JPH10102038A - Cerium oxide abrasive and grinding of substrate - Google Patents

Cerium oxide abrasive and grinding of substrate

Info

Publication number
JPH10102038A
JPH10102038A JP8258767A JP25876796A JPH10102038A JP H10102038 A JPH10102038 A JP H10102038A JP 8258767 A JP8258767 A JP 8258767A JP 25876796 A JP25876796 A JP 25876796A JP H10102038 A JPH10102038 A JP H10102038A
Authority
JP
Japan
Prior art keywords
cerium oxide
water
polishing
insulating film
soluble
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.)
Withdrawn
Application number
JP8258767A
Other languages
Japanese (ja)
Inventor
Masato Yoshida
誠人 吉田
Jun Matsuzawa
純 松沢
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.)
Showa Denko Materials Co Ltd
Original Assignee
Hitachi Chemical 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 Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to JP8258767A priority Critical patent/JPH10102038A/en
Priority to RU99109040/28A priority patent/RU2178599C2/en
Priority to KR1020077015361A priority patent/KR100775228B1/en
Priority to KR1020067021504A priority patent/KR100759182B1/en
Priority to CNB03119818XA priority patent/CN1245471C/en
Priority to EP07109339.7A priority patent/EP1833084B1/en
Priority to AU43231/97A priority patent/AU4323197A/en
Priority to CNB031198198A priority patent/CN1323124C/en
Priority to CN2006101425095A priority patent/CN1935927B/en
Priority to PCT/JP1997/003490 priority patent/WO1998014987A1/en
Priority to EP05106514A priority patent/EP1610367B1/en
Priority to KR1020027006123A priority patent/KR100622519B1/en
Priority to DE69739813T priority patent/DE69739813D1/en
Priority to KR1020067021503A priority patent/KR100761636B1/en
Priority to KR1020047006307A priority patent/KR100710779B1/en
Priority to US09/269,650 priority patent/US6221118B1/en
Priority to KR10-1999-7002723A priority patent/KR100420087B1/en
Priority to CA002263241A priority patent/CA2263241C/en
Priority to EP97941287A priority patent/EP0939431B1/en
Priority to DE69739413T priority patent/DE69739413D1/en
Priority to CNB97199370XA priority patent/CN1282226C/en
Priority to EP09178160A priority patent/EP2164095A1/en
Publication of JPH10102038A publication Critical patent/JPH10102038A/en
Priority to US09/782,241 priority patent/US6863700B2/en
Priority to US10/960,941 priority patent/US7708788B2/en
Priority to US11/276,161 priority patent/US7867303B2/en
Priority to US11/276,157 priority patent/US20060118524A1/en
Withdrawn legal-status Critical Current

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  • Mechanical Treatment Of Semiconductor (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain the subject abrasive capable of high-speed grinding without scratching a surface to be ground such as of electric insulating film, comprising a slurry prepared by dispersing cerium oxide particles each of specific size in a medium. SOLUTION: This abrasive comprises a slurry prepared by dispersing in a medium cerium oxide particles with such size that the primary particles each 100-300nm in size determined by observation using a transmission electron microscope accounts for >=90wt.% of the total particles. In this case, it is preferable that the medium is water, the dispersant is at least one kind selectted from esp. water-soluble organict polymers, water-soluble anionic surfactants, water-soluble nonionic surfactants and water-soluble amines, and the final abrasive is set at pH 7-10.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、酸化セリウム研磨
剤及び基板の研磨法を提供するものである。
The present invention provides a cerium oxide abrasive and a method for polishing a substrate.

【0002】[0002]

【従来の技術】従来、半導体装置の製造工程において、
プラズマ−CVD、低圧−CVD等の方法で形成される
SiO2絶縁膜等無機絶縁膜層を平坦化するための化学
機械研磨剤としてコロイダルシリカ系の研磨剤が一般的
に検討されている。コロイダルシリカ系の研磨剤は、シ
リカ粒子を四塩化珪酸を熱分解する等の方法で粒成長さ
せ、アンモニア等のアルカリ金属を含まないアルカリ溶
液でpH調整を行って製造している。しかしながら、こ
の様な研磨剤は無機絶縁膜の研磨速度が充分な速度を持
たず、実用化には低研磨速度という技術課題がある。
2. Description of the Related Art Conventionally, in the manufacturing process of a semiconductor device,
Colloidal silica-based polishing agents are generally studied as chemical mechanical polishing agents for planarizing an inorganic insulating film layer such as a SiO 2 insulating film formed by a method such as plasma-CVD or low-pressure-CVD. Colloidal silica-based abrasives are produced by growing silica particles by a method such as thermal decomposition of silicic acid tetrachloride and adjusting the pH with an alkali solution containing no alkali metal such as ammonia. However, such a polishing agent does not have a sufficient polishing rate for the inorganic insulating film, and there is a technical problem of a low polishing rate for practical use.

【0003】一方、フォトマスク用ガラス表面研磨とし
て、酸化セリウム研磨剤が用いられている。酸化セリウ
ム粒子はシリカ粒子やアルミナ粒子に比べ硬度が低く、
したがって研磨表面に傷が入りにくいことから仕上げ鏡
面研磨に有用である。また、酸化セリウムは強い酸化剤
として知られるように化学的活性な性質を有している。
この利点を活かし、絶縁膜用化学機械研磨剤への適用が
有用である。しかしながら、フォトマスク用ガラス表面
研磨用酸化セリウム研磨剤をそのまま無機絶縁膜研磨に
適用すると、1次粒子径が大きく、そのため絶縁膜表面
に目視で観察できる研磨傷が入ってしまう。
On the other hand, cerium oxide abrasives have been used for polishing the glass surface for photomasks. Cerium oxide particles have lower hardness than silica particles and alumina particles,
Therefore, it is useful for finish mirror polishing because the polishing surface is hardly damaged. Also, cerium oxide has chemically active properties as known as strong oxidizing agents.
Taking advantage of this advantage, application to a chemical mechanical polishing agent for an insulating film is useful. However, when a cerium oxide abrasive for polishing a glass surface for a photomask is directly applied to polishing of an inorganic insulating film, the primary particle diameter is large, so that a visually observable polishing scratch is formed on the insulating film surface.

【0004】[0004]

【発明が解決しようとする課題】本発明は、SiO2
縁膜等の被研磨面を傷なく高速に研磨することが可能な
酸化セリウム研磨剤及び基板の研磨法を提供するもので
ある。
SUMMARY OF THE INVENTION An object of the present invention is to provide a cerium oxide abrasive and a substrate polishing method capable of polishing a surface to be polished such as a SiO 2 insulating film at a high speed without any damage.

【0005】[0005]

【課題を解決するための手段】本発明の酸化セリウム研
磨剤は、透過型電子顕微鏡による観察で粒子径が100
nm以上300nm以下である1次粒子が全数の90%
以上である酸化セリウム粒子を媒体に分散させたスラリ
ーを含むものである。
The cerium oxide abrasive of the present invention has a particle diameter of 100 when observed with a transmission electron microscope.
90% of the total number of primary particles of not less than 300 nm and not more than 300 nm
It includes a slurry in which the cerium oxide particles described above are dispersed in a medium.

【0006】本発明の基板の研磨法は、上記の酸化セリ
ウム研磨剤で所定の基板を研磨することを特徴とするも
のである。
The method of polishing a substrate according to the present invention is characterized in that a predetermined substrate is polished with the above-mentioned cerium oxide abrasive.

【0007】本発明は、透過型電子顕微鏡による観察で
粒子径が100nm以上300nm以下である1次粒子
が全数の90%以上である酸化セリウム粒子を使用する
ことにより、SiO2絶縁膜等の被研磨面に傷をつける
ことなくかつ、高速に研磨できることを見い出したこと
によりなされたものである。
According to the present invention, the use of cerium oxide particles in which 90% or more of the total number of primary particles having a particle diameter of 100 nm or more and 300 nm or less as observed by a transmission electron microscope is used to cover a SiO 2 insulating film or the like. This is achieved by finding that high-speed polishing can be performed without damaging the polished surface.

【0008】[0008]

【発明の実施の形態】一般に酸化セリウムは、炭酸塩、
硫酸塩、蓚酸塩等のセリウム化合物を焼成することによ
って得られる。TEOS−CVD法等で形成されるSi
2絶縁膜は1次粒子径が大きく、かつ結晶歪が少ない
ほど、すなわち結晶性がよいほど高速研磨が可能である
が、研磨傷が入りやすい傾向がある。そこで、本発明で
用いる酸化セリウム粒子は、あまり結晶性を上げないで
作製される。また、半導体チップ研磨に使用することか
ら、アルカリ金属およびハロゲン類の含有率は1ppm
以下に抑えることが好ましい。
DETAILED DESCRIPTION OF THE INVENTION Generally, cerium oxide is a carbonate,
It is obtained by calcining cerium compounds such as sulfates and oxalates. Si formed by a TEOS-CVD method or the like
The O 2 insulating film can be polished at a high speed as the primary particle diameter is large and the crystal distortion is small, that is, as the crystallinity is good. Therefore, the cerium oxide particles used in the present invention are produced without increasing crystallinity. Further, since it is used for polishing semiconductor chips, the content of alkali metals and halogens is 1 ppm.
It is preferable to suppress it to the following.

【0009】本発明において、酸化セリウム粒子を作製
する方法として焼成法が使用できる。ただし、研磨傷が
入らない粒子を作製するためにできるだけ結晶性を上げ
ない低温焼成が好ましい。セリウム化合物の酸化温度が
300℃であることから、焼成温度は700℃以上90
0℃以下が好ましい。
In the present invention, a firing method can be used as a method for producing cerium oxide particles. However, low-temperature sintering that does not increase the crystallinity as much as possible is preferable in order to produce particles that do not cause polishing scratches. Since the oxidation temperature of the cerium compound is 300 ° C., the firing temperature is 700 ° C. or more and 90 ° C.
0 ° C. or lower is preferred.

【0010】本発明における酸化セリウムスラリーは、
上記の方法により製造された酸化セリウム粒子を含有す
る水溶液又はこの水溶液から回収した酸化セリウム粒
子、水及び必要に応じて分散剤らなる組成物を分散させ
ることによって得られる。ここで、酸化セリウム粒子の
濃度には制限は無いが、懸濁液の取り扱い易さから0.
5〜10重量%の範囲が好ましい。また分散剤として
は、金属イオン類を含まないものとして、アクリル酸重
合体及びそのアンモニウム塩、メタクリル酸重合体及び
そのアンモニウム塩、ポリビニルアルコール等の水溶性
有機高分子類、ラウリル硫酸アンモニウム、ポリオキシ
エチレンラウリルエーテル硫酸アンモニウム等の水溶性
陰イオン性界面活性剤、ポリオキシエチレンラウリルエ
ーテル、ポリエチレングリコールモノステアレート等の
水溶性非イオン性界面活性剤、モノエタノールアミン、
ジエタノールアミン等の水溶性アミン類などが挙げられ
る。これらの分散剤の添加量は、スラリー中の粒子の分
散性及び沈降防止性などから酸化セリウム粒子100重
量部に対して0.01重量部から5重量部の範囲が好ま
しく、その分散効果を高めるためには分散処理時に分散
機の中に粒子と同時に入れることが好ましい。
[0010] The cerium oxide slurry in the present invention comprises:
It is obtained by dispersing an aqueous solution containing cerium oxide particles produced by the above method or a composition comprising cerium oxide particles recovered from this aqueous solution, water and, if necessary, a dispersant. Here, there is no limitation on the concentration of the cerium oxide particles, but the concentration of the cerium oxide particles is set at 0.
A range of 5 to 10% by weight is preferred. As the dispersant, those containing no metal ions include acrylic acid polymers and their ammonium salts, methacrylic acid polymers and their ammonium salts, water-soluble organic polymers such as polyvinyl alcohol, ammonium lauryl sulfate, and polyoxyethylene. Water-soluble anionic surfactants such as ammonium lauryl ether sulfate, polyoxyethylene lauryl ether, water-soluble nonionic surfactants such as polyethylene glycol monostearate, monoethanolamine,
And water-soluble amines such as diethanolamine. The addition amount of these dispersants is preferably in the range of 0.01 part by weight to 5 parts by weight based on 100 parts by weight of the cerium oxide particles in view of the dispersibility and anti-settling properties of the particles in the slurry, and enhances the dispersing effect For this purpose, it is preferable that the particles are simultaneously placed in the disperser during the dispersion treatment.

【0011】これらの酸化セリウム粒子を水中に分散さ
せる方法としては、通常の撹拌機による分散処理の他
に、ホモジナイザー、超音波分散機、ボールミルなどを
用いることができる。特に酸化セリウム粒子を1μm以
下の微粒子として分散させるためには、ボールミル、振
動ボールミル、遊星ボールミル、媒体撹拌式ミルなどの
湿式分散機を用いることが好ましい。また、スラリーの
アルカリ性を高めたい場合には、分散処理時又は処理後
にアンモニア水などの金属イオンを含まないアルカリ性
物質を添加することができる。
As a method for dispersing these cerium oxide particles in water, a homogenizer, an ultrasonic disperser, a ball mill, or the like can be used in addition to the usual dispersion treatment using a stirrer. In particular, in order to disperse cerium oxide particles as fine particles of 1 μm or less, it is preferable to use a wet disperser such as a ball mill, a vibrating ball mill, a planetary ball mill, and a medium stirring mill. When it is desired to increase the alkalinity of the slurry, an alkaline substance not containing metal ions, such as aqueous ammonia, can be added during or after the dispersion treatment.

【0012】本発明の酸化セリウム研磨剤は、上記スラ
リ−をそのまま使用してもよいが、N,N−ジエチルエ
タノ−ルアミン、N,N−ジメチルエタノ−ルアミン、
アミノエチルエタノ−ルアミン等の添加剤を添加して研
磨剤とすることができる。
In the cerium oxide abrasive of the present invention, the above slurry may be used as it is, but N, N-diethylethanolamine, N, N-dimethylethanolamine,
Additives such as aminoethylethanolamine can be added to make an abrasive.

【0013】本発明の酸化セリウム研磨剤が使用される
無機絶縁膜の作製方法として、定圧CVD法、プラズマ
CVD法等が挙げられる。定圧CVD法によるSiO2
絶縁膜形成は、Si源としてモノシラン:SiH4、酸
素源として酸素:O2を用いる。このSiH4−O2系酸
化反応を400℃程度以下の低温で行わせることにより
得られる。高温リフローによる表面平坦化を図るために
リン:Pをドープするときには、SiH4−O2−PH3
系反応ガスを用いることが好ましい。プラズマCVD法
は、通常の熱平衡下では高温を必要とする化学反応が低
温でできる利点を有する。プラズマ発生法には、容量結
合型と誘導結合型の2つが挙げられる。反応ガスとして
は、Si源としてSiH4、酸素源としてN2Oを用いた
SiH4−N2O系ガスとテトラエトキシシラン(TEO
S)をSi源に用いたTEOS−O2系ガス(TEOS
−プラズマCVD法)が挙げられる。基板温度は250
℃〜400℃、反応圧力は67〜400Paの範囲が好
ましい。このように、本発明のSiO2絶縁膜にはリ
ン、ホウ素等の元素がド−プされていても良い。
As a method for forming an inorganic insulating film using the cerium oxide abrasive of the present invention, there are a constant pressure CVD method, a plasma CVD method and the like. SiO 2 by constant pressure CVD
In forming the insulating film, monosilane: SiH 4 is used as a Si source, and oxygen: O 2 is used as an oxygen source. This is obtained by performing the SiH 4 —O 2 -based oxidation reaction at a low temperature of about 400 ° C. or less. When doping phosphorus: P for planarizing the surface by high temperature reflow, SiH 4 —O 2 —PH 3
It is preferable to use a system reaction gas. The plasma CVD method has an advantage that a chemical reaction requiring a high temperature can be performed at a low temperature under normal thermal equilibrium. The plasma generation method includes two types, a capacitive coupling type and an inductive coupling type. As a reaction gas, a SiH 4 —N 2 O-based gas using SiH 4 as a Si source and N 2 O as an oxygen source, and tetraethoxysilane (TEO)
S) as a Si source using a TEOS-O 2 based gas (TEOS
-Plasma CVD method). Substrate temperature is 250
The reaction pressure is preferably in the range of 67 to 400 Pa. As described above, the elements such as phosphorus and boron may be doped in the SiO 2 insulating film of the present invention.

【0014】所定の基板として、半導体基板すなわち回
路素子と配線パターンが形成された段階の半導体基板、
回路素子が形成された段階の半導体基板等の半導体基板
上にSiO2絶縁膜層が形成された基板が使用できる。
このような半導体基板上に形成されたSiO2絶縁膜層
を上記酸化セリウム研磨剤で研磨することによって、S
iO2絶縁膜層表面の凹凸を解消し、半導体基板全面に
渡って平滑な面とする。ここで、研磨する装置として
は、半導体基板を保持するホルダーと研磨布(パッド)
を貼り付けた(回転数が変更可能なモータ等を取り付け
てある)定盤を有する一般的な研磨装置が使用できる。
研磨布としては、一般的な不織布、発泡ポリウレタン、
多孔質フッ素樹脂などが使用でき、特に制限がない。ま
た、研磨布にはスラリーが溜まる様な溝加工を施すこと
が好ましい。研磨条件には制限はないが、定盤の回転速
度は半導体が飛び出さない様に100rpm以下の低回
転が好ましく、半導体基板にかける圧力は研磨後に傷が
発生しない様に1kg/cm2以下が好ましい。研磨し
ている間、研磨布にはスラリーをポンプ等で連続的に供
給する。この供給量には制限はないが、研磨布の表面が
常にスラリーで覆われていることが好ましい。
A semiconductor substrate at a stage where circuit elements and wiring patterns are formed,
A substrate in which a SiO 2 insulating film layer is formed on a semiconductor substrate such as a semiconductor substrate at a stage where circuit elements are formed can be used.
By polishing the SiO 2 insulating film layer formed on such a semiconductor substrate with the cerium oxide polishing agent,
The unevenness on the surface of the iO 2 insulating film layer is eliminated, and a smooth surface is formed over the entire surface of the semiconductor substrate. Here, as a polishing apparatus, a holder for holding a semiconductor substrate and a polishing cloth (pad) are used.
A general polishing apparatus having a surface plate on which is attached (a motor or the like whose rotation speed can be changed) is attached can be used.
As a polishing cloth, general nonwoven fabric, foamed polyurethane,
A porous fluorine resin or the like can be used, and there is no particular limitation. Further, it is preferable that the polishing cloth is subjected to a groove processing for storing the slurry. Although there is no limitation on the polishing conditions, the rotational speed of the platen 100rpm or lower rotational preferably so that no semiconductor protrude, pressure applied to the semiconductor substrate is a 1 kg / cm 2 or less as scratches is not generated after polishing preferable. During polishing, the slurry is continuously supplied to the polishing cloth by a pump or the like. Although the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with the slurry.

【0015】研磨終了後の半導体基板は、流水中で良く
洗浄後、スピンドライヤ等を用いて半導体基板上に付着
した水滴を払い落としてから乾燥させることが好まし
い。このようにして平坦化されたSiO2絶縁膜層の上
に、第2層目のアルミニウム配線を形成し、その配線間
および配線上に再度上記方法によりSiO2絶縁膜を形
成後、上記酸化セリウム研磨剤を用いて研磨することに
よって、絶縁膜表面の凹凸を解消し、半導体基板全面に
渡って平滑な面とする。この工程を所定数繰り返すこと
により、所望の層数の半導体を製造する。
After the polishing is completed, the semiconductor substrate is preferably washed well in running water, and then dried using a spin drier or the like to remove water droplets adhering to the semiconductor substrate. On this way, the SiO 2 insulating film layer which is flattened, forming an aluminum wiring of the second layer, after forming the SiO 2 insulating film again by the above method on the inter-wiring and the wiring, the cerium oxide By polishing using an abrasive, unevenness on the surface of the insulating film is eliminated, and a smooth surface is formed over the entire surface of the semiconductor substrate. By repeating this process a predetermined number of times, a semiconductor having a desired number of layers is manufactured.

【0016】本発明の酸化セリウム研磨剤は、半導体基
板に形成されたSiO2絶縁膜だけでなく、所定の配線
を有する配線板に形成されたSiO2絶縁膜、ガラス、
窒化ケイ素等の無機絶縁膜、フォトマスク・レンズ・プ
リズムなどの光学ガラス、ITO等の無機導電膜、ガラ
ス及び結晶質材料で構成される光集積回路・光スイッチ
ング素子・光導波路、光ファイバ−の端面、シンチレ−
タ等の光学用単結晶、固体レ−ザ単結晶、青色レ−ザ用
LEDサファイア基板、SiC、GaP、GaAS等の
半導体単結晶、磁気ディスク用ガラス基板、磁気ヘッド
等を研磨するために使用される。このように本発明にお
いて所定の基板とは、SiO2絶縁膜が形成された半導
体基板、SiO2絶縁膜が形成された配線板、ガラス、
窒化ケイ素等の無機絶縁膜、フォトマスク・レンズ・プ
リズムなどの光学ガラス、ITO等の無機導電膜、ガラ
ス及び結晶質材料で構成される光集積回路・光スイッチ
ング素子・光導波路、光ファイバ−の端面、シンチレ−
タ等の光学用単結晶、固体レ−ザ単結晶、青色レ−ザ用
LEDサファイア基板、SiC、GaP、GaAS等の
半導体単結晶、磁気ディスク用ガラス基板、磁気ヘッド
等を含む。
The cerium oxide abrasive of the present invention can be used not only for an SiO 2 insulating film formed on a semiconductor substrate but also for a SiO 2 insulating film formed on a wiring board having predetermined wiring, glass,
Inorganic insulating films such as silicon nitride, optical glasses such as photomasks, lenses, and prisms; inorganic conductive films such as ITO; optical integrated circuits, optical switching elements, optical waveguides, and optical fibers composed of glass and crystalline materials. End face, scintillation
Used for polishing optical single crystals such as lasers, solid laser single crystals, LED sapphire substrates for blue lasers, semiconductor single crystals such as SiC, GaP, GaAs, glass substrates for magnetic disks, magnetic heads, etc. Is done. Thus the predetermined substrate in the present invention, a semiconductor substrate which SiO 2 insulating film is formed, SiO 2 wiring board on which an insulating film is formed, glass,
Inorganic insulating films such as silicon nitride, optical glasses such as photomasks, lenses, and prisms; inorganic conductive films such as ITO; optical integrated circuits, optical switching elements, optical waveguides, and optical fibers composed of glass and crystalline materials. End face, scintillation
Optical single crystal such as laser, solid laser single crystal, blue laser LED sapphire substrate, semiconductor single crystal such as SiC, GaP, GaAs, magnetic disk glass substrate, magnetic head, etc.

【0017】[0017]

【実施例】【Example】

(酸化セリウム粒子の作製)炭酸セリウム水和物(9
9.9%)600gを白金製の容器に入れ、800℃で
2時間空気中で焼成することにより黄白色の粉末を得
た。この粉末をX線回折法で相同定を行ったところ酸化
セリウムであることを確認した。さらに透過型電子顕微
鏡による観察で粒子が100〜300nmの1次粒子が
全数の90%以上であることも確認した。
(Preparation of Cerium Oxide Particles) Cerium carbonate hydrate (9
(9.9%) was placed in a platinum container and baked in air at 800 ° C. for 2 hours to obtain a yellow-white powder. When this powder was subjected to phase identification by an X-ray diffraction method, it was confirmed that the powder was cerium oxide. Further, observation by a transmission electron microscope confirmed that 90% or more of the total number of primary particles having a particle size of 100 to 300 nm was at least 90%.

【0018】(酸化セリウムスラリーの作製)上記の酸
化セリウム粉末80gを脱イオン水800g中に分散し
て、これにポリアクリル酸アンモニウム塩8gを添加
後、遊星ボールミル(フリッチェ社製、商品名P−5
型)を用いて2300rpmで30分間分散処理を施す
ことにより、乳白色の酸化セリウムスラリーを得た。こ
のスラリーpHは9.1であった。スラリーの粒度分布
を調べたところ(Master Sizer製)、平均
粒子径が270nmと小さく、その半値幅も300nm
と比較的分布も狭いことがわかった。
(Preparation of cerium oxide slurry) 80 g of the above cerium oxide powder was dispersed in 800 g of deionized water, and 8 g of ammonium polyacrylate was added thereto. 5
The resulting mixture was subjected to a dispersion treatment at 2300 rpm for 30 minutes using a mold to obtain a milky white cerium oxide slurry. The slurry pH was 9.1. When the particle size distribution of the slurry was examined (manufactured by Master Sizer), the average particle size was as small as 270 nm and the half width was also 300 nm.
It was found that the distribution was relatively narrow.

【0019】(絶縁膜層の研磨)保持する基板取り付け
用の吸着パッドを貼り付けたホルダーにTEOS−プラ
ズマCVD法で作製したSiO2絶縁膜を形成させたS
iウエハをセットし、多孔質ウレタン樹脂製の研磨パッ
ドを貼り付けた定盤上に絶縁膜面を下にしてホルダーを
載せ、さらに加工加重が160g/cm2になるように
重しを載せた。定盤上に上記の酸化セリウムスラリー
(固形分:2.5wt%)を35cc/minの速度で
滴下しながら、定盤を30rpmで3分間回転させ、絶
縁膜を研磨した。研磨後ウエハをホルダーから取り外し
て、流水で良く洗浄後、超音波洗浄機によりさらに20
分間洗浄した。洗浄後、ウエハをスピンドライヤーで水
滴を除去し、120℃の乾燥機で10分間乾燥させた。
光干渉式膜厚測定装置を用いて、研磨前後の膜厚変化を
測定した結果、この研磨により640nmの絶縁膜が削
られ、ウエハ全面に渡って均一の厚みになっていること
がわかった。また、目視では絶縁膜表面には傷が見られ
なかった。
(Polishing of Insulating Film Layer) An SiO 2 insulating film formed by a TEOS-plasma CVD method was formed on a holder to which a suction pad for attaching a substrate to be held was attached.
The i-wafer was set, and the holder was placed with the insulating film surface down on a surface plate on which a polishing pad made of a porous urethane resin was attached, and a weight was further placed so that the processing load was 160 g / cm 2 . . While the cerium oxide slurry (solid content: 2.5 wt%) was dropped at a rate of 35 cc / min on the platen, the platen was rotated at 30 rpm for 3 minutes to polish the insulating film. After polishing, the wafer is removed from the holder, washed well with running water, and then further cleaned with an ultrasonic cleaner.
Washed for minutes. After the cleaning, water droplets were removed from the wafer with a spin dryer, and the wafer was dried with a dryer at 120 ° C. for 10 minutes.
The change in film thickness before and after polishing was measured using an optical interference type film thickness measuring apparatus. As a result, it was found that the 640 nm insulating film was shaved by this polishing and had a uniform thickness over the entire surface of the wafer. In addition, no scratch was observed on the surface of the insulating film visually.

【0020】比較例 実施例と同様にTEOS−CVD法で作製したSiO2
絶縁膜を形成させたSiウエハについて、市販シリカス
ラリー(キャボット社製、商品名SS225)を用いて
研磨を行った。この市販スラリーのpHは10.3で、
SiO2粒子を12.5wt%含んでいるものである。
研磨条件は実施例と同一である。その結果、研磨による
傷は見られず、また均一に研磨がなされたが、3分間の
研磨により75nmの絶縁膜層しか削れなかった。
Comparative Example SiO 2 prepared by the TEOS-CVD method in the same manner as in the example.
The Si wafer on which the insulating film was formed was polished using a commercially available silica slurry (manufactured by Cabot Corp., trade name SS225). The pH of this commercial slurry was 10.3,
It contains 12.5 wt% of SiO 2 particles.
The polishing conditions are the same as in the embodiment. As a result, no scratches were found due to the polishing, and the polishing was performed uniformly, but only the insulating film layer of 75 nm was removed by the polishing for 3 minutes.

【0021】[0021]

【発明の効果】本発明の研磨剤により、SiO2絶縁膜
等の被研磨面を傷なく高速に研磨することが可能とな
る。
According to the polishing agent of the present invention, a surface to be polished such as an SiO 2 insulating film can be polished at high speed without being damaged.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI H01L 21/304 321 H01L 21/304 321P ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI H01L 21/304 321 H01L 21/304 321P

Claims (7)

【特許請求の範囲】[Claims] 【請求項1】 透過型電子顕微鏡による観察で粒子径が
100nm以上300nm以下である1次粒子が全数の
90%以上である酸化セリウム粒子を媒体に分散させた
スラリーを含む酸化セリウム研磨剤。
1. A cerium oxide abrasive comprising a slurry in which cerium oxide particles having 90% or more of all primary particles having a particle diameter of 100 nm or more and 300 nm or less as observed by a transmission electron microscope are dispersed in a medium.
【請求項2】 スラリーが分散剤を含む請求項1記載の
酸化セリウム研磨剤。
2. The cerium oxide abrasive according to claim 1, wherein the slurry contains a dispersant.
【請求項3】 媒体が水である請求項1又は2記載の酸
化セリウム研磨剤。
3. The cerium oxide abrasive according to claim 1, wherein the medium is water.
【請求項4】 分散剤が水溶性有機高分子、水溶性陰イ
オン性界面活性剤、水溶性非イオン性界面活性剤及び水
溶性アミンから選ばれる少なくとも1種である請求項2
記載の酸化セリウム研磨剤。
4. The dispersant is at least one selected from a water-soluble organic polymer, a water-soluble anionic surfactant, a water-soluble nonionic surfactant and a water-soluble amine.
The cerium oxide abrasive as described.
【請求項5】 スラリーのpHが7以上10以下のスラ
リーである請求項1〜4各項記載の酸化セリウム研磨
剤。
5. The cerium oxide abrasive according to claim 1, wherein the slurry has a pH of 7 or more and 10 or less.
【請求項6】 請求項1〜5各項記載の酸化セリウム研
磨剤で所定の基板を研磨することを特徴とする基板の研
磨法。
6. A method for polishing a substrate, comprising polishing a predetermined substrate with the cerium oxide abrasive according to any one of claims 1 to 5.
【請求項7】 所定の基板がSiO2絶縁膜が形成され
た基板である請求項6記載の基板の研磨法。
7. The method according to claim 6, wherein the predetermined substrate is a substrate on which an SiO 2 insulating film is formed.
JP8258767A 1996-09-30 1996-09-30 Cerium oxide abrasive and grinding of substrate Withdrawn JPH10102038A (en)

Priority Applications (26)

Application Number Priority Date Filing Date Title
JP8258767A JPH10102038A (en) 1996-09-30 1996-09-30 Cerium oxide abrasive and grinding of substrate
KR1020067021504A KR100759182B1 (en) 1996-09-30 1997-09-30 A Cerium Oxide Particle
CNB97199370XA CN1282226C (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and method of abrading substrates
KR1020067021503A KR100761636B1 (en) 1996-09-30 1997-09-30 A Cerium Oxide Particle
CNB03119818XA CN1245471C (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and method of polishing substrates
EP07109339.7A EP1833084B1 (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and method of polishing substrates
AU43231/97A AU4323197A (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and method of abrading substrates
CNB031198198A CN1323124C (en) 1996-09-30 1997-09-30 Cerium oxide abrasive material and grinding method of base plate
CN2006101425095A CN1935927B (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and method of polishing substrates
PCT/JP1997/003490 WO1998014987A1 (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and method of abrading substrates
EP05106514A EP1610367B1 (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and method of polishing substrates
KR1020027006123A KR100622519B1 (en) 1996-09-30 1997-09-30 A Cerium Oxide Particle
DE69739813T DE69739813D1 (en) 1996-09-30 1997-09-30 Ceria-based abrasive and process for polishing surfaces
RU99109040/28A RU2178599C2 (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and substrate polishing technique
KR1020047006307A KR100710779B1 (en) 1996-09-30 1997-09-30 A Cerium Oxide Particle
US09/269,650 US6221118B1 (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and method of polishing substrates
KR10-1999-7002723A KR100420087B1 (en) 1996-09-30 1997-09-30 Cerium Oxide Abrasive and Method of Abrading Substrates
CA002263241A CA2263241C (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and method of abrading substrates
EP97941287A EP0939431B1 (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and method of abrading substrates
DE69739413T DE69739413D1 (en) 1996-09-30 1997-09-30 ABRASIVES OF CERIUM OXIDE AND METHOD FOR GRINDING SUBSTRATES
KR1020077015361A KR100775228B1 (en) 1996-09-30 1997-09-30 A Cerium Oxide Particle
EP09178160A EP2164095A1 (en) 1996-09-30 1997-09-30 Cerium oxide abrasive and method of polishing substrates
US09/782,241 US6863700B2 (en) 1996-09-30 2001-02-13 Cerium oxide abrasive and method of polishing substrates
US10/960,941 US7708788B2 (en) 1996-09-30 2004-10-12 Cerium oxide abrasive and method of polishing substrates
US11/276,161 US7867303B2 (en) 1996-09-30 2006-02-16 Cerium oxide abrasive and method of polishing substrates
US11/276,157 US20060118524A1 (en) 1996-09-30 2006-02-16 Cerium oxide abrasive and method of polishing substrates

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8258767A JPH10102038A (en) 1996-09-30 1996-09-30 Cerium oxide abrasive and grinding of substrate

Publications (1)

Publication Number Publication Date
JPH10102038A true JPH10102038A (en) 1998-04-21

Family

ID=17324811

Family Applications (1)

Application Number Title Priority Date Filing Date
JP8258767A Withdrawn JPH10102038A (en) 1996-09-30 1996-09-30 Cerium oxide abrasive and grinding of substrate

Country Status (1)

Country Link
JP (1) JPH10102038A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000269172A (en) * 1999-03-17 2000-09-29 Sharp Corp Method for altering polishing pattern dependence in chemical mechanical polishing
JP2001072962A (en) * 1999-06-28 2001-03-21 Nissan Chem Ind Ltd Hard disc abrasive made of glass
US6863700B2 (en) 1996-09-30 2005-03-08 Hitachi Chemical Company, Ltd. Cerium oxide abrasive and method of polishing substrates
JP2008543577A (en) * 2005-06-13 2008-12-04 バスフ エスイー Slurry composition for polishing color filters
US8853082B2 (en) 2009-12-28 2014-10-07 Hitachi Chemical Company, Ltd. Polishing liquid for CMP and polishing method using the same
WO2023013683A1 (en) 2021-08-06 2023-02-09 昭和電工マテリアルズ株式会社 Polishing liquid for cmp, polishing liquid set for cmp and polishing method

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7867303B2 (en) 1996-09-30 2011-01-11 Hitachi Chemical Co., Ltd. Cerium oxide abrasive and method of polishing substrates
US6863700B2 (en) 1996-09-30 2005-03-08 Hitachi Chemical Company, Ltd. Cerium oxide abrasive and method of polishing substrates
US7708788B2 (en) 1996-09-30 2010-05-04 Hitachi Chemical Co, Ltd. Cerium oxide abrasive and method of polishing substrates
JP2000269172A (en) * 1999-03-17 2000-09-29 Sharp Corp Method for altering polishing pattern dependence in chemical mechanical polishing
JP2001072962A (en) * 1999-06-28 2001-03-21 Nissan Chem Ind Ltd Hard disc abrasive made of glass
JP4544379B2 (en) * 1999-06-28 2010-09-15 日産化学工業株式会社 Glass hard disk abrasive
JP2008543577A (en) * 2005-06-13 2008-12-04 バスフ エスイー Slurry composition for polishing color filters
US8853082B2 (en) 2009-12-28 2014-10-07 Hitachi Chemical Company, Ltd. Polishing liquid for CMP and polishing method using the same
WO2023013683A1 (en) 2021-08-06 2023-02-09 昭和電工マテリアルズ株式会社 Polishing liquid for cmp, polishing liquid set for cmp and polishing method
WO2023013695A1 (en) 2021-08-06 2023-02-09 昭和電工マテリアルズ株式会社 Polishing liquid for cmp, polishing liquid set for cmp, and polishing method
WO2023013692A1 (en) 2021-08-06 2023-02-09 昭和電工マテリアルズ株式会社 Polishing liquid for cmp, polishing liquid set for cmp, and polishing method
KR20240024993A (en) 2021-08-06 2024-02-26 가부시끼가이샤 레조낙 Polishing liquid for CMP, polishing liquid set for CMP and polishing method
KR20240027830A (en) 2021-08-06 2024-03-04 가부시끼가이샤 레조낙 Polishing liquid for CMP, polishing liquid set for CMP and polishing method
KR20240027827A (en) 2021-08-06 2024-03-04 가부시끼가이샤 레조낙 Polishing liquid for CMP, polishing liquid set for CMP and polishing method

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