JP2007036271A - Cerium oxide abrasive, and method of polishing substrate - Google Patents
Cerium oxide abrasive, and method of polishing substrate Download PDFInfo
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本発明は、酸化セリウム研磨剤及び基板の研磨法に関する。 The present invention relates to a cerium oxide abrasive and a method for polishing a substrate.
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。 Conventionally, colloidal silica-based abrasives have been used as chemical mechanical abrasives for planarizing inorganic insulating film layers such as SiO 2 insulating films formed by methods such as plasma-CVD and low-pressure CVD in the manufacturing process of semiconductor devices. Generally considered. Colloidal silica-based abrasives are produced by growing silica particles by a method such as thermal decomposition of tetrachlorosilicic acid and adjusting the pH with an alkaline solution containing no alkali metal such as ammonia. However, such an abrasive 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.
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, a cerium oxide abrasive is used for photomask glass surface polishing. Cerium oxide particles have a lower hardness than silica particles and alumina particles, and are therefore useful for finishing mirror polishing because they do not easily scratch the polished surface. Moreover, cerium oxide has a chemically active property as known as a strong oxidizing agent. Taking advantage of this advantage, application to a chemical mechanical polishing agent for insulating films is useful. However, when the cerium oxide abrasive for polishing a glass surface for a photomask is applied as it is to the polishing of an inorganic insulating film, the primary particle size is large, so that a polishing flaw that can be visually observed enters the insulating film surface.
本発明は、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。 The present invention provides a cerium oxide abrasive capable of polishing a surface to be polished such as a SiO 2 insulating film at a high speed without damage and a method for polishing a substrate.
本発明の酸化セリウム研磨剤は、一次粒子径の中央値が３０〜２５０ｎｍであり粒子径の中央値が１５０〜６００ｎｍ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。また本発明の酸化セリウム研磨剤は、一次粒子径の中央値が１００〜２５０ｎｍであり粒子径の中央値が１５０〜３５０ｎｍ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ことができる。上記の酸化セリウム粒子では、一次粒子の最大径は６００ｎｍ以下が好ましく、一次粒子径は１０〜６００ｎｍであることが好ましい。 The cerium oxide abrasive of the present invention contains a slurry in which cerium oxide particles having a median primary particle diameter of 30 to 250 nm and a median particle diameter of 150 to 600 nm are dispersed in a medium. Moreover, the cerium oxide abrasive | polishing agent of this invention can contain the slurry which disperse | distributed to the medium the cerium oxide particle | grains whose median value of a primary particle diameter is 100-250 nm and whose median value of particle diameter is 150-350 nm. In the cerium oxide particles, the maximum primary particle diameter is preferably 600 nm or less, and the primary particle diameter is preferably 10 to 600 nm.
また本発明の酸化セリウム研磨剤は、一次粒子径の中央値が３０〜７０ｎｍであり粒子径の中央値が２５０〜６００ｎｍ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ことができる。上記の酸化セリウム粒子では、一次粒子径は１０〜１００ｎｍであることが好ましい。本発明の酸化セリウム研磨剤では、酸化セリウム粒子の最大径は３０００ｎｍ以下であることが好ましい。 Moreover, the cerium oxide abrasive | polishing agent of this invention can contain the slurry which disperse | distributed to the medium the cerium oxide particle | grains whose median value of a primary particle diameter is 30-70 nm and whose median value of particle diameter is 250-600 nm. In the cerium oxide particles, the primary particle diameter is preferably 10 to 100 nm. In the cerium oxide abrasive of the present invention, the maximum diameter of the cerium oxide particles is preferably 3000 nm or less.
媒体として水を使用することができ、例えば水溶性有機高分子、水溶性陰イオン界面活性剤、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種である分散剤が使用され、ポリアクリル酸アンモニウム塩が好ましい。酸化セリウム粒子は炭酸セリウムを焼成した酸化セリウムが好ましく使用される。本発明の酸化セリウム研磨剤で、例えばシリカ膜が形成された半導体チップ等の所定の基板を研磨することができる。 Water can be used as the medium. For example, a dispersant that 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 is used. Polyacrylic acid ammonium salt is preferred. The cerium oxide particles are preferably cerium oxide obtained by firing cerium carbonate. For example, a predetermined substrate such as a semiconductor chip on which a silica film is formed can be polished with the cerium oxide abrasive of the present invention.
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。 The polishing agent of the present invention, it is possible to polish the surface to be polished such as SiO 2 insulating film is wound without a high speed.
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ＳｉＯ２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。本発明の研磨剤は高純度のもので、Ｎａ、Ｋ、Ｓｉ、Ｍｇ、Ｃａ、Ｚｒ、Ｔｉ、Ｎｉ、Ｃｒ、Ｆｅはそれぞれ１ｐｐｍ以下、Ａｌは１０ｐｐｍ以下である。 In general, cerium oxide is obtained by firing a cerium compound such as carbonate, sulfate, or oxalate. The SiO 2 insulating film formed by TEOS-CVD or the like has a larger primary particle diameter and a smaller crystal distortion, that is, a higher crystallinity allows higher-speed polishing, but there is a tendency for polishing flaws to occur. . Therefore, the cerium oxide particles used in the present invention are produced without increasing crystallinity. Moreover, since it uses for semiconductor chip grinding | polishing, it is preferable to suppress the content rate of an alkali metal and halogens to 1 ppm or less. The abrasive | polishing agent of this invention is a highly purified thing, Na, K, Si, Mg, Ca, Zr, Ti, Ni, Cr, and Fe are 1 ppm or less respectively, and Al is 10 ppm or less.
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６００℃以上９００℃以下が好ましい。炭酸セリウムを６００℃以上９００℃以下で５〜３００分、酸素ガス等の酸化雰囲気で焼成すること好ましい。焼成された酸化セリウムは、ジェットミル等の乾式粉砕、ビ−ズミル等の湿式粉砕で粉砕することができる。ジェットミルは例えば化学工業論文集第６巻第５号（１９８０）５２７〜５３２頁に説明されている。焼成された酸化セリウムをジェットミル等の乾式粉砕で粉砕すると粉砕残りの発生が観察された。 In the present invention, a firing method can be used as a method for producing cerium oxide particles. However, low temperature firing that does not increase the crystallinity as much as possible is preferable in order to produce particles free from abrasive scratches. Since the oxidation temperature of the cerium compound is 300 ° C, the firing temperature is preferably 600 ° C or higher and 900 ° C or lower. It is preferable to calcine cerium carbonate at 600 ° C. or higher and 900 ° C. or lower for 5 to 300 minutes in an oxidizing atmosphere such as oxygen gas. The calcined cerium oxide can be pulverized by dry pulverization such as a jet mill or wet pulverization such as a bead mill. The jet mill is described, for example, in Chemical Industrial Papers Vol. 6 No. 5 (1980) pp. 527-532. When the calcined cerium oxide was pulverized by dry pulverization such as a jet mill, generation of pulverized residue was observed.
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か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０．１〜１０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。 The cerium oxide slurry in the present invention 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. It is done. Although there is no restriction | limiting in the density | concentration of a cerium oxide particle here, the range of 0.1-10 weight% is preferable from the ease of handling of suspension. The dispersant does not contain metal ions, and includes acrylic acid polymer and its ammonium salt, methacrylic acid polymer and its ammonium salt, water-soluble organic polymers such as polyvinyl alcohol, ammonium lauryl sulfate, and polyoxyethylene. Water-soluble anionic surfactants such as ammonium lauryl ether sulfate, water-soluble nonionic surfactants such as polyoxyethylene lauryl ether and polyethylene glycol monostearate, and water-soluble amines such as monoethanolamine and diethanolamine It is done.
ポリアクリル酸アンモニウム塩、特に重量平均分子量５０００〜２００００のポリアクリル酸アンモニウム塩が好ましい。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。 Polyacrylic acid ammonium salts, particularly polyacrylic acid ammonium salts having a weight average molecular weight of 5000 to 20000 are preferred. The amount of these dispersants added is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the cerium oxide particles in view of the dispersibility of the particles in the slurry and the anti-settling property. For this purpose, it is preferable to put the particles in the disperser at the same time as the particles during the dispersion treatment.
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 a dispersion treatment using a normal stirrer. In particular, in order to disperse the cerium oxide particles as fine particles having a size of 1 μm or less, it is preferable to use a wet disperser such as a ball mill, a vibration ball mill, a planetary ball mill, or a medium stirring mill. When it is desired to increase the alkalinity of the slurry, an alkaline substance that does not contain metal ions such as aqueous ammonia can be added during or after the dispersion treatment.
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。 The cerium oxide abrasive of the present invention may use the above slurry as it is, but an additive such as N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethylethanolamine is added. Thus, an abrasive can be obtained.
本発明のスラリーに分散される酸化セリウム粒子を構成する一次粒子径の中央値は３０〜２５０ｎｍであり、粒子径の中央値は１５０〜６００ｎｍである。一次粒子径の中央値が３０ｎｍ未満又は粒子径の中央値が１５０ｎｍ未満であればＳｉＯ２絶縁膜等の被研磨面を高速に研磨することができず、一次粒子径の中央値が２５０ｎｍを越える又は粒子径の中央値が６００ｎｍを越えるとＳｉＯ２絶縁膜等の被研磨面に傷が発生する。 The median primary particle size constituting the cerium oxide particles dispersed in the slurry of the present invention is 30 to 250 nm, and the median particle size is 150 to 600 nm. If the median of the primary particle diameter is less than 30 nm or the median of the particle diameter is less than 150 nm, the surface to be polished such as the SiO 2 insulating film cannot be polished at high speed, and the median of the primary particle diameter exceeds 250 nm. Alternatively, when the median particle diameter exceeds 600 nm, scratches occur on the surface to be polished such as the SiO 2 insulating film.
また一次粒子径の中央値が１００〜２５０ｎｍであり粒子径の中央値が１５０〜３５０ｎｍである酸化セリウム粒子が好ましく、それぞれの中央値が上記下限値未満であると研磨速度が小さくなり、上限値を越えると傷が発生しやすい。上記の酸化セリウム粒子では、一次粒子の最大径は６００ｎｍ以下が好ましく、一次粒子径は１０〜６００ｎｍであることが好ましい。一次粒子が６００ｎｍを上限値を越えると傷が発生しやすく、１０ｎｍ未満であると研磨速度が小さくなる。 Further, cerium oxide particles having a median primary particle diameter of 100 to 250 nm and a median particle diameter of 150 to 350 nm are preferable. When each median value is less than the above lower limit value, the polishing rate is decreased, and the upper limit value is reached. If it exceeds, scratches are likely to occur. In the cerium oxide particles, the maximum primary particle diameter is preferably 600 nm or less, and the primary particle diameter is preferably 10 to 600 nm. If the primary particle exceeds 600 nm, scratches are likely to occur, and if it is less than 10 nm, the polishing rate decreases.
また一次粒子径の中央値が３０〜７０ｎｍであり粒子径の中央値が２５０〜６００ｎｍである酸化セリウム粒子が好ましく、それぞれの中央値が上記下限値未満であると研磨速度が小さくなり、上限値を越えると傷が発生しやすい。 Further, cerium oxide particles having a median primary particle diameter of 30 to 70 nm and a median particle diameter of 250 to 600 nm are preferable. When each median value is less than the above lower limit value, the polishing rate is reduced, and the upper limit value is reached. If it exceeds, scratches are likely to occur.
上記の酸化セリウム粒子では、一次粒子径は１０〜１００ｎｍであることが好ましく、一次粒子が１０ｎｍ未満であると研磨速度が小さくなり、１００ｎｍを上限値を越えると傷が発生しやすくなる。 In the cerium oxide particles, the primary particle diameter is preferably 10 to 100 nm. When the primary particles are less than 10 nm, the polishing rate is low, and when the primary particles exceed 100 nm, scratches tend to occur.
本発明の酸化セリウム研磨剤では、酸化セリウム粒子の最大径は３０００ｎｍ以下であることが好ましい。酸化セリウム粒子の最大径が３０００ｎｍを越えると傷が発生しやすい。 In the cerium oxide abrasive of the present invention, the maximum diameter of the cerium oxide particles is preferably 3000 nm or less. If the maximum diameter of the cerium oxide particles exceeds 3000 nm, scratches are likely to occur.
焼成酸化セリウムをジェットミル等の乾式粉砕で粉砕した酸化セリウム粒子には粉砕残りが含まれ、この粉砕残り粒子は一次粒子が再凝集した凝集体とは異なっており、研磨時の応力により破壊され活性面を発生すると推定され、ＳｉＯ２絶縁膜等の被研磨面を傷なく高速に研磨することに寄与していると考えられる。本発明のスラリ−には、３０００ｎｍ以下の粉砕残り粒子を含むことができる。 The cerium oxide particles obtained by pulverizing calcined cerium oxide by dry pulverization such as a jet mill contain pulverized residue, and this pulverized residual particle is different from the aggregate in which primary particles are re-agglomerated, and is destroyed by stress during polishing. It is estimated that an active surface is generated, and it is considered that it contributes to polishing the surface to be polished such as the SiO 2 insulating film at high speed without scratches. The slurry of the present invention can contain residual grinding particles of 3000 nm or less.
本発明で、一次粒子径は走査型電子顕微鏡（例えば（株）日立製作所製 Ｓ−９００型）による観察で測定する。スラリ−粒子である酸化セリウム粒子径はレ−ザ回折法（例えばマルバーンインスツルメンツ社製 Ｍａｓｔｅｒ Ｓｉｚｅｒ ｍｉｃｒｏｐｌｕｓ、屈折率：１．９２８５、光源：Ｈｅ−Ｎｅレーザー、吸収０）によって測定する。 In the present invention, the primary particle diameter is measured by observation with a scanning electron microscope (for example, S-900 type manufactured by Hitachi, Ltd.). The cerium oxide particle diameter, which is a slurry particle, is measured by a laser diffraction method (for example, Master Sizer microplus, refractive index: 1.9285, light source: He—Ne laser, absorption 0) manufactured by Malvern Instruments.
本発明のスラリ−に分散された酸化セリウム粒子を構成する一次粒子のアスペクト比は１〜２、中央値１．３が好ましい。アスペクト比は走査型電子顕微鏡（例えば（株）日立製作所製 Ｓ−９００型）による観察で測定する。 The aspect ratio of the primary particles constituting the cerium oxide particles dispersed in the slurry of the present invention is preferably 1 to 2, and the median value is 1.3. The aspect ratio is measured by observation with a scanning electron microscope (for example, S-900 type manufactured by Hitachi, Ltd.).
本発明のスラリ−に分散された酸化セリウム粒子として、粉末Ｘ線リートベルト法（ＲＩＥＴＡＮ−９４）による解析で等方的微小歪を表わす構造パラメーター：Ｙの値が０．０１以上０．７０以下である酸化セリウム粒子を使用することができる。このような結晶歪みを有する酸化セリウム粒子を使用することにより、被研磨表面に傷をつけることなく、かつ高速に研磨することができる。 As the cerium oxide particles dispersed in the slurry of the present invention, a structural parameter representing an isotropic fine strain as analyzed by the powder X-ray Rietveld method (RIETAN-94): the value of Y is 0.01 or more and 0.70 or less The cerium oxide particles can be used. By using cerium oxide particles having such crystal distortion, polishing can be performed at high speed without damaging the surface to be polished.
本発明のスラリ−に分散された酸化セリウム粒子の比表面積は７〜４５ｍ２／ｇが好ましい。比表面積が７ｍ２／ｇ未満だと被研磨表面に傷をつけるやすくなり、４５ｍ２／ｇを越えると研磨速度が遅くなる傾向にある。スラリ−の酸化セリウム粒子の比表面積は分散される酸化セリウム粒子の比表面積と同じである。 The specific surface area of the cerium oxide particles dispersed in the slurry of the present invention is preferably 7 to 45 m 2 / g. When the specific surface area is less than 7 m 2 / g, the surface to be polished tends to be damaged, and when it exceeds 45 m 2 / g, the polishing rate tends to be slow. The specific surface area of the slurry cerium oxide particles is the same as that of the dispersed cerium oxide particles.
本発明のスラリ−中の酸化セリウム粒子のゼ−タ電位は−１００ｍＶ以上−１０ｍＶが好ましい。これにより酸化セリウム粒子の分散性を良好にし被研磨表面に傷をつけることなく、かつ高速に研磨することができる。 The zeta potential of the cerium oxide particles in the slurry of the present invention is preferably -100 mV or more and -10 mV. As a result, the dispersibility of the cerium oxide particles is improved, and the surface to be polished can be polished at a high speed without being damaged.
本発明のスラリ−に分散された酸化セリウム粒子は平均粒径が２００ｎｍ以上４００ｎｍ以下で粒度分布の半値幅が３００ｎｍ以下とすることができる。本発明のスラリ−のｐＨは７以上１０以下が好ましく、８以上９以下がより好ましい。 The cerium oxide particles dispersed in the slurry of the present invention can have an average particle size of 200 nm to 400 nm and a half width of the particle size distribution of 300 nm or less. The pH of the slurry of the present invention is preferably from 7 to 10, more preferably from 8 to 9.
スラリ−調整後、ポリエチレン等の容器に入れ５〜５５℃で７日以上、より好ましくは３０日以上放置して使用すれば傷の発生が少なくなる。 After the slurry is adjusted, if it is used in a container such as polyethylene at 5 to 55 ° C. for 7 days or longer, more preferably 30 days or longer, the generation of scratches is reduced.
本発明のスラリ−は分散性に優れ沈降速度が遅く、直径１０ｃｍ高さ１ｍの円中のどの高さの位置でも２時間放置濃度変化率が１０％未満である。 The slurry of the present invention is excellent in dispersibility and has a slow sedimentation rate, and the rate of change in the concentration for 2 hours is less than 10% at any height position in a circle having a diameter of 10 cm and a height of 1 m.
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、低圧ＣＶＤ法、プラズマＣＶＤ法等が挙げられる。低圧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（ＴＥＯＳ）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。 Examples of a method for manufacturing an inorganic insulating film in which the cerium oxide abrasive of the present invention is used include a low pressure CVD method and a plasma CVD method. In the formation of the SiO 2 insulating film by the low pressure CVD method, monosilane: SiH 4 is used as the Si source, and oxygen: O 2 is used as the oxygen source. It can be obtained by performing this SiH 4 —O 2 -based oxidation reaction at a low temperature of about 400 ° C. or less. When doping phosphorus: P in order to achieve surface flattening by high-temperature reflow, it is preferable to use a SiH 4 —O 2 —PH 3 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. There are two plasma generation methods, capacitive coupling type and inductive coupling type. The reaction as a gas, SiH 4 as an Si source, an oxygen source as N 2 O was used was SiH 4 -N 2 O-based gas and TEOS-O 2 based gas using tetraethoxysilane (TEOS) in an Si source (TEOS- Plasma CVD method). The substrate temperature is preferably 250 to 400 ° C., and the reaction pressure is preferably 67 to 400 Pa. Thus, elements such as phosphorus and boron may be doped in the SiO 2 insulating film of the present invention.
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、ＳｉＯ２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。 As the predetermined substrate, a semiconductor substrate, that is, a semiconductor substrate in which a circuit element and a wiring pattern are formed, or a substrate in which a SiO 2 insulating film layer is formed on a semiconductor substrate such as a semiconductor substrate in which a circuit element is formed is used. it can. By polishing the SiO 2 insulating film layer formed on such a semiconductor substrate with the cerium oxide abrasive, unevenness on the surface of the SiO 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 general polishing apparatus having a surface plate with a holder for holding a semiconductor substrate and a polishing cloth (pad) attached (a motor etc. capable of changing the number of rotations) is used. it can. As an abrasive cloth, a general nonwoven fabric, a polyurethane foam, a porous fluororesin, etc. can be used, and there is no restriction | limiting in particular. Further, it is preferable that the polishing cloth is subjected to groove processing so that slurry is accumulated. The polishing conditions are not limited, but the rotation speed of the surface plate is preferably low rotation of 100 rpm or less so that the semiconductor does not jump out, and the pressure applied to the semiconductor substrate is 1 kg / cm 2 or less so that no scratches are generated after polishing. preferable. During polishing, slurry is continuously supplied to the polishing cloth with a pump or the like. Although there is no restriction | limiting in this supply amount, it is preferable that the surface of polishing cloth is always covered with the slurry.
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。 The semiconductor substrate after completion of polishing is preferably washed in running water and then dried after removing water droplets adhering to the semiconductor substrate using a spin dryer or the like. A second-layer aluminum wiring is formed on the thus planarized SiO 2 insulating film layer, and the SiO 2 insulating film is formed again between the wirings and on the wiring by the above method, and then the cerium oxide. By polishing with 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 desired number of semiconductor layers are manufactured.
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。 Cerium oxide abrasive of the present invention is not only SiO 2 insulating film formed on a semiconductor substrate, SiO 2 insulating film formed on the wiring board having a predetermined wiring, glass, inorganic insulating films such as silicon nitride, Photo Optical glass for masks, lenses, prisms, etc., optical conductive circuits such as ITO, inorganic conductive films such as ITO, glass and crystalline materials, optical switching elements, optical waveguides, end faces of optical fibers, scintillators, etc. It is used to polish single crystals, solid laser single crystals, LED sapphire substrates for blue lasers, semiconductor single crystals such as SiC, GaP, and GaAS, glass substrates for magnetic disks, magnetic heads, and the like.
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 predetermined substrate in the present invention as described above, SiO 2 semiconductor substrate on which an insulating film is formed, SiO 2 insulating film is formed wiring board, glass, inorganic insulating films such as silicon nitride, photomask lenses and prisms Optical glass such as ITO, inorganic conductive films such as ITO, optical integrated circuits / optical switching elements / waveguides composed of glass and crystalline materials, optical fiber end faces, optical single crystals such as scintillators, solid layers, etc. -The single crystal, LED sapphire substrate for blue laser, semiconductor single crystal such as SiC, GaP, GaAS, etc., glass substrate for magnetic disk, magnetic head, etc.
実施例１
（酸化セリウム粒子の作製１）
炭酸セリウム水和物２ｋｇを白金製容器に入れ、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約１ｋｇ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。焼成粉末粒子径は３０〜１００ミクロンであった。焼成粉末粒子表面を走査型電子顕微鏡で観察したところ、酸化セリウムの粒界が観察された。粒界に囲まれた酸化セリウム一次粒子径を測定したところ、その分布の中央値が１９０ｎｍ、最大値が５００ｎｍであった。焼成粉末についてＸ線回折精密測定を行い、その結果についてリートベルト法（ＲＩＥＴＡＮ−９４）による解析で、一次粒子径を表わす構造パラメータ−：Ｘの値が０．０８０、等方的微少歪みを表わす構造パラメータ−：Ｙの値が０．２２３であった。酸化セリウム粉末１ｋｇをジェットミルを用いて乾式粉砕を行った。粉砕粒子について走査型電子顕微鏡で観察したところ、一次粒子径と同等サイズの小さな粒子の他に、１ミクロンから３ミクロンの大きな粉砕残り粒子と０．５から１ミクロンの粉砕残り粒子が混在していた。粉砕残り粒子は、一次粒子の凝集体ではない。粉砕粒子についてＸ線回折精密測定を行い、その結果についてリートベルト法（ＲＩＥＴＡＮ−９４）による解析で、一次粒子径を表わす構造パラメータ−：Ｘの値が０．０８５、等方的微少歪みを表わす構造パラメータ−：Ｙの値が０．２６４であった。この結果、粉砕による一次粒子径変量はほとんどなく、また粉砕により粒子に歪みが導入されていた。さらにＢＥＴ法による比表面積測定の結果、１０ｍ２／ｇであることがわかった。
Example 1
(Preparation of cerium oxide particles 1)
About 1 kg of yellowish white powder was obtained by putting 2 kg of cerium carbonate hydrate into a platinum container and firing in air at 800 ° C. for 2 hours. When this powder was phase-identified by X-ray diffraction, it was confirmed to be cerium oxide. The calcined powder particle size was 30-100 microns. When the surface of the fired powder particles was observed with a scanning electron microscope, grain boundaries of cerium oxide were observed. When the primary particle diameter of cerium oxide surrounded by the grain boundaries was measured, the median value of the distribution was 190 nm and the maximum value was 500 nm. The X-ray diffraction precision measurement is performed on the calcined powder, and the result is analyzed by the Rietveld method (RIETAN-94). The structural parameter indicating the primary particle diameter: X value is 0.080, and isotropic isometric strain Structure parameter-: The value of Y was 0.223. 1 kg of cerium oxide powder was dry pulverized using a jet mill. When the pulverized particles were observed with a scanning electron microscope, a large pulverized residual particle of 1 to 3 microns and a pulverized residual particle of 0.5 to 1 micron were mixed in addition to small particles having the same size as the primary particle size. It was. The unmilled particles are not aggregates of primary particles. The X-ray diffraction precision measurement is performed on the pulverized particles, and the result is analyzed by the Rietveld method (RIETAN-94). The structural parameter indicating the primary particle diameter: the value of X is 0.085, and isotropic strain is expressed. Structural parameter-: Y value was 0.264. As a result, there was almost no change in the primary particle size due to pulverization, and distortion was introduced into the particles due to pulverization. Furthermore, as a result of measuring the specific surface area by the BET method, it was found to be 10 m 2 / g.
（酸化セリウム粒子の作製２）
炭酸セリウム水和物２ｋｇを白金製容器に入れ、７５０℃で２時間空気中で焼成することにより黄白色の粉末を約１ｋｇ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。焼成粉末粒子径は３０〜１００ミクロンであった。焼成粉末粒子表面を走査型電子顕微鏡で観察したところ、酸化セリウムの粒界が観察された。粒界に囲まれた酸化セリウム一次粒子径を測定したところ、その分布の中央値が１４１ｎｍ、最大値が４００ｎｍであった。焼成粉末についてＸ線回折精密測定を行い、その結果についてリートベルト法（ＲＩＥＴＡＮ−９４）による解析で、一次粒子径を表わす構造パラメータ−：Ｘの値が０．１０１、等方的微少歪みを表わす構造パラメータ−：Ｙの値が０．２２３であった。酸化セリウム粉末１ｋｇをジェットミルを用いて乾式粉砕を行った。粉砕粒子について走査型電子顕微鏡で観察したところ、一次粒子径と同等サイズの小さな粒子の他に、１ミクロンから３ミクロンの大きな粉砕残り粒子と０．５から１ミクロンの粉砕残り粒子が混在していた。粉砕残り粒子は、一次粒子の凝集体ではない。粉砕粒子についてＸ線回折精密測定を行い、その結果についてリートベルト法（ＲＩＥＴＡＮ−９４）による解析で、一次粒子径を表わす構造パラメータ−：Ｘの値が０．１０４、等方的微少歪みを表わす構造パラメータ−：Ｙの値が０．３１５であった。この結果、粉砕による一次粒子径変量はほとんどなく、また粉砕により粒子に歪みが導入されていた。さらにＢＥＴ法による比表面積測定の結果、１６ｍ２／ｇであることがわかった。
(Preparation of cerium oxide particles 2)
About 1 kg of yellowish white powder was obtained by putting 2 kg of cerium carbonate hydrate in a platinum container and firing in air at 750 ° C. for 2 hours. When this powder was phase-identified by X-ray diffraction, it was confirmed to be cerium oxide. The calcined powder particle size was 30-100 microns. When the surface of the fired powder particles was observed with a scanning electron microscope, grain boundaries of cerium oxide were observed. When the primary particle diameter of cerium oxide surrounded by the grain boundaries was measured, the median value of the distribution was 141 nm and the maximum value was 400 nm. The X-ray diffraction precision measurement is performed on the calcined powder, and the result is analyzed by the Rietveld method (RIETAN-94). The structural parameter representing the primary particle size: X value is 0.101, and isotropic strain is represented. Structure parameter-: The value of Y was 0.223. 1 kg of cerium oxide powder was dry pulverized using a jet mill. When the pulverized particles were observed with a scanning electron microscope, a large pulverized residual particle of 1 to 3 microns and a pulverized residual particle of 0.5 to 1 micron were mixed in addition to small particles having the same size as the primary particle size. It was. The unmilled particles are not aggregates of primary particles. The X-ray diffraction precision measurement is performed on the pulverized particles, and the result is analyzed by the Rietveld method (RIETAN-94). The structural parameter representing the primary particle diameter: X value is 0.104, and isotropic strain is represented. Structural parameter-: Y value was 0.315. As a result, there was almost no change in the primary particle size due to pulverization, and distortion was introduced into the particles due to pulverization. Furthermore, as a result of measuring the specific surface area by the BET method, it was found to be 16 m 2 / g.
（酸化セリウムスラリーの作製）
上記作製１，２の酸化セリウム粒子１ｋｇとポリアクリル酸アンモニウム塩水溶液（４０重量％）２３ｇと脱イオン水８９７７ｇを混合し、攪拌しながら超音波分散を１０分間施した。得られたスラリーを１ミクロンフィルターでろ過をし、さらに脱イオン水を加えることにより３ｗｔ．％研磨剤を得た。スラリーｐＨは８．３であった。スラリー粒子の粒度分布をレーザー回折法（測定装置：マルバーンインスツルメンツ社製Ｍａｓｔｅｒ Ｓｉｚｅｒ ｍｉｃｒｏｐｌｕｓ、屈折率：１．９２８５、光源：Ｈｅ−Ｎｅレーザー、吸収０で測定）を用いて調べたところ、中央値がともに２００ｎｍであった。最大粒子径は７８０ｎｍ以上の粒子が０体積％であった。スラリーの分散性およびスラリー粒子の電荷を調べるため、スラリーのゼータ電位を調べた。両側に白金製電極を取り付けてある測定セルに酸化セリウムスラリーを入れ、両電極に１０Ｖの電圧を印加した。電圧を印加することにより電荷を持ったスラリー粒子はその電荷と反対の極を持つ電極側に移動する。この移動速度を求めることにより粒子のゼータ電位を求めることができる。ゼータ電位測定の結果、それぞれマイナスに荷電し、−５０ｍＶ、−６３ｍＶと絶対値が大きく分散性が良好であることを確認した。
(Preparation of cerium oxide slurry)
1 kg of the cerium oxide particles of Preparations 1 and 2 above, 23 g of ammonium polyacrylate aqueous solution (40% by weight) and 8977 g of deionized water were mixed and subjected to ultrasonic dispersion for 10 minutes while stirring. The resulting slurry was filtered through a 1 micron filter and further deionized water was added to add 3 wt. % Abrasive was obtained. The slurry pH was 8.3. When the particle size distribution of the slurry particles was examined using a laser diffraction method (measuring device: Master Sizer microplus manufactured by Malvern Instruments, refractive index: 1.9285, light source: He-Ne laser, measured by absorption 0), the median value was Both were 200 nm. The maximum particle size was 0% by volume of particles having a particle size of 780 nm or more. To examine the dispersibility of the slurry and the charge of the slurry particles, the zeta potential of the slurry was examined. A cerium oxide slurry was placed in a measurement cell having platinum electrodes on both sides, and a voltage of 10 V was applied to both electrodes. When a voltage is applied, the charged slurry particles move to the side of the electrode having a pole opposite to the charge. By obtaining this moving speed, the zeta potential of the particles can be obtained. As a result of the zeta potential measurement, it was confirmed that each was negatively charged and had a large absolute value of −50 mV and −63 mV and good dispersibility.
（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Ｓｉ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、さらに加工荷重が３００ｇ／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：３重量％）を５０ｃｃ／ｍｉｎの速度で滴下しながら、定盤を３０ｒｐｍで２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、この研磨によりそれぞれ６００ｎｍ、５８０ｎｍ（研磨速度：３００ｎｍ／ｍｉｎ．、２９０ｎｍ／ｍｉｎ．）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、光学顕微鏡を用いて絶縁膜表面を観察したところ、明確な傷は見られなかった。
(Polishing the insulating film layer)
A surface plate on which a Si wafer on which a SiO 2 insulating film produced by TEOS-plasma CVD method is formed is set in a holder on which a holding pad for attaching a substrate to be held is attached, and a polishing pad made of porous urethane resin is attached. A holder was placed thereon with the insulating film face down, and a weight was placed so that the processing load would be 300 g / cm 2 . While the above cerium oxide slurry (solid content: 3% by weight) was dropped on the surface plate at a speed of 50 cc / min, the surface plate was rotated at 30 rpm for 2 minutes to polish the insulating film. After polishing, the wafer was removed from the holder, washed thoroughly with running water, and further washed with an ultrasonic cleaner for 20 minutes. After washing, 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. As a result of measuring the change in film thickness before and after polishing using an optical interference type film thickness measuring device, 600 nm and 580 nm (polishing rate: 300 nm / min., 290 nm / min.) Of the insulating film were removed by this polishing, It was found that the thickness was uniform over the entire wafer surface. Further, when the surface of the insulating film was observed using an optical microscope, no clear scratch was found.
実施例２
（酸化セリウム粒子の作製）
炭酸セリウム水和物２ｋｇを白金製容器に入れ、７００℃で２時間空気中で焼成することにより黄白色の粉末を約１ｋｇ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。焼成粉末粒子径は３０〜１００ミクロンであった。焼成粉末粒子表面を走査型電子顕微鏡で観察したところ、酸化セリウムの粒界が観察された。粒界に囲まれた酸化セリウム一次粒子径を測定したところ、その分布の中央値が５０ｎｍ、最大値が１００ｎｍであった。焼成粉末についてＸ線回折精密測定を行い、その結果についてリートベルト法（ＲＩＥＴＡＮ−９４）による解析で、一次粒子径を表わす構造パラメータ−：Ｘの値が０．３００、等方的微少歪みを表わす構造パラメータ−：Ｙの値が０．３５０であった。酸化セリウム粉末１ｋｇをジェットミルを用いて乾式粉砕を行った。粉砕粒子について走査型電子顕微鏡で観察したところ、一次粒子径と同等サイズの小さな粒子の他に、２ミクロンから４ミクロンの大きな粉砕残り粒子と０．５から１．２ミクロンの粉砕残り粒子が混在していた。粉砕残り粒子は、一次粒子の凝集体ではない。粉砕粒子についてＸ線回折精密測定を行い、その結果についてリートベルト法（ＲＩＥＴＡＮ−９４）による解析で、一次粒子径を表わす構造パラメータ−：Ｘの値が０．３０２、等方的微少歪みを表わす構造パラメータ−：Ｙの値が０．４１２であった。この結果、粉砕による一次粒子径変量はほとんどなく、また粉砕により粒子に歪みが導入されていた。さらにＢＥＴ法による比表面積測定の結果、４０ｍ２／ｇであることがわかった。
Example 2
(Production of cerium oxide particles)
About 1 kg of yellowish white powder was obtained by putting 2 kg of cerium carbonate hydrate in a platinum container and firing in air at 700 ° C. for 2 hours. When this powder was phase-identified by X-ray diffraction, it was confirmed to be cerium oxide. The calcined powder particle size was 30-100 microns. When the surface of the fired powder particles was observed with a scanning electron microscope, grain boundaries of cerium oxide were observed. When the primary particle diameter of cerium oxide surrounded by the grain boundaries was measured, the median value of the distribution was 50 nm, and the maximum value was 100 nm. The X-ray diffraction precision measurement is performed on the calcined powder, and the result is analyzed by the Rietveld method (RIETAN-94). The structural parameter representing the primary particle diameter: X value is 0.300, representing isotropic strain Structure parameter-: The value of Y was 0.350. 1 kg of cerium oxide powder was dry pulverized using a jet mill. When pulverized particles were observed with a scanning electron microscope, small particles of the same size as the primary particle size were mixed with large pulverized residual particles of 2 to 4 microns and pulverized residual particles of 0.5 to 1.2 microns. Was. The unmilled particles are not aggregates of primary particles. The X-ray diffraction precision measurement is performed on the pulverized particles, and the result is analyzed by the Rietveld method (RIETAN-94). The structural parameter representing the primary particle diameter: X value is 0.302, and isotropic isometric strain is represented. Structure parameter-: The value of Y was 0.412. As a result, there was almost no change in the primary particle size due to pulverization, and distortion was introduced into the particles due to pulverization. Furthermore, as a result of measuring the specific surface area by the BET method, it was found to be 40 m 2 / g.
（酸化セリウムスラリーの作製）
上記作製の酸化セリウム粒子１ｋｇとポリアクリル酸アンモニウム塩水溶液（４０重量％）２３ｇと脱イオン水８９７７ｇを混合し、攪拌しながら超音波分散を１０分間施した。得られたスラリーを２ミクロンフィルターでろ過をし、さらに脱イオン水を加えることにより３ｗｔ．％研磨剤を得た。スラリーｐＨは８．０であった。スラリー粒子の粒度分布をレーザー回折法（測定装置：Ｍａｓｔｅｒ Ｓｉｚｅｒ製ｍｉｃｒｏｐｌｕｓ、屈折率：１．９２８５）を用いて調べたところ、中央値が５１０ｎｍで、最大粒子径は１４３０ｎｍ以上の粒子が０％であった。スラリーの分散性およびスラリー粒子の電荷を調べるため、スラリーのゼータ電位を調べた。両側に白金製電極を取り付けてある測定セルに酸化セリウムスラリーを入れ、両電極に１０Ｖの電圧を印加した。電圧を印加することにより電荷を持ったスラリー粒子はその電荷と反対の極を持つ電極側に移動する。この移動速度を求めることにより粒子のゼータ電位を求めることができる。ゼータ電位測定の結果、マイナスに荷電し、−６４ｍＶと絶対値が大きく分散性が良好であることを確認した。
(Preparation of cerium oxide slurry)
1 kg of the cerium oxide particles prepared above, 23 g of an aqueous polyacrylic acid ammonium salt solution (40% by weight), and 8977 g of deionized water were mixed and subjected to ultrasonic dispersion for 10 minutes while stirring. The resulting slurry was filtered through a 2 micron filter and deionized water was added to add 3 wt. % Abrasive was obtained. The slurry pH was 8.0. The particle size distribution of the slurry particles was examined using a laser diffraction method (measuring device: Microplus manufactured by Master Sizer, refractive index: 1.9285). The median value was 510 nm and the maximum particle size was 0% for particles having a particle size of 1430 nm or more. there were. To examine the dispersibility of the slurry and the charge of the slurry particles, the zeta potential of the slurry was examined. A cerium oxide slurry was placed in a measurement cell having platinum electrodes on both sides, and a voltage of 10 V was applied to both electrodes. When a voltage is applied, the charged slurry particles move to the side of the electrode having a pole opposite to the charge. By obtaining this moving speed, the zeta potential of the particles can be obtained. As a result of the zeta potential measurement, it was confirmed that it was negatively charged, had an absolute value of -64 mV and a large dispersibility.
（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Ｓｉ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３００ｇ／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：３重量％）を３５ｃｃ／ｍｉｎの速度で滴下しながら、定盤を３０ｒｐｍで２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７４０ｎｍ（研磨速度：３７０ｎｍ／ｍｉｎ．）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、光学顕微鏡を用いて絶縁膜表面を観察したところ、明確な傷は見られなかった。
(Polishing the insulating film layer)
A surface plate on which a Si wafer on which a SiO 2 insulating film produced by TEOS-plasma CVD method is formed is set in a holder on which a holding pad for attaching a substrate to be held is attached, and a polishing pad made of porous urethane resin is attached. A holder was placed thereon with the insulating film face down, and a weight was placed so that the processing load was 300 g / cm 2 . While the above cerium oxide slurry (solid content: 3% by weight) was dropped on the surface plate at a rate of 35 cc / min, the surface plate was rotated at 30 rpm for 2 minutes to polish the insulating film. After polishing, the wafer was removed from the holder, washed thoroughly with running water, and further washed with an ultrasonic cleaner for 20 minutes. After washing, 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. As a result of measuring the film thickness change before and after polishing using an optical interference type film thickness measuring apparatus, the insulating film having a thickness of 740 nm (polishing rate: 370 nm / min.) Was cut by this polishing, and the thickness was uniform over the entire surface of the wafer. I found out that Further, when the surface of the insulating film was observed using an optical microscope, no clear scratch was found.
実施例３
（酸化セリウム粒子の作製）
炭酸セリウム水和物２ｋｇを白金製容器に入れ、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約１ｋｇ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。焼成粉末粒子径は３０〜１００ミクロンであった。焼成粉末粒子表面を走査型電子顕微鏡で観察したところ、酸化セリウムの粒界が観察された。粒界に囲まれた酸化セリウム一次粒子径を測定したところ、その分布の中央値が１９０ｎｍ、最大値が５００ｎｍであった。焼成粉末についてＸ線回折精密測定を行い、その結果についてリートベルト法（ＲＩＥＴＡＮ−９４）による解析で、一次粒子径を表わす構造パラメータ−：Ｘの値が０．０８０、等方的微少歪みを表わす構造パラメータ−：Ｙの値が０．２２３であった。酸化セリウム粉末１ｋｇをビーズミルを用いて湿式粉砕を行った。粉砕粒子を含む液を乾燥し、乾燥粒子をボールミル粉砕を行った。粉砕粒子について走査型電子顕微鏡で観察したところ、一次粒子径と同等サイズの粒子まで粉砕されており、大きな粉砕残りは見られなかった。粉砕粒子についてＸ線回折精密測定を行い、その結果についてリートベルト法（ＲＩＥＴＡＮ−９４）による解析で、一次粒子径を表わす構造パラメータ−：Ｘの値が０．０８５、等方的微少歪みを表わす構造パラメータ−：Ｙの値が０．３００であった。この結果、粉砕による一次粒子径変量はほとんどなく、また粉砕により粒子に歪みが導入されていた。さらにＢＥＴ法による比表面積測定の結果、１０ｍ２／ｇであることがわかった。
Example 3
(Production of cerium oxide particles)
About 1 kg of yellowish white powder was obtained by putting 2 kg of cerium carbonate hydrate into a platinum container and firing in air at 800 ° C. for 2 hours. When this powder was phase-identified by X-ray diffraction, it was confirmed to be cerium oxide. The calcined powder particle size was 30-100 microns. When the surface of the fired powder particles was observed with a scanning electron microscope, grain boundaries of cerium oxide were observed. When the primary particle diameter of cerium oxide surrounded by the grain boundaries was measured, the median value of the distribution was 190 nm and the maximum value was 500 nm. The X-ray diffraction precision measurement is performed on the calcined powder, and the result is analyzed by the Rietveld method (RIETAN-94). The structural parameter indicating the primary particle diameter: X value is 0.080, and isotropic isometric strain Structure parameter-: The value of Y was 0.223. 1 kg of cerium oxide powder was wet-ground using a bead mill. The liquid containing the pulverized particles was dried, and the dried particles were ball milled. Observation of the pulverized particles with a scanning electron microscope revealed that the pulverized particles were pulverized to the same size as the primary particle size, and no large pulverized residue was observed. The X-ray diffraction precision measurement is performed on the pulverized particles, and the result is analyzed by the Rietveld method (RIETAN-94). The structural parameter indicating the primary particle diameter: the value of X is 0.085, and isotropic strain is expressed. Structure parameter-: Y value was 0.300. As a result, there was almost no change in the primary particle size due to pulverization, and distortion was introduced into the particles due to pulverization. Furthermore, as a result of measuring the specific surface area by the BET method, it was found to be 10 m 2 / g.
（酸化セリウムスラリーの作製）
上記作製の酸化セリウム粒子１ｋｇとポリアクリル酸アンモニウム塩水溶液（４０重量％）２３ｇと脱イオン水８９７７ｇを混合し、攪拌しながら超音波分散を１０分間施した。得られたスラリーを１ミクロンフィルターでろ過をし、さらに脱イオン水を加えることにより３ｗｔ．％研磨剤を得た。スラリーｐＨは８．３であった。スラリー粒子の粒度分布をレーザー回折法（測定装置：ＭａｓｔｅｒＳｉｚｅｒ製ｍｉｃｒｏｐｌｕｓ、屈折率：１．９２８５）を用いて調べたところ、中央値が２９０ｎｍで、最大粒子径は７８０ｎｍ以上の粒子が０％であった。スラリーの分散性およびスラリー粒子の電荷を調べるため、スラリーのゼータ電位を調べた。両側に白金製電極を取り付けてある測定セルに酸化セリウムスラリーを入れ、両電極に１０Ｖの電圧を印加した。電圧を印加することにより電荷を持ったスラリー粒子はその電荷と反対の極を持つ電極側に移動する。この移動速度を求めることにより粒子のゼータ電位を求めることができる。ゼータ電位測定の結果、マイナスに荷電し、−５０ｍＶと絶対値が大きく分散性が良好であることを確認した。
(Preparation of cerium oxide slurry)
1 kg of the cerium oxide particles prepared above, 23 g of an aqueous polyacrylic acid ammonium salt solution (40% by weight), and 8977 g of deionized water were mixed and subjected to ultrasonic dispersion for 10 minutes while stirring. The resulting slurry was filtered through a 1 micron filter and further deionized water was added to add 3 wt. % Abrasive was obtained. The slurry pH was 8.3. When the particle size distribution of the slurry particles was examined using a laser diffraction method (measuring device: Microplus manufactured by MasterSizer, refractive index: 1.9285), the median value was 290 nm, and the maximum particle size was 0% for particles having a particle size of 780 nm or more. It was. To examine the dispersibility of the slurry and the charge of the slurry particles, the zeta potential of the slurry was examined. A cerium oxide slurry was placed in a measurement cell having platinum electrodes on both sides, and a voltage of 10 V was applied to both electrodes. When a voltage is applied, the charged slurry particles move to the side of the electrode having a pole opposite to the charge. By obtaining this moving speed, the zeta potential of the particles can be obtained. As a result of the zeta potential measurement, it was confirmed that it was negatively charged, had an absolute value of −50 mV and a large dispersibility.
（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Ｓｉ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３００ｇ／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：３重量％）を３５ｃｃ／ｍｉｎの速度で滴下しながら、定盤を３０ｒｐｍで２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５６０ｎｍ（研磨速度：２８０ｎｍ／ｍｉｎ．）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、光学顕微鏡を用いて絶縁膜表面を観察したところ、明確な傷は見られなかった。
(Polishing the insulating film layer)
A surface plate on which a Si wafer on which a SiO 2 insulating film produced by TEOS-plasma CVD method is formed is set in a holder on which a holding pad for attaching a substrate to be held is attached, and a polishing pad made of porous urethane resin is attached. A holder was placed thereon with the insulating film face down, and a weight was placed so that the processing load was 300 g / cm 2 . While the above cerium oxide slurry (solid content: 3% by weight) was dropped on the surface plate at a rate of 35 cc / min, the surface plate was rotated at 30 rpm for 2 minutes to polish the insulating film. After polishing, the wafer was removed from the holder, washed thoroughly with running water, and further washed with an ultrasonic cleaner for 20 minutes. After washing, 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. As a result of measuring the film thickness change before and after polishing using an optical interference type film thickness measuring device, an insulating film of 560 nm (polishing rate: 280 nm / min.) Was shaved by this polishing, and the thickness was uniform over the entire wafer surface. I found out that Further, when the surface of the insulating film was observed using an optical microscope, no clear scratch was found.
実施例４
（酸化セリウム粒子の作製）
炭酸セリウム水和物２ｋｇを白金製容器に入れ、７００℃で２時間空気中で焼成することにより黄白色の粉末を約１ｋｇ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。焼成粉末粒子径は３０〜１００ミクロンであった。焼成粉末粒子表面を走査型電子顕微鏡で観察したところ、酸化セリウムの粒界が観察された。粒界に囲まれた酸化セリウム一次粒子径を測定したところ、その分布の中央値が５０ｎｍ、最大値が１００ｎｍであった。焼成粉末についてＸ線回折精密測定を行い、その結果についてリートベルト法（ＲＩＥＴＡＮ−９４）による解析で、一次粒子径を表わす構造パラメータ−：Ｘの値が０．３００、等方的微少歪みを表わす構造パラメータ−：Ｙの値が０．３５０であった。酸化セリウム粉末１ｋｇをビーズミルを用いて湿式粉砕を行った。粉砕粒子を含む液を乾燥し、乾燥粒子をボールミル粉砕を行った。粉砕粒子について走査型電子顕微鏡で観察したところ、一次粒子径と同等サイズの粒子まで粉砕されており、大きな粉砕残りは見られなかった。粉砕粒子についてＸ線回折精密測定を行い、その結果についてリートベルト法（ＲＩＥＴＡＮ−９４）による解析で、一次粒子径を表わす構造パラメータ−：Ｘの値が０．３０２、等方的微少歪みを表わす構造パラメータ−：Ｙの値が０．４５０であった。この結果、粉砕による一次粒子径変量はほとんどなく、また粉砕により粒子に歪みが導入されていた。さらにＢＥＴ法による比表面積測定の結果、４０ｍ２／ｇであることがわかった。
Example 4
(Production of cerium oxide particles)
About 1 kg of yellowish white powder was obtained by putting 2 kg of cerium carbonate hydrate in a platinum container and firing in air at 700 ° C. for 2 hours. When this powder was phase-identified by X-ray diffraction, it was confirmed to be cerium oxide. The calcined powder particle size was 30-100 microns. When the surface of the fired powder particles was observed with a scanning electron microscope, grain boundaries of cerium oxide were observed. When the primary particle diameter of cerium oxide surrounded by the grain boundaries was measured, the median value of the distribution was 50 nm, and the maximum value was 100 nm. The X-ray diffraction precision measurement is performed on the calcined powder, and the result is analyzed by the Rietveld method (RIETAN-94). The structural parameter representing the primary particle diameter: X value is 0.300, representing isotropic strain Structure parameter-: The value of Y was 0.350. 1 kg of cerium oxide powder was wet-ground using a bead mill. The liquid containing the pulverized particles was dried, and the dried particles were ball milled. Observation of the pulverized particles with a scanning electron microscope revealed that the pulverized particles were pulverized to the same size as the primary particle size, and no large pulverized residue was observed. The X-ray diffraction precision measurement is performed on the pulverized particles, and the result is analyzed by the Rietveld method (RIETAN-94). The structural parameter representing the primary particle diameter: X value is 0.302, and isotropic isometric strain is represented. Structure parameter-: The value of Y was 0.450. As a result, there was almost no change in the primary particle size due to pulverization, and distortion was introduced into the particles due to pulverization. Furthermore, as a result of measuring the specific surface area by the BET method, it was found to be 40 m 2 / g.
（酸化セリウムスラリーの作製）
上記作製の酸化セリウム粒子１ｋｇとポリアクリル酸アンモニウム塩水溶液（４０重量％）２３ｇと脱イオン水８９７７ｇを混合し、攪拌しながら超音波分散を１０分間施した。得られたスラリーを１ミクロンフィルターでろ過をし、さらに脱イオン水を加えることにより３ｗｔ．％研磨剤を得た。スラリーｐＨは８．５であった。スラリー粒子の粒度分布をレーザー回折法（測定装置：ＭａｓｔｅｒＳｉｚｅｒ製ｍｉｃｒｏｐｌｕｓ、屈折率：１．９２８５）を用いて調べたところ、中央値が２９０ｎｍで、最大粒子径は７８０ｎｍ以上の粒子が０％であった。スラリーの分散性およびスラリー粒子の電荷を調べるため、スラリーのゼータ電位を調べた。両側に白金製電極を取り付けてある測定セルに酸化セリウムスラリーを入れ、両電極に１０Ｖの電圧を印加した。電圧を印加することにより電荷を持ったスラリー粒子はその電荷と反対の極を持つ電極側に移動する。この移動速度を求めることにより粒子のゼータ電位を求めることができる。ゼータ電位測定の結果、マイナスに荷電し、−６５ｍＶと絶対値が大きく分散性が良好であることを確認した。
(Preparation of cerium oxide slurry)
1 kg of the cerium oxide particles prepared above, 23 g of an aqueous polyacrylic acid ammonium salt solution (40% by weight), and 8977 g of deionized water were mixed and subjected to ultrasonic dispersion for 10 minutes while stirring. The resulting slurry was filtered through a 1 micron filter and further deionized water was added to add 3 wt. % Abrasive was obtained. The slurry pH was 8.5. When the particle size distribution of the slurry particles was examined using a laser diffraction method (measuring device: Microplus manufactured by MasterSizer, refractive index: 1.9285), the median value was 290 nm, and the maximum particle size was 0% for particles having a particle size of 780 nm or more. It was. To examine the dispersibility of the slurry and the charge of the slurry particles, the zeta potential of the slurry was examined. A cerium oxide slurry was placed in a measurement cell having platinum electrodes on both sides, and a voltage of 10 V was applied to both electrodes. When a voltage is applied, the charged slurry particles move to the side of the electrode having a pole opposite to the charge. By obtaining this moving speed, the zeta potential of the particles can be obtained. As a result of the zeta potential measurement, it was confirmed that it was negatively charged and had a large absolute value of -65 mV and good dispersibility.
（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Ｓｉ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３００ｇ／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：３重量％）を３５ｃｃ／ｍｉｎの速度で滴下しながら、定盤を３０ｒｐｍで２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４００ｎｍ（研磨速度：２００ｎｍ／ｍｉｎ．）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、光学顕微鏡を用いて絶縁膜表面を観察したところ、明確な傷は見られなかった。
(Polishing the insulating film layer)
A surface plate on which a Si wafer on which a SiO 2 insulating film produced by TEOS-plasma CVD method is formed is set in a holder on which a holding pad for attaching a substrate to be held is attached, and a polishing pad made of porous urethane resin is attached. A holder was placed thereon with the insulating film face down, and a weight was placed so that the processing load was 300 g / cm 2 . While the above cerium oxide slurry (solid content: 3% by weight) was dropped on the surface plate at a rate of 35 cc / min, the surface plate was rotated at 30 rpm for 2 minutes to polish the insulating film. After polishing, the wafer was removed from the holder, washed thoroughly with running water, and further washed with an ultrasonic cleaner for 20 minutes. After washing, 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. As a result of measuring the film thickness change before and after polishing using an optical interference type film thickness measuring apparatus, the insulating film having a thickness of 400 nm (polishing rate: 200 nm / min.) Was cut by this polishing, and the thickness was uniform over the entire surface of the wafer. I found out that Further, when the surface of the insulating film was observed using an optical microscope, no clear scratch was found.
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、２分間の研磨により１５０ｎｍ（研磨速度：７５ｎｍ／ｍｉｎ．）の絶縁膜層しか削れなかった。
For Si wafer having formed an SiO 2 insulating film was prepared in the same manner as in Comparative Example Example in TEOS-CVD method, it was polished using a commercially available silica slurry (manufactured by Cabot Corporation, trade name SS225). In this pH commercial slurry 10.3 are those containing a SiO 2 particles 12.5 wt%. The polishing conditions are the same as in the example. As a result, scratches due to polishing were not observed, and polishing was performed uniformly, but only an insulating film layer having a thickness of 150 nm (polishing rate: 75 nm / min.) Was removed by polishing for 2 minutes.
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| JP2006246046A JP5023626B2 (en) | 1996-09-30 | 2006-09-11 | Polishing method of cerium oxide slurry and substrate |
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| JP1996258774 | 1996-09-30 | ||
| JP2006246046A JP5023626B2 (en) | 1996-09-30 | 2006-09-11 | Polishing method of cerium oxide slurry and substrate |
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| JP2001103923A Withdrawn JP2001329251A (en) | 1996-09-30 | 2001-04-02 | Cerium oxide abrasive and polishing method for substrate |
| JP2001103920A Withdrawn JP2001329250A (en) | 1996-09-30 | 2001-04-02 | Cerium oxide abrasive and polishing method for substrate |
| JP2001275530A Withdrawn JP2002138275A (en) | 1996-09-30 | 2001-09-11 | Cerium oxide abrasive agent and method for abrading base |
| JP2006246039A Expired - Lifetime JP4971731B2 (en) | 1996-09-30 | 2006-09-11 | Polishing method of cerium oxide slurry and substrate |
| JP2006246046A Expired - Lifetime JP5023626B2 (en) | 1996-09-30 | 2006-09-11 | Polishing method of cerium oxide slurry and substrate |
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| JP2001103923A Withdrawn JP2001329251A (en) | 1996-09-30 | 2001-04-02 | Cerium oxide abrasive and polishing method for substrate |
| JP2001103920A Withdrawn JP2001329250A (en) | 1996-09-30 | 2001-04-02 | Cerium oxide abrasive and polishing method for substrate |
| JP2001275530A Withdrawn JP2002138275A (en) | 1996-09-30 | 2001-09-11 | Cerium oxide abrasive agent and method for abrading base |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2012169648A (en) | 2012-09-06 |
| JP3462052B2 (en) | 2003-11-05 |
| JP2001329250A (en) | 2001-11-27 |
| JPH10152673A (en) | 1998-06-09 |
| JP5023626B2 (en) | 2012-09-12 |
| JP2002138275A (en) | 2002-05-14 |
| JP4971731B2 (en) | 2012-07-11 |
| JP2001329251A (en) | 2001-11-27 |
| JP2007036270A (en) | 2007-02-08 |
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