage et utilisation associée
KR20190058572A (ko) * 2016-11-14 2019-05-29 니끼 쇼꾸바이 카세이 가부시키가이샤 세리아계 복합미립자 분산액, 그의 제조방법 및 세리아계 복합미립자 분산액을 포함하는 연마용 지립분산액
US10319601B2 (en) 2017-03-23 2019-06-11 Applied Materials, Inc. Slurry for polishing of integrated circuit packaging
JP2019172533A (ja) * 2018-03-29 2019-10-10 日揮触媒化成株式会社 セリア系複合微粒子分散液、その製造方法及びセリア系複合微粒子分散液を含む研磨用砥粒分散液
EP3608378A1 (fr) 2018-08-09 2020-02-12 Versum Materials US, LLC Composition de planarisation mécanique et chimique pour polir des matériaux d'oxyde et procédé d'utilisation associé
WO2021105169A1 (fr) * 2019-11-26 2021-06-03 Rhodia Operations Dispersion liquide et poudre de particules de type noyau-enveloppe à base de cérium, procédé de production de celles-ci et utilisations de celles-ci dans le polissage
CN114591687A (zh) * 2022-03-18 2022-06-07 深圳市瑞来稀土材料有限公司 一种用于半导体晶圆抛光处理的稀土抛光粉及其制备方法

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KR101279970B1 (ko) * 2008-12-31 2013-07-05 제일모직주식회사 금속 배선 연마용 cmp 슬러리 조성물
TWI444437B (zh) 2010-06-18 2014-07-11 Everlight Chem Ind Corp 藍色、紅色及黃色染料化合物及所組成之黑色墨水組成物
CN106675519A (zh) * 2016-12-21 2017-05-17 安徽中创电子信息材料有限公司 一种无机复合磨料及其制备方法

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US5855841A (en) * 1991-12-23 1999-01-05 Commonwealth Scientific And Industrial Research Organisation Process for producing dense ceramic product
US5429647A (en) * 1992-09-25 1995-07-04 Minnesota Mining And Manufacturing Company Method for making abrasive grain containing alumina and ceria
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Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010139603A1 (fr) 2009-06-05 2010-12-09 Basf Se Nanostructures d'oxyde de métal de type framboise enrobées avec des nanoparticules de ceo2 pour la planarisation chimique-mécanique (cmp)
US20120077419A1 (en) * 2009-06-05 2012-03-29 Basf Se Raspberry-type metal oxide nanostructures coated with ceo2 nanoparticles for chemical mechanical planarization (cmp)
EP2428541A1 (fr) 2010-09-08 2012-03-14 Basf Se Composition aqueuse de polissage et procédé de polissage mécanique chimique de substrats contenant des films diélectriques en oxyde de silicium et polysilicone
WO2012032466A1 (fr) 2010-09-08 2012-03-15 Basf Se Compositions de polissage aqueuses contenant des dioxydes de diazénium n-substitués et/ou des sels d'oxyde de n'-hydroxy-diazénium
WO2012032469A1 (fr) 2010-09-08 2012-03-15 Basf Se Composition aqueuse de polissage et procédé de polissage chimico-mécanique de matériaux de substrat pour dispositifs optiques, mécaniques et électriques
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