JP2005268799A - Cerium oxide slurry for polishing semiconductor thin film - Google Patents
Cerium oxide slurry for polishing semiconductor thin film Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- Mechanical Treatment Of Semiconductor (AREA)
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Abstract
Description
本発明は、半導体薄膜研磨用酸化セリウムスラリーに関し、特に遠心分離によるスラリー濃度試験における重量変化が２０％以下であって、高い研磨速度と優れたスクラッチ特性を有する酸化セリウムスラリーに関する。 The present invention relates to a cerium oxide slurry for polishing a semiconductor thin film, and more particularly to a cerium oxide slurry having a high polishing rate and excellent scratch characteristics, with a weight change of 20% or less in a slurry concentration test by centrifugation.
半導体の化学的機械研磨（ＣＭＰ）の用途には、主に酸化セリウムを水中懸濁液に分散させてスラリー化した後使用しているが、これまでは高い研磨速度を有することを酸化セリウムスラリーの主な目的としてきた。しかし、最近、半導体工程の配線が次第に微細化され、チップ間の間隔が減少するにつれ、化学的機械研磨用スラリーは研磨速度以外にもスクラッチ発生の防止、及び発生したスクラッチのサイズ減少の特性が要求されている。 For chemical mechanical polishing (CMP) of semiconductors, cerium oxide is mainly used after being dispersed in a suspension in water and slurried. Has been the main purpose of. However, recently, as the wiring of semiconductor processes is gradually miniaturized and the distance between chips decreases, the slurry for chemical mechanical polishing has the characteristics of preventing the generation of scratches and reducing the size of the generated scratches in addition to the polishing rate. It is requested.
従来の化学的機械研磨用スラリーに用いられた酸化セリウムは比重が高いため、長時間保管した場合大部分の粒子が沈み、再分散の際、粒子が凝集し、スクラッチの原因となっている。したがって、分散安定性を有するスラリーを製造するために多くの努力を注いでおり、研磨粒子に合う界面活性剤の適用と分散機の開発によって分散安定性は相当改善されている。 Since cerium oxide used in conventional chemical mechanical polishing slurries has a high specific gravity, most of the particles sink when stored for a long time, and when redispersed, the particles aggregate and cause scratches. Therefore, much effort has been put into producing a slurry having dispersion stability, and the dispersion stability has been considerably improved by the application of a surfactant suitable for abrasive particles and the development of a disperser.
近来では、研磨後の不良製品発生は主にスクラッチによるもので、特にスラリー中に微量存在する大きい粒子がその原因であることが明らかにされている。このようなスクラッチを減少させるための努力として、特許文献１は、凝集した粒子の粒径を３ミクロン以下に保持しているが、これもまた実際０．１６μｍ以下の微細パターンではスクラッチによって収率が著しく落ちるという問題が生じる。これは、実際ウエハ表面にスクラッチを発生させる粒子が７００ｎｍ以上、特に１μｍ以上の粒子であるためである。 In recent years, it has been clarified that the generation of defective products after polishing is mainly caused by scratches, and in particular, large particles present in a minute amount in the slurry. As an effort to reduce such scratches, Patent Document 1 keeps the particle size of aggregated particles at 3 microns or less, and this also yields yields by scratching in fine patterns of 0.16 μm or less. The problem arises that the sag drops significantly. This is because the particles that generate scratches on the wafer surface are actually 700 nm or more, particularly 1 μm or more.
また、近来、半導体の製造において線幅が大幅に減少し、従来に比べて一枚のウエハから生産されるチップの数が増加したが、このような線幅が減少したパターンを有する半導体チップの製造工程に従来のスラリーをそのまま用いる場合、マイクロサイズのスクラッチも致命的に作用するので、生産量を高めるのには限界がある。さらに、半導体製造工程に化学的機械研磨工程を適用する場合が次第に増加する趨勢であるので、このような研磨工程後のスクラッチの有無およびサイズはウエハ内のチップの収率と密接な関係がある。 In recent years, the line width has been greatly reduced in the manufacture of semiconductors, and the number of chips produced from a single wafer has increased compared to the prior art. When the conventional slurry is used as it is in the production process, micro-sized scratches also act fatally, so there is a limit to increasing the production amount. In addition, since the chemical mechanical polishing process is increasingly applied to the semiconductor manufacturing process, the presence and size of scratches after the polishing process are closely related to the yield of chips in the wafer. .
したがって、スクラッチの発生と直接関連のある大きい粒子の除去はさらに重要な技術であると言えるが、このようにスクラッチを減少させるためにスラリーの平均粒径を減らす場合、研磨速度の減少によって生産量が減少するという問題が生じる。たとえば、特許文献２は、スクラッチを減少させるために０．５６μｍ以上の研磨粒子量を制御しているが、実際使用したスラリーは平均粒径が３０〜８８ｎｍと非常に小さいため、実際の研磨工程に使用した場合、研磨速度の減少および研磨後のウエハの平坦度にも問題を引き起し得るため、実効性が低い。
したがって、本発明の目的は、研磨速度を減少させることなく、大きい粒子を効率よく除去し、スクラッチの低減はもちろん、発生するスクラッチのサイズを小さくすることによりスクラッチによる不良率を最小化できる酸化セリウムスラリーを提供することである。 Accordingly, an object of the present invention is to remove cerium oxide efficiently by removing large particles efficiently without reducing the polishing rate, and by reducing the size of the generated scratch as well as by reducing the size of the generated scratch. Providing a slurry.
前記目的を達成するために、本発明は、平均粒径が０．１〜０．２μｍ範囲の酸化セリウム粉末を含み、下記式（１）を満足する、半導体薄膜研磨用酸化セリウムスラリーを提供する。 In order to achieve the above object, the present invention provides a cerium oxide slurry for polishing a semiconductor thin film, which contains cerium oxide powder having an average particle size in the range of 0.1 to 0.2 μm and satisfies the following formula (1). .
（Ｃ０−Ｃ１）／Ｃ０×１００≦２０ ・・・（１）
（式中、Ｃ０は、原スラリーの固形分濃度であり、Ｃ１は、スラリーが受ける平均遠心力ｇが１９７０ｇ０である条件で２分間遠心分離した後の固形分濃度であり、ｇ０は重力加速度である。）
(C 0 -C 1 ) / C 0 × 100 ≦ 20 (1)
(Wherein, C 0 is the solids concentration of the starting slurry, C 1 is the solid content concentration after the average centrifugal force g of the slurry is subjected is centrifuged for 2 minutes at a 1970g 0, g 0 Is gravitational acceleration.)
本発明に係る、所定の条件で遠心分離によるスラリー濃度減少（ＣＳＬ）試験における重量％の濃度変化が２０％以下である酸化セリウムスラリーは、化学的機械研磨の際、発生するスクラッチ数が顕著に少なく、サイズが小さく、また、貯蔵容器の底に沈む粒子がほとんどないため、粒子間の凝集が発生しないので、長期間保管後に使用してもスクラッチ数が増加しないなどの優れた性能を示す。 In the cerium oxide slurry according to the present invention, in which the concentration change of weight% in a slurry concentration reduction (CSL) test by centrifugation under a predetermined condition is 20% or less, the number of scratches generated during chemical mechanical polishing is remarkable. It is small, small in size, and has few particles that sink to the bottom of the storage container, so that no aggregation occurs between the particles. Therefore, it exhibits excellent performance such that the number of scratches does not increase even after use for a long period of storage.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明のスラリーは、前記式（１）を満足する、特定の条件での遠心分離時、重量変化が２０％以下であることを特徴とし、粒度分析機（laser scattering particle size distribution analyzer）での測定時、平均粒径（mean volume size）が０．１〜０．２μｍ範囲であり、Ｄ１００（粒度分布機で測定時、分布累積値が１００となる粒径）が約０．５〜０．７μｍ範囲である。 The slurry of the present invention satisfies the above formula (1) and has a weight change of 20% or less upon centrifugation under specific conditions. At the time of measurement, the average particle size (mean volume size) is in the range of 0.1 to 0.2 μm, and D 100 (the particle size at which the cumulative distribution value becomes 100 when measured with a particle size distribution machine) is about 0.5 to 0. .7 μm range.
通常の分散工程、たとえば、対抗衝突機または超音波機を通過させるか、ウェットミリング工程を経た酸化セリウムスラリーは、大部分の粒子が数十マイクロから数百ナノサイズの粒子に粉砕されて水中に均一に分散するが、これまではこのように分散機を通過させて分散されたスラリーをそのまま使用するか、フィルターを用いて粉砕されていない大きい粒子を濾過した後用いる程度であった。しかし、半導体配線の幅が０．１６μｍ以下となるに伴い、スクラッチは半導体ウエハの収率を低下させる最も大きな原因となり、この直接の原因は０．７μｍ以上の大きい粒子の存在であるという事実が明らかになった。一方、従来のスラリーの場合、酸化セリウムスラリーの粒径分布の平均粒径は３５０ｎｍ前後であり、１μｍ以上の大きい粒子も少量存在し、このような大きい粒子はスラリー中に極微量存在してもＣＭＰ工程において薄膜に多数のスクラッチを発生させ、発生したスクラッチのサイズや深さが大きすぎるため、収率に致命的な影響を及ぼす。しかし、前記条件を満足する本発明に係るスラリーは、長期間保管しても容器の底に沈む固形分量が少ないため、酸化セリウム粒子間の凝集を防止できるので、安定性も大きく向上でき、したがって、長期間保管後に使用してもスクラッチの数が増加しない。 The cerium oxide slurry that has been passed through a normal dispersion process, for example, an anti-collision machine or an ultrasonic machine, or that has undergone a wet milling process, is pulverized into particles of tens of micrometers to hundreds of nanosizes in water. Although it is uniformly dispersed, until now, the slurry dispersed through the disperser in this way is used as it is, or it is only used after filtering large particles that have not been pulverized using a filter. However, as the width of the semiconductor wiring becomes 0.16 μm or less, scratches are the biggest cause of reducing the yield of the semiconductor wafer, and the direct cause is the presence of large particles of 0.7 μm or more. It was revealed. On the other hand, in the case of a conventional slurry, the average particle size distribution of the cerium oxide slurry is around 350 nm, and there are a small amount of large particles of 1 μm or more. Even if such large particles exist in a very small amount in the slurry. A large number of scratches are generated in the thin film in the CMP process, and the size and depth of the generated scratches are too large, which has a fatal effect on the yield. However, since the slurry according to the present invention that satisfies the above conditions has a small solid content that sinks to the bottom of the container even if stored for a long period of time, it can prevent agglomeration between the cerium oxide particles, so that the stability can be greatly improved, and therefore The number of scratches does not increase even when used after long-term storage.
本発明に係る酸化セリウムスラリーは、酸化セリウム粉末を水に分散させて得られたスラリーを遠心分離工程および任意に追加のフィルタリング工程を経て得られる。 The cerium oxide slurry according to the present invention is obtained by subjecting a slurry obtained by dispersing cerium oxide powder in water to a centrifugal separation step and optionally an additional filtering step.
具体的に、本発明に係る酸化セリウムスラリーの製造に用いられる酸化セリウム粉末は、その製造方法に特に制限はなく、通常の方法で製造できる。たとえば、炭酸セリウム、水酸化セリウム、窒化セリウム、塩化セリウム、酢酸セリウムなどの原料を６５０〜９００℃で焼成し、酸化させて酸化セリウムを得た後、これをウェットミル、ドライミルなどを用いて粉砕することによって得られ、１０〜１００ｎｍ範囲の平均サイズを有する。前記焼成工程およびミリング工程は順序を変えて行うこともできる。 Specifically, the production method of the cerium oxide powder used for producing the cerium oxide slurry according to the present invention is not particularly limited, and can be produced by a usual method. For example, raw materials such as cerium carbonate, cerium hydroxide, cerium nitride, cerium chloride, cerium acetate are fired at 650 to 900 ° C. and oxidized to obtain cerium oxide, which is then pulverized using a wet mill, dry mill, etc. And has an average size in the range of 10-100 nm. The firing process and milling process may be performed in different order.
このようにして製造された酸化セリウム粉末を水に入れて分散させるが、この際、分散を容易にするための酸化セリウムの濃度は０．５〜２０重量％の範囲が好ましい。分散工程も特に制限されず、対抗衝突方式、超音波方式、ウェットミル方式などを用いることができる。 The cerium oxide powder produced in this manner is dispersed in water. At this time, the concentration of cerium oxide for facilitating dispersion is preferably in the range of 0.5 to 20% by weight. The dispersion process is not particularly limited, and a counter collision method, an ultrasonic method, a wet mill method, or the like can be used.
前記分散の際、分散を容易にするために分散剤を使用でき、分散剤は酸化セリウムが水中で帯びる表面電位値を考慮して選択することが好ましいが、特に制限されない。酸化セリウムの分散は通常ｐＨ４〜９の範囲で行われ、この際、酸化セリウムの表面電位値はプラスの値を有するので、陰イオン性有機化合物が好ましく用いられ、その具体的な例としては、ポリアクリル酸、ポリビニル硫酸、ポリメタクリル酸、ポリアクリルアミド、ポリアリールアミンなどがある。前記分散剤は重量平均分子量が１，０００以上５０，０００以下のものが好ましく、分子量が１，０００未満の場合は酸化セリウムスラリーの分散安定性を確保することが難しく、５０，０００を超える場合はスラリーの粘度が増加するため、長期安定性を確保することが難しい。 In the dispersion, a dispersing agent can be used for facilitating dispersion, and the dispersing agent is preferably selected in consideration of the surface potential value that cerium oxide is charged in water, but is not particularly limited. Dispersion of cerium oxide is usually carried out in the range of pH 4 to 9, and at this time, since the surface potential value of cerium oxide has a positive value, an anionic organic compound is preferably used. Examples include polyacrylic acid, polyvinyl sulfate, polymethacrylic acid, polyacrylamide, and polyarylamine. The dispersant preferably has a weight average molecular weight of 1,000 or more and 50,000 or less. When the molecular weight is less than 1,000, it is difficult to ensure the dispersion stability of the cerium oxide slurry, and the dispersing agent exceeds 50,000. Since the viscosity of the slurry increases, it is difficult to ensure long-term stability.
前述のように分散処理された酸化セリウムスラリーに対してスラリー中に存在する大きい粒子を除去するため、本発明では遠心分離機を用いて粒径が０．７μｍ以上である大きい粒子を強制的に遠心分離することによって除去する。たとえば、数千ｒｐｍ、好ましくは１，０００〜５，０００ｒｐｍで回転する円筒にスラリーを通過させることによって円筒の内壁にスラリー中の大きい粒子を付着させて除去できる。スラリーが一定流速で円筒の内部を通過することになると、大きい粒子の場合、遠心力が大きく作用して機壁に付着し、サイズが小さい粒子は円筒を通過するようになる。 In order to remove the large particles existing in the slurry from the cerium oxide slurry dispersed as described above, the present invention forcibly uses a centrifuge to force large particles having a particle size of 0.7 μm or more. Remove by centrifugation. For example, by passing the slurry through a cylinder rotating at several thousand rpm, preferably 1,000 to 5,000 rpm, large particles in the slurry can be adhered and removed from the inner wall of the cylinder. When the slurry passes through the inside of the cylinder at a constant flow rate, in the case of large particles, the centrifugal force acts greatly and adheres to the machine wall, and the particles having a small size pass through the cylinder.
前記のように遠心分離工程により大きい粒子を除去したセリアスラリーは、本発明に従って、スラリーが受ける平均遠心力が１９７０ｇ０（ｇ０＝重力加速度；９．８ｍ／ｓｅｃ２）である条件で２分間回転させて粒子を強制沈降させた後試験前後の重量を比較する試験（「遠心分離スラリー濃度減少試験」）を行う場合、２０重量％以下、好ましくは１０重量％以下のスラリー濃度（すなわち、固形分）の減少を示す。 Ceria slurry to remove larger particles in the centrifugal separation step as described above, in accordance with the present invention, the average centrifugal force the slurry is subjected is 1970g 0 (g 0 = gravitational acceleration; 9.8 m / sec 2) at a condition in 2 min When performing a test to compare the weight before and after the test after the particles are forced to settle by rotation (“centrifugal slurry reduction test”), the slurry concentration is 20 wt% or less, preferably 10 wt% or less (that is, solids) Min) decrease.
通常の粒度分析機を用いて分析する場合、１％以下の量で存在する大きい粒子に関する情報を得ることは難しい反面、本発明に係る遠心分離スラリー濃度減少試験法は平均粒径が同じスラリーにおける大きい粒子含量を区別できる方法であると言える。 When analyzing using a normal particle size analyzer, it is difficult to obtain information on large particles present in an amount of 1% or less, but the centrifugal slurry concentration reduction test method according to the present invention is used in a slurry having the same average particle size. It can be said that this method can distinguish large particle content.
このようにして製造された本発明のスラリーは既に大きい粒子の大部分が除去されたものであって、化学的機械研磨工程に研磨剤完成品として使用する場合、研磨性能に優れていながらも、従来の分散機のみを用いたスラリーと比較して高いスクラッチ低減効果が得られる。すなわち、本発明に係るセリアスラリーは大きい粒子のみが除去されるだけで、平均粒径は０．１〜０．２μｍ範囲に保持されるので、従来の工程通り研磨を行う場合、研磨生産性は保持しながら９０％以上のスクラッチ低減効果が得られる。 The slurry of the present invention produced in this way has already had most of the large particles removed, and when used as a finished abrasive product in a chemical mechanical polishing process, while having excellent polishing performance, A high scratch reduction effect is obtained as compared with a slurry using only a conventional disperser. That is, since the ceria slurry according to the present invention only removes large particles and the average particle size is maintained in the range of 0.1 to 0.2 μm, when polishing is performed according to the conventional process, the polishing productivity is A scratch reduction effect of 90% or more can be obtained while holding.
本発明に係るスラリーは、スラリーの製造過程において、上述のように大きい粒子を除去するための遠心分離工程を経た後必要に応じてフィルタリング工程を経て製造してもよい。 The slurry according to the present invention may be manufactured through a filtering step as necessary after passing through a centrifugal separation step for removing large particles as described above in the manufacturing process of the slurry.
本発明に係る酸化セリウムスラリーは０．１６μｍ以下の微細パターン用半導体薄膜の研磨だけでなく、従来のシリカスラリーで研磨されていた半導体層間絶縁膜層（ＩＬＤ層）とＳＴＩ（shallow trench isolation）のＣＭＰ研磨にも適用が可能であり、長期間保管しても沈む粒子の量が少ないため、長期安定性もまた非常に優れている。 The cerium oxide slurry according to the present invention not only polishes a semiconductor thin film for fine patterns of 0.16 μm or less, but also includes a semiconductor interlayer insulating film layer (ILD layer) and an STI (shallow trench isolation) polished with a conventional silica slurry. It can also be applied to CMP polishing, and since the amount of particles that sink even after long-term storage is small, long-term stability is also very good.
（実施例）
以下、本発明を下記実施例によってさらに詳細に説明する。ただし、これらは本発明を例示するためのものであり、本発明の範囲を制限しない。
(Example)
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these are for illustrating the present invention and do not limit the scope of the present invention.
（製造例１）酸化セリウム粉末の調製
水酸化セリウムを７５０℃で熱処理して酸化セリウムを得た後、これをボールミルで粉砕して平均粒径４０ｎｍ（ＸＲＤで測定）の酸化セリウムを得た。
Production Example 1 Preparation of Cerium Oxide Powder Cerium hydroxide was heat treated at 750 ° C. to obtain cerium oxide, which was then pulverized by a ball mill to obtain cerium oxide having an average particle size of 40 nm (measured by XRD).
（製造例２）被研磨膜の製造
８インチシリコンウエハ上に、ＴＥＯＳ（オルトケイ酸テトラエチル（tetraethyl orthosilicate)）を用いるＰＥ−ＣＶＤ（plasma enhanced-chemical vapor deposition）方式、すなわち、ＰＥ−ＴＥＯＳ工程によって１０，０００Åの厚さに二酸化ケイ素膜を成膜して被研磨膜を製造した。
(Manufacturing Example 2) Manufacturing of Polishing Film PE-CVD (plasma enhanced-chemical vapor deposition) method using TEOS (tetraethyl orthosilicate) on an 8-inch silicon wafer, that is, 10 by a PE-TEOS process. A silicon dioxide film having a thickness of 1,000 mm was formed to produce a film to be polished.
（製造例３）酸化セリウムスラリーの製造
製造例１で得られた酸化セリウム粉末８００ｇを脱イオン水９１６０ｇに加えた後、酸化セリウム粉末の調製時、凝集した粉末塊が水中に残らないようにプロペラ攪拌機を用いて３０分間攪拌した。分散剤であるポリアクリル酸（重量平均分子量３０００、濃度４０重量％）２０ｇを攪拌しながら加えた後、対抗衝突分散機を用いて２００ＭＰａの圧力で粒子を衝突させることにより、水中に均一に分散された８重量％濃度の酸化セリウムスラリーを得た。
Production Example 3 Production of Cerium Oxide Slurry After adding 800 g of the cerium oxide powder obtained in Production Example 1 to 9160 g of deionized water, a propeller is used so that no agglomerated powder lump remains in the water when preparing the cerium oxide powder. It stirred for 30 minutes using the stirrer. Disperse uniformly in water by adding 20 g of polyacrylic acid (weight average molecular weight 3000, concentration 40% by weight) as a dispersing agent while stirring, and then colliding the particles at a pressure of 200 MPa using a counter collision disperser. An 8 wt% concentration cerium oxide slurry was obtained.
酸化セリウム研磨スラリーの製造
（実施例１）
製造例３の酸化セリウムスラリーを１，５００ｒｐｍで回転する円筒状の遠心分離機の下段から注入して上段に排出する方式（この際、大きい粒子は遠心分離機の機壁に付着し、小さい粒子のみが遠心分離機の上段に排出される）により大きい粒子を除去した。その後、スラリーの濃度を測定した後、脱イオン水を加えて５ｗｔ％セリアスラリーを製造した。
Production of cerium oxide polishing slurry (Example 1)
A method in which the cerium oxide slurry of Production Example 3 is injected from the lower stage of a cylindrical centrifuge rotating at 1,500 rpm and discharged to the upper stage (at this time, large particles adhere to the wall of the centrifuge, and small particles Only the larger particles were removed). Then, after measuring the density | concentration of a slurry, deionized water was added and 5 wt% ceria slurry was manufactured.
（実施例２）
遠心分離機の回転速度が２，０００ｒｐｍであることを除いては、実施例１と同様な方法で行って５ｗｔ％セリアスラリーを製造した。
(Example 2)
A 5 wt% ceria slurry was produced in the same manner as in Example 1 except that the rotational speed of the centrifuge was 2,000 rpm.
（実施例３）
製造例３の酸化セリウムスラリーを１，５００ｒｐｍで遠心分離して大きい粒子を１次的に除去した後、１μｍサイズのフィルターを用いて濾過し、以降の工程は実施例１と同様な方法で行って５ｗｔ％セリアスラリーを製造した。
(Example 3)
The cerium oxide slurry of Production Example 3 was centrifuged at 1,500 rpm to primarily remove large particles, and then filtered using a 1 μm size filter. The subsequent steps were performed in the same manner as in Example 1. 5 wt% ceria slurry was produced.
（比較例１）
製造例３の酸化セリウムスラリーを遠心分離せず、脱イオン水のみを加えて５ｗｔ％セリアスラリーを製造した。
(Comparative Example 1)
The cerium oxide slurry of Production Example 3 was not centrifuged, and only deionized water was added to produce a 5 wt% ceria slurry.
（比較例２）
製造例３の酸化セリウムスラリーを遠心分離せず、直接３μｍサイズのフィルターに１０Ｌ／分の流速で濾過し、以降の工程は実施例１と同様な方法で行って５ｗｔ％セリアスラリーを製造した。
(Comparative Example 2)
The cerium oxide slurry of Production Example 3 was directly filtered through a 3 μm size filter at a flow rate of 10 L / min without centrifuging, and the subsequent steps were performed in the same manner as in Example 1 to produce a 5 wt% ceria slurry.
（比較例３）
水酸化セリウムを６５０℃で熱処理して酸化セリウムを得た後、これをボールミルで粉砕して平均粒径２５ｎｍ（ＸＲＤで測定）の酸化セリウム粉末を得た。これを製造例３および実施例１と同様な方法で行って５ｗｔ％セリアスラリーを製造した。
(Comparative Example 3)
Cerium hydroxide was heat-treated at 650 ° C. to obtain cerium oxide, which was then pulverized by a ball mill to obtain a cerium oxide powder having an average particle size of 25 nm (measured by XRD). This was performed in the same manner as in Production Example 3 and Example 1 to produce a 5 wt% ceria slurry.
（参照例）
実施例１による酸化セリウムスラリーに対してｒｐｍと時間を変えてＣＳＬ試験を行い、その結果を下記表１に示す。
The CSL test was performed on the cerium oxide slurry according to Example 1 while changing the rpm and time, and the results are shown in Table 1 below.
スラリー中の粒子の粒径測定
前記実施例１〜３および比較例１〜３のスラリーに対して、日本ホリバ（Horiba）社の粒度分析器ＬＡ９１０を用いて平均粒径を測定し、その結果を表２に示す。
Particle size measurement of particles in slurry The average particle size was measured using the particle size analyzer LA910 of Japan Horiba, Inc. for the slurry of Examples 1-3 and Comparative Examples 1-3, and the results were obtained. It shows in Table 2.
遠心分離による沈降濃度減少試験および大きい粒子含量試験
前記実施例１〜３および比較例１〜３のスラリーに対して、長期間保管した場合のスラリー保管容器の底に沈んで凝集する可能性がある粒子の含量を調べるために、チューブ型遠心分離機（Hanil Science Industrial MF80）を用いて強制沈降させて酸化セリウム固形分の濃度減少量を互いに比較した。試験は、高さ１１．５ｃｍ、体積５０ｍｌの遠心分離用試験管に５重量％酸化セリウムスラリー４０ｍｌを各々充填し、４，０００ｒｐｍで２分間回転（この際、試験管は水平状態となり、遠心分離機の回転中心側から試験管入口までの距離は２．５ｃｍ、試験管底面までの距離は１４ｃｍとなる。すなわち、スラリーが受ける遠心力は１９７０ｇ０となる。）させた後、試験管の底に沈んだ硬いケークを除いた上澄液を他の試験管に移した後、上澄液の濃度を測定することにより行い、前記式（１）のように計算して遠心分離による沈降濃度減少％（ＣＳＬ％）を求めた。減少％が少ないことが大きい粒子の濃度が低いことを意味する。この試験を通じて長期安定性を確認でき、大きい粒子の含有程度も確認できる。試験結果を表２に示す。
Sediment concentration reduction test by centrifugation and large particle content test The slurries of Examples 1 to 3 and Comparative Examples 1 to 3 may sink and agglomerate at the bottom of the slurry storage container when stored for a long time. In order to examine the content of the particles, forced precipitation was performed using a tube centrifuge (Hanil Science Industrial MF80), and the amount of decrease in the concentration of cerium oxide solids was compared with each other. In the test, a centrifuge test tube having a height of 11.5 cm and a volume of 50 ml was filled with 40 ml of 5 wt% cerium oxide slurry, and rotated at 4,000 rpm for 2 minutes (at this time, the test tube was in a horizontal state and centrifuged. The distance from the rotation center side of the machine to the test tube inlet is 2.5 cm, and the distance from the test tube bottom surface is 14 cm (that is, the centrifugal force applied to the slurry is 1970 g 0 ). After removing the hard cake submerged in the sample, transfer it to another test tube, measure the concentration of the supernatant, and reduce the sediment concentration by centrifugation as calculated by equation (1) above. % (CSL%) was determined. A small percentage reduction means a low concentration of large particles. Through this test, long-term stability can be confirmed, and the content of large particles can also be confirmed. The test results are shown in Table 2.
被研磨膜の研磨特性
実施例１〜３、および比較例１〜３で得られた各々の酸化セリウムスラリーを用いて、８インチ用のＣＭＰ研磨機であるミラー（Mirra）装置（米国ＡＭＡＴ社）で製造例２で得られた被研磨膜を３．５ｐｓｉの圧力で９０秒間研磨した。前記スラリーは１５０ｍｌ／ｍｉｎの速度で供給し、上定盤ウエハヘッド（wafer head）の回転速度は１０４ｒｐｍであり、下定盤の回転速度は１１０ｒｐｍであった。パッドとしては、米国ローデル（Rodel）社のIC1000/suba IV stacked padを用いた。
Polishing Characteristics of Film to be Polished Using each cerium oxide slurry obtained in Examples 1 to 3 and Comparative Examples 1 to 3, a mirror (Mirra) apparatus (AMAT Corp., USA) which is a CMP polishing machine for 8 inches The polished film obtained in Production Example 2 was polished for 90 seconds at a pressure of 3.5 psi. The slurry was supplied at a speed of 150 ml / min, the rotation speed of the upper surface plate wafer head was 104 rpm, and the rotation speed of the lower surface plate was 110 rpm. As the pad, IC1000 / suba IV stacked pad manufactured by Rodel, USA was used.
被研磨膜の研磨後、米国ＫＬＡ−Ｔｅｎｃｏ社のスクラッチ評価装備であるＡＩＴ−ＸＰを用いてサイズが０．１６μｍ以上になるスクラッチ数を測定し、また米国THERMA-WAVE社のTherma-wave Optiprobe 300 seriesを用いて研磨前後の膜厚で研磨速度を測定し、その結果を表２に示す。
前記表２から、本発明に係る酸化セリウムスラリーは、平均粒径０．１〜０．２μｍを保持し、研磨速度に優れていながらもＣＳＬ％が少ないため、長期安定性に優れており、半導体の研磨時に生成するスクラッチ数を著しく減少できることが分かる。 From Table 2 above, the cerium oxide slurry according to the present invention has an average particle size of 0.1 to 0.2 μm and has excellent polishing rate, but has low CSL%, and thus has excellent long-term stability. It can be seen that the number of scratches generated during polishing can be significantly reduced.
Claims (5)
（Ｃ０−Ｃ１）／Ｃ０×１００≦２０ ・・・（１）
（式中、Ｃ０は、原スラリーの固形分濃度であり、Ｃ１は、スラリーが受ける平均遠心力ｇが１９７０ｇ０である条件で２分間遠心分離した後の固形分濃度であり、ｇ０は重力加速度である。） A cerium oxide slurry for polishing a semiconductor thin film, which contains cerium oxide powder having an average particle size of 0.1 to 0.2 μm and satisfies the following formula (1).
(C 0 -C 1 ) / C 0 × 100 ≦ 20 (1)
(Wherein, C 0 is the solids concentration of the starting slurry, C 1 is the solid content concentration after the average centrifugal force g of the slurry is subjected is centrifuged for 2 minutes at a 1970g 0, g 0 Is gravitational acceleration.)
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| KR (1) | KR100588404B1 (en) |
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| JP2009524236A (en) * | 2006-01-25 | 2009-06-25 | エルジー・ケム・リミテッド | CMP slurry and semiconductor wafer polishing method using the same |
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| KR100864996B1 (en) * | 2004-09-28 | 2008-10-23 | 히다치 가세고교 가부시끼가이샤 | Cmp polishing compound and method for polishing substrate |
| KR101107524B1 (en) * | 2008-09-25 | 2012-01-31 | 솔브레인 주식회사 | A method for preparing aqueous cerium oxide dispersion |
| JP2015120845A (en) * | 2013-12-24 | 2015-07-02 | 旭硝子株式会社 | Polishing agent production method, polishing method, and semiconductor integrated circuit device production method |
| KR101706975B1 (en) * | 2014-02-14 | 2017-02-16 | 주식회사 케이씨텍 | Manufacturing method of slurry composition and slurry composition thereby |
| US10319601B2 (en) | 2017-03-23 | 2019-06-11 | Applied Materials, Inc. | Slurry for polishing of integrated circuit packaging |
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| TWI370843B (en) | 2012-08-21 |
| KR100588404B1 (en) | 2006-06-12 |
| TW200536930A (en) | 2005-11-16 |
| KR20060043627A (en) | 2006-05-15 |
| CN1680510A (en) | 2005-10-12 |
| JP4927342B2 (en) | 2012-05-09 |
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