JP4532149B2 - Silicon wafer polishing composition and silicon wafer polishing method - Google Patents
Silicon wafer polishing composition and silicon wafer polishing method Download PDFInfo
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- JP4532149B2 JP4532149B2 JP2004100610A JP2004100610A JP4532149B2 JP 4532149 B2 JP4532149 B2 JP 4532149B2 JP 2004100610 A JP2004100610 A JP 2004100610A JP 2004100610 A JP2004100610 A JP 2004100610A JP 4532149 B2 JP4532149 B2 JP 4532149B2
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- 238000005498 polishing Methods 0.000 title claims description 129
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 68
- 229910052710 silicon Inorganic materials 0.000 title claims description 68
- 239000010703 silicon Substances 0.000 title claims description 68
- 239000000203 mixture Substances 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 18
- 229920002873 Polyethylenimine Polymers 0.000 claims description 21
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 235000012431 wafers Nutrition 0.000 description 75
- 230000000052 comparative effect Effects 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000006061 abrasive grain Substances 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000003002 pH adjusting agent Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- -1 alkaline earth metal hydrogen carbonate Chemical class 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 229920000333 poly(propyleneimine) Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Mechanical Treatment Of Semiconductor (AREA)
Description
本発明は、シリコンウエハ研磨処理に用いるシリコンウエハ研磨用組成物およびシリコンウエハの研磨方法に関する。 The present invention relates to a method of polishing a silicon wafer polishing compound and a silicon wafer for use in a silicon wafer polishing process.
半導体製造の分野では、半導体素子の微細化および多層化による高集積化に伴い、半導体層や金属層の平坦化技術が重要な要素技術となっている。ウエハに集積回路を形成する際、電極配線などによる凹凸を平坦化せずに層を重ねると、段差が大きくなり、平坦性が極端に悪くなる。また段差が大きくなった場合、フォトリソグラフィにおいて凹部と凸部の両方に焦点を合わせることが困難になり微細化を実現することができなくなる。したがって、積層中の然るべき段階でウエハ表面の凹凸を除去するための平坦化処理を行う必要がある。平坦化処理には、エッチングにより凹凸部を除去するエッチバック法、プラズマＣＶＤ（Chemical Vapor Deposition）などにより平坦な膜を形成する成膜法、熱処理によって平坦化する流動化法、選択ＣＶＤなどにより凹部の埋め込みを行う選択成長法などがある。 In the field of semiconductor manufacturing, with the high integration by miniaturization and multilayering of semiconductor elements, the planarization technology of semiconductor layers and metal layers has become an important elemental technology. When forming an integrated circuit on a wafer, if the layers are stacked without flattening the unevenness due to the electrode wiring or the like, the step becomes large and the flatness becomes extremely poor. Further, when the step becomes large, it becomes difficult to focus on both the concave portion and the convex portion in photolithography, and miniaturization cannot be realized. Therefore, it is necessary to perform a planarization process for removing irregularities on the wafer surface at an appropriate stage during the lamination. For the flattening process, an etching back method for removing uneven portions by etching, a film forming method for forming a flat film by plasma CVD (Chemical Vapor Deposition), a fluidizing method for flattening by heat treatment, a concave portion by selective CVD, etc. There is a selective growth method for embedding.
以上の方法は、絶縁膜、金属膜など膜の種類によって適否があること、また特に平坦化できる領域がきわめて狭いという問題がある。このような問題を克服することができる平坦化処理技術としてＣＭＰによる平坦化がある。 The above method has problems that it is appropriate depending on the type of film such as an insulating film and a metal film, and that the region that can be flattened is particularly narrow. As a planarization technique that can overcome such problems, there is planarization by CMP.
ＣＭＰによる平坦化処理では、微細なシリカ粒子（砥粒）を懸濁したスラリを研磨パッド表面に供給しながら、圧接した研磨パッドと、被研磨物である例えばシリコンウエハとを相対移動させて表面を研磨することにより、広範囲にわたるウエハ表面を高精度に平坦化することができる。 In the planarization process by CMP, while supplying a slurry in which fine silica particles (abrasive grains) are suspended to the surface of the polishing pad, the surface of the polishing pad is moved relative to the surface to be polished, for example, a silicon wafer. By polishing the surface, the wafer surface over a wide range can be planarized with high accuracy.
ＣＭＰによるシリコンウエハ研磨は、３段階または４段階の複数段階の研磨を行うことで高精度の平坦化を実現している。第１段階および第２段階に行う１次研磨および２次研磨は、表面平滑化を主な目的とし、高い研磨レートが求められる。１次研磨および２次研磨では、研磨後のウエハ表面が疎水性となり、ウエハ周辺の浮遊微粒子などの汚染粒子が付着しやすくなる。粒子汚染を防止するために、従来では、研磨直後にウエハ表面の親水化処理を行ったり、次工程に進むまでの間、研磨直後のウエハ表面に水を吹き付けたり、研磨直後のウエハを水中に保管したりする必要がある。 Polishing of a silicon wafer by CMP realizes high-precision flattening by performing three-step or four-step polishing. The primary polishing and secondary polishing performed in the first stage and the second stage mainly aim at surface smoothing and require a high polishing rate. In primary polishing and secondary polishing, the polished wafer surface becomes hydrophobic, and contaminant particles such as suspended fine particles around the wafer are likely to adhere. In order to prevent particle contamination, conventionally, the wafer surface is subjected to a hydrophilic treatment immediately after polishing, or water is sprayed on the wafer surface immediately after polishing, or the wafer immediately after polishing is submerged in water until the next process is performed. It is necessary to keep it.
第３段階または第４段階の最終段階に行う仕上げ研磨は、ヘイズ（表面曇り）の抑制を主な目的とし、さらに粒子汚染を防止するために表面の親水化が求められる。具体的には、加工圧力を低くしてヘイズを抑制するとともに、スラリ組成を１次研磨および２次研磨に使用する組成から変更して研磨と同時に表面の親水化も行う。 The final polishing performed in the final stage of the third stage or the fourth stage mainly aims to suppress haze (surface haze), and further requires hydrophilic surface to prevent particle contamination. Specifically, the processing pressure is lowered to suppress haze, and the slurry composition is changed from the composition used for primary polishing and secondary polishing to make the surface hydrophilic at the same time as polishing.
仕上げ研磨において、ウエハ表面を親水化するために用いるスラリの従来例が特許文献１に記載されている。特許文献１記載の研磨用組成物は、水溶性高分子化合物であるセルロース誘導体またはポリビニルアルコールを含み、研磨時に水溶性高分子化合物でコーティングしてウエハ表面を親水化している。セルロース誘導体としては、特にヒドロキシエチルセルロースが好ましく、その分子量および濃度などの最適化が行われている。 Patent Document 1 describes a conventional example of a slurry used to make a wafer surface hydrophilic in finish polishing. The polishing composition described in Patent Document 1 contains a cellulose derivative or polyvinyl alcohol which is a water-soluble polymer compound, and is coated with the water-soluble polymer compound during polishing to make the wafer surface hydrophilic. As the cellulose derivative, hydroxyethyl cellulose is particularly preferable, and its molecular weight and concentration are optimized.
今後、半導体素子の微細化がさらに進むと、シリコンウエハ研磨に対してもさらなる高精度化が求められることとなる。仕上げ研磨前に行う２次研磨後のウエハの表面状態が、仕上げ研磨後のウエハの表面状態に及ぼす影響が大きいため、さらなる高精度化に対応するには、２次研磨において、高い研磨レートのみならず表面の親水化も必要となる。特許文献１記載の研磨組成物のように、セルロース誘導体などを用いることでウエハ表面の親水化は可能であるが、セルロース誘導体が砥粒であるシリカ粒子をも覆ってしまい、研磨レートが低下してしまう。 In the future, further miniaturization of semiconductor elements will require higher precision for silicon wafer polishing. Since the surface condition of the wafer after the secondary polishing performed before the final polishing has a large influence on the surface condition of the wafer after the final polishing, only a high polishing rate is required in the secondary polishing in order to cope with higher accuracy. It is also necessary to make the surface hydrophilic. As in the polishing composition described in Patent Document 1, it is possible to make the wafer surface hydrophilic by using a cellulose derivative or the like, but the cellulose derivative also covers silica particles that are abrasive grains, and the polishing rate is lowered. End up.
本発明の目的は、被研磨物であるシリコンウエハの表面を親水化するとともに研磨レートを低下させないシリコンウエハ研磨用組成物およびシリコンウエハの研磨方法を提供することである。 An object of the present invention is to provide a method for polishing a silicon wafer polishing compound and a silicon wafer not to lower the polishing rate as well as hydrophilic a surface of a silicon wafer to be polished.
本発明は、砥粒と、ポリアルキレンイミンと、アルカリ金属の水酸化物および第四級アンモニウム塩からなる研磨促進剤とを含み、複数段階の研磨において仕上げ段階より前の段階で用いることを特徴とするシリコンウエハ研磨用組成物である。 The present invention comprises an abrasive, a polyalkyleneimine, a polishing accelerator composed of an alkali metal hydroxide and a quaternary ammonium salt, and is used in a stage before the finishing stage in a multi-stage polishing. A composition for polishing a silicon wafer .
また本発明は、ポリアルキレンイミンの分子量が、２００〜５００,０００であることを特徴とする。 In the present invention, the molecular weight of the polyalkyleneimine is 200 to 500,000.
また本発明は、ポリアルキレンイミンが、ポリエチレンイミンであることを特徴とする。 In the present invention, the polyalkyleneimine is polyethyleneimine .
また本発明は、複数段階の研磨を行うシリコンウエハの研磨方法において、
仕上げ段階より前の段階で、上記のシリコンウエハ研磨用組成物を用いてシリコンウエハの研磨を行うことを特徴とするシリコンウエハの研磨方法である。
The present invention also relates to a method for polishing a silicon wafer that performs multiple stages of polishing.
A silicon wafer polishing method characterized by polishing a silicon wafer using the above-described composition for polishing a silicon wafer in a stage prior to a finishing stage.
本発明によれば、シリコンウエハ研磨用組成物は、砥粒と、ポリアルキレンイミンと、アルカリ金属の水酸化物および第四級アンモニウム塩からなる研磨促進剤とを含み、複数段階の研磨において仕上げ段階より前の段階で用いることを特徴とする。ポリアルキレンイミンとしては、ポリエチレンイミン、ポリプロピレンイミンおよびポリブチレンイミンなどを使用することができるが、特にポリエチレンイミンを用いることが好ましい。 According to the present invention, a silicon wafer polishing composition comprises abrasive grains, a polyalkyleneimine, and a polishing accelerator comprising an alkali metal hydroxide and a quaternary ammonium salt, and is finished in a multi-stage polishing. It is used in the stage before the stage . As the polyalkyleneimine, polyethyleneimine, polypropyleneimine, polybutyleneimine and the like can be used, and it is particularly preferable to use polyethyleneimine.
ポリエチレンイミンは、被研磨物であるシリコンウエハとの反応性が高く、シリコンウエハ表面を親水化すると同時にシリコンウエハに対するエッチング作用も有しているため、ポリエチレンイミンが、砥粒であるシリカ粒子を覆っても研磨レートを低下させることなく被研磨物表面を親水化することができる。
また、アルカリ金属の水酸化物および第四級アンモニウム塩からなる研磨促進剤を含むことにより、研磨レートを高くすることができる。
Polyethyleneimine has a high reactivity with the silicon wafer that is the object to be polished , and has an etching action on the silicon wafer at the same time as making the silicon wafer surface hydrophilic, so that polyethyleneimine covers the silica particles that are abrasive grains. However, the surface of the object to be polished can be made hydrophilic without reducing the polishing rate.
Further, the polishing rate can be increased by including a polishing accelerator comprising an alkali metal hydroxide and a quaternary ammonium salt.
また本発明によれば、ポリアルキレンイミンの好ましい分子量の範囲は、２００〜５００,０００であり、さらに好ましくは５,０００〜１００,０００である。ポリアルキレンイミンの分子量が小さすぎると十分な親水化が発揮できず、分子量が大きすぎると砥粒であるシリカ粒子が凝集してしまう。 According to the invention, the preferred molecular weight range of the polyalkyleneimine is 200 to 500,000, more preferably 5,000 to 100,000. If the molecular weight of the polyalkyleneimine is too small, sufficient hydrophilicity cannot be exerted, and if the molecular weight is too large, silica particles as abrasive grains are aggregated.
また本発明によれば、複数段階の研磨を行うシリコンウエハの研磨方法においては、仕上げ段階より前の段階で、上記のシリコンウエハ研磨用組成物を用いて研磨を行う。仕上げ段階より前の、たとえば２次研磨などで、高い研磨レートを維持して、シリコンウエハ表面を親水化することができるので、シリコンウエハ研磨のさらなる高精度化に対応することができる。 According to the present invention, in the method for polishing a silicon wafer in which polishing is performed in a plurality of stages, polishing is performed using the above-described silicon wafer polishing composition at a stage prior to the finishing stage. Since the silicon wafer surface can be hydrophilized while maintaining a high polishing rate, for example, in the secondary polishing before the finishing stage, it is possible to cope with higher precision of silicon wafer polishing.
本発明のシリコンウエハ研磨用組成物は、砥粒と、ポリアルキレンイミンと、アルカリ金属の水酸化物および第四級アンモニウム塩からなる研磨促進剤とを含み、複数段階の研磨において仕上げ段階より前の段階で用いることを特徴とする。ポリアルキレンイミンとしては、ポリエチレンイミン、ポリプロピレンイミンおよびポリブチレンイミンなどを使用することができるが、特にポリエチレンイミンを用いることが好ましい。 The silicon wafer polishing composition of the present invention comprises abrasive grains, a polyalkyleneimine, and a polishing accelerator composed of an alkali metal hydroxide and a quaternary ammonium salt, and includes a polishing step prior to the finishing step in a plurality of steps. It is used in the stage of . As the polyalkyleneimine, polyethyleneimine, polypropyleneimine, polybutyleneimine and the like can be used, and it is particularly preferable to use polyethyleneimine.
ポリエチレンイミンは、主鎖および側鎖に１〜３級のアミノ基を有しており、被研磨物であるシリコンウエハとの反応性が高く、シリコンウエハ表面を親水化すると同時にシリコンウエハに対するエッチング作用も有している。従来のように、シリコンウエハ表面を親水化するためにセルロースなどの水溶性高分子を用いると、研磨レートが低下してしまうが、ポリエチレンイミンを用いることにより、このポリエチレンイミンが砥粒であるシリカ粒子を覆っても研磨レートを低下させることなくシリコンウエハ表面を親水化することができる。 Polyethyleneimine has primary to tertiary amino groups in the main chain and side chain, and is highly reactive with the silicon wafer that is the object to be polished . Also have. As in the past, when a water-soluble polymer such as cellulose is used to make the silicon wafer surface hydrophilic, the polishing rate decreases. However, by using polyethyleneimine, this polyethyleneimine is a silica that is an abrasive grain. Even if the particles are covered, the silicon wafer surface can be hydrophilized without lowering the polishing rate.
さらに、ポリエチレンイミン自体がシリコンウエハおよびシリカ粒子だけでなく、研磨パッド表面にも付着し、研磨パッドの表面電位をプラスに帯電させることで研磨パッドのライフタイム（使用寿命）をのばすことも可能である。これは、研磨パッド表面の電位をプラスに帯電させることで、砥粒であるシリコン粒子および削り取られたシリコン（加工屑）が研磨パッド表面へ付着するのを防ぎ、研磨パッドの目詰まりを防止するからである。 Furthermore, polyethyleneimine itself adheres not only to silicon wafers and silica particles, but also to the surface of the polishing pad, and the surface potential of the polishing pad can be positively charged to extend the life of the polishing pad. is there. This prevents the clogging of the polishing pad by preventing the silicon particles as abrasive grains and scraped silicon (processing waste) from adhering to the polishing pad surface by charging the polishing pad surface positively. Because.
このようなポリエチレンイミンを含むシリコンウエハ研磨用組成物は、複数段階の研磨を行うシリコンウエハの研磨方法において、仕上げ段階より前の段階で用いる。仕上げ段階より前の、たとえば２次研磨などで、高い研磨レートを維持して、シリコンウエハ表面を親水化することができるので、シリコンウエハ研磨のさらなる高精度化に対応することができる。 The silicon wafer polishing compound comprising a polyethylenimine such as, in the polishing method of a silicon wafer to polish a plurality of steps, Ru used in the previous step from the finishing phase. Since the silicon wafer surface can be hydrophilized while maintaining a high polishing rate, for example, in the secondary polishing before the finishing stage, it is possible to cope with higher precision of silicon wafer polishing.
ポリアルキレンイミンの分子量の範囲は、２００〜５００,０００が好ましく、５,０００〜１００,０００がさらに好ましい。ポリアルキレンイミンの分子量が小さすぎると十分な親水化が発揮できず、分子量が大きすぎると砥粒であるシリカ粒子が凝集してしまう。 The molecular weight range of the polyalkyleneimine is preferably from 200 to 500,000, more preferably from 5,000 to 100,000. If the molecular weight of the polyalkyleneimine is too small, sufficient hydrophilicity cannot be exhibited, and if the molecular weight is too large, silica particles as abrasive grains are aggregated.
本発明のシリコンウエハ研磨用組成物は、研磨促進剤を含み、少なくともｐＨ調整剤などの添加剤を含有することができる。 The composition for polishing a silicon wafer of the present invention contains a polishing accelerator and can contain at least an additive such as a pH adjuster.
研磨促進剤としては、無機アルカリ化合物であるアルカリ金属の水酸化物、第四級アンモニウム塩および炭酸塩などを用いることができる。 As the polishing accelerator, alkali metal hydroxides , quaternary ammonium salts and carbonates which are inorganic alkali compounds can be used.
ｐＨ調整剤としては、アルカリ金属またはアルカリ土類金属の炭酸水素塩、または有機酸などを用いることができる。なお、有機酸はｐＨ調整剤として働くだけでなく、錯化剤としても働く。 As the pH adjuster, an alkali metal or alkaline earth metal hydrogen carbonate, an organic acid, or the like can be used. The organic acid not only functions as a pH adjusting agent but also functions as a complexing agent.
本発明のシリコンウエハ研磨用組成物は、たとえば以下のような工程で製造する。
（１）アルカリ水溶液の調整
ポリエチレンイミンと、研磨促進剤と、少なくともｐＨ調整剤などの添加剤とを添加してアルカリ水溶液を得る。
（２）混合
シリカ粒子分散液とアルカリ水溶液とを混合し、本発明のシリコンウエハ研磨用組成物を得る。
必要に応じて、混合後にフィルターを用いた分級を行い、シリカ粒子の凝集物を除去してもよい。
The silicon wafer polishing composition of the present invention is produced, for example, by the following steps.
(1) Preparation of alkaline aqueous solution Polyethyleneimine, a polishing accelerator, and at least an additive such as a pH adjusting agent are added to obtain an alkaline aqueous solution.
(2) Mixing The silica particle dispersion and the alkaline aqueous solution are mixed to obtain the silicon wafer polishing composition of the present invention.
If necessary, classification using a filter may be performed after mixing to remove aggregates of silica particles.
以下では、本発明の実施例および比較例について説明する。
［比較例および実施例組成］
なお、以下に示す組成は、希釈済みの組成で、残部は水である。
Hereinafter, examples and comparative examples of the present invention will be described.
[Comparative Example and Example Composition]
In addition, the composition shown below is a diluted composition and the remainder is water.
（実施例１）
砥粒 ：シリカ粒子 0.30重量％
ポリアルキレンイミン：ポリエチレンイミン（分子量10,000） 0.10重量％
研磨促進剤， ：水酸化カリウム、第四級アンモニウム塩 0.067重量％
pH調整剤 ：炭酸塩 0.30重量％
（実施例２）
砥粒 ：シリカ粒子 0.30重量％
ポリアルキレンイミン：ポリエチレンイミン (分子量10,000) 0.05重量％
研磨促進剤， ：水酸化カリウム、第四級アンモニウム塩 0.067重量％
pH調整剤 ：炭酸塩 0.30重量％
Example 1
Abrasive grain: 0.30% by weight of silica particles
Polyalkyleneimine: Polyethyleneimine (molecular weight 10,000) 0.10% by weight
Polishing accelerator,: Potassium hydroxide, quaternary ammonium salt 0.067 wt%
pH adjuster: Carbonate 0.30% by weight
(Example 2)
Abrasive grain: 0.30% by weight of silica particles
Polyalkyleneimine: Polyethyleneimine (molecular weight 10,000) 0.05% by weight
Polishing accelerator,: Potassium hydroxide, quaternary ammonium salt 0.067 wt%
pH adjuster: Carbonate 0.30% by weight
（比較例１）商品名：Nalco2350、ONDEO Nalco社製(30倍希釈)
砥粒 ：シリカ粒子 1.7重量％
研磨促進剤 ：アミン化合物
（比較例２）
砥粒 ：シリカ粒子 0.30重量％
研磨促進剤， ：水酸化カリウム、第四級アンモニウム塩 0.067重量％
pH調整剤 ：炭酸塩 0.30重量％
（比較例３）
砥粒 ：シリカ粒子 0.30重量％
ヒドロキシエチルセルロース（分子量1,000,000） 0.01重量％
研磨促進剤， ：水酸化カリウム、第四級アンモニウム塩 0.067重量％
pH調整剤 ：炭酸塩 0.30重量％
(Comparative Example 1) Product name: Nalco2350, manufactured by ONDEO Nalco (diluted 30 times)
Abrasive grain: 1.7% by weight of silica particles
Polishing accelerator: amine compound (Comparative Example 2)
Abrasive grain: 0.30% by weight of silica particles
Polishing accelerator,: Potassium hydroxide, quaternary ammonium salt 0.067 wt%
pH adjuster: Carbonate 0.30% by weight
(Comparative Example 3)
Abrasive grain: 0.30% by weight of silica particles
Hydroxyethyl cellulose (molecular weight 1,000,000) 0.01% by weight
Polishing accelerator,: Potassium hydroxide, quaternary ammonium salt 0.067 wt%
pH adjuster: Carbonate 0.30% by weight
上記のように実施例１、２は、ウエハの親水化が得ることを目的とし、ポリエチレンイミンを添加したシリコンウエハ研磨用組成物である。実施例１と実施例２との違いは、ポリエチレンイミンの含有量の違いであり、実施例１は、分子量１０,０００のポリエチレンイミンを全体量の０．１０重量％含有し、実施例２は、０．０５重量％含有している。 As described above, Examples 1 and 2 are silicon wafer polishing compositions to which polyethyleneimine is added for the purpose of obtaining hydrophilicity of the wafer . The difference between Example 1 and Example 2 is the difference in the content of polyethyleneimine. Example 1 contains polyethyleneimine with a molecular weight of 10,000 in an amount of 0.10% by weight, and Example 2 0.05% by weight.
比較例１は、仕上げ段階より前の２次研磨などで従来用いられているシリコンウエハ研磨用組成物として、ONDEO Nalco社製のNalco2350（商品名）を用いた。 In Comparative Example 1, Nalco 2350 (trade name) manufactured by ONDEO Nalco was used as a silicon wafer polishing composition conventionally used in secondary polishing before the finishing stage.
比較例２は、ポリアルキレンイミンを含有していないこと以外は、実施例１および実施例２と同様である。比較例３は、ポリアルキレンイミンに代えて、従来の仕上げ研磨においてウエハ表面を親水化するために含有させるヒドロキシエチルセルロースを含有していること以外は、実施例１および実施例２と同様である。 Comparative Example 2 is the same as Example 1 and Example 2 except that it does not contain polyalkyleneimine. Comparative Example 3 is the same as Example 1 and Example 2 except that, instead of polyalkyleneimine, it contains hydroxyethyl cellulose that is contained to make the wafer surface hydrophilic in conventional finish polishing.
［液体−固体接触角（θ）測定］
シリコンウエハ表面の親水化を確認するために、実施例１〜２および比較例１〜３で表面処理したシリコンウエハと、水との液体−固体接触角（θ）を測定した。
[Measurement of liquid-solid contact angle (θ)]
In order to confirm the hydrophilization of the silicon wafer surface, the liquid-solid contact angle (θ) between the silicon wafer surface-treated in Examples 1-2 and Comparative Examples 1-3 and water was measured.
液体−固体接触角とは、液体（水）が固体面（シリコンウエハ表面）に接触しているとき、液面と固体面のなす角度である。接触角が小さければ小さいほど液体による固体表面のぬれ性がよく、液体として水を用いた場合、固体表面が親水性であることを示す。 The liquid-solid contact angle is an angle formed by the liquid surface and the solid surface when the liquid (water) is in contact with the solid surface (silicon wafer surface). The smaller the contact angle, the better the wettability of the solid surface with the liquid. When water is used as the liquid, the solid surface is hydrophilic.
実施例１、２および比較例１〜３のシリコンウエハ研磨用組成物を用いて、シリコンウエハを研磨し、シリコンウエハの表面を純水リンス洗浄したのち、シリコンウエハ表面に高さが１．５２ｍｍとなるように純水を滴下し、接触角測定装置（商品名：ＣＡ−Ｓ１５０、協和界面科学株式会社製）によって接触角（θ）を測定した。研磨条件は以下のとおりである。 Using the compositions for polishing silicon wafers of Examples 1 and 2 and Comparative Examples 1 to 3, the silicon wafer was polished, the surface of the silicon wafer was rinsed with pure water, and the height of the silicon wafer was 1.52 mm. Pure water was dropped so that the contact angle (θ) was measured by a contact angle measuring device (trade name: CA-S150, manufactured by Kyowa Interface Science Co., Ltd.). The polishing conditions are as follows.
シリコンウエハ：３インチシリコンウエハ
研磨装置：商品名ＭＡ−２００Ｄ、ムサシノ電子株式会社製
研磨パッド：商品名Ｗｈｉｔｅｘ ＲＧＳ、ロデール・ニッタ株式会社製
研磨定盤回転速度：１４５ｒｐｍ
加圧ヘッド回転速度：１４５ｒｐｍ
研磨荷重面圧：約１３ｋＰａ（１３０ｇｆ／ｃｍ２）
シリコンウエハ研磨用組成物の流量：８０ｍｌ／分
研磨時間：６分間
測定結果を表１に示す。
Silicon wafer: 3 inch silicon wafer Polishing apparatus: Brand name MA-200D, manufactured by Musashino Electronics Co., Ltd. Polishing pad: Product name, Whiteex RGS, manufactured by Rodel Nitta Co., Ltd. Polishing platen rotational speed: 145 rpm
Pressure head rotation speed: 145 rpm
Polishing load surface pressure: about 13 kPa (130 gf / cm 2 )
Flow rate of silicon wafer polishing composition: 80 ml / min Polishing time: 6 minutes Table 1 shows the measurement results.
実施例１，２および比較例３（ヒドロキシエチルセルロース含有）を用いた場合、接触角が１５°未満と小さく研磨後のシリコンウエハの表面が親水化されていることがわかる。従来製品である比較例１およびポリエチレンイミンを含有しない比較例２を用いた場合、接触角が２５°より大きくなっており、研磨後のシリコンウエハの表面が疎水性であることがわかる。 When Examples 1 and 2 and Comparative Example 3 (containing hydroxyethyl cellulose) are used, it can be seen that the contact angle is as small as less than 15 ° and the surface of the polished silicon wafer is hydrophilized. When the comparative example 1 which is a conventional product and the comparative example 2 which does not contain polyethyleneimine are used, the contact angle is larger than 25 °, and it can be seen that the surface of the polished silicon wafer is hydrophobic.
このように、ポリエチレンイミンを含むシリコンウエハ研磨用組成物を用いることで、シリコンウエハの表面を十分に親水化できることがわかった。 Thus, it was found that the surface of the silicon wafer can be sufficiently hydrophilized by using the silicon wafer polishing composition containing polyethyleneimine.
［研磨レート測定］
実施例１、２および比較例１〜３のシリコンウエハ研磨用組成物を用いてシリコンウエハの研磨を行い、研磨レートを測定した。研磨レートとは、単位時間（分）当たりに研磨によって除去されたシリコンウエハの厚み（Å）である。研磨レート測定のために行った研磨処理の条件は、接触角測定の条件と同様である。
[Polishing rate measurement]
The silicon wafer was polished using the silicon wafer polishing compositions of Examples 1 and 2 and Comparative Examples 1 to 3, and the polishing rate was measured. The polishing rate is the thickness (Å) of the silicon wafer removed by polishing per unit time (minute). The conditions for the polishing treatment performed for measuring the polishing rate are the same as the conditions for measuring the contact angle.
図１は、実施例および比較例のシリコンウエハ研磨用組成物を用いたときの相対研磨レートを示す図である。縦軸は、比較例１を基準としたときの相対的な研磨レートである相対研磨レートを示す。 FIG. 1 is a graph showing relative polishing rates when the silicon wafer polishing compositions of Examples and Comparative Examples are used. The vertical axis represents the relative polishing rate, which is a relative polishing rate when Comparative Example 1 is used as a reference.
図からわかるように、実施例１の相対研磨レートが１．０１、実施例２の相対研磨レートが０．９８であり、仕上げ段階より前の２次研磨などで従来用いられている比較例１の研磨レートと同等の研磨レートを実現することが可能であった。 As can be seen from the figure, the relative polishing rate of Example 1 is 1.01, the relative polishing rate of Example 2 is 0.98, and Comparative Example 1 conventionally used in secondary polishing before the finishing stage. It was possible to achieve a polishing rate equivalent to the polishing rate.
比較例３の相対研磨レートは０．２０であり、従来の仕上げ研磨においてウエハ表面を親水化するために含有させるヒドロキシエチルセルロースの添加により、ウエハを親水化することはできるが、研磨レートが極めて低下している。 The relative polishing rate of Comparative Example 3 is 0.20, and the wafer can be hydrophilized by adding hydroxyethyl cellulose to make the wafer surface hydrophilic in the conventional finish polishing, but the polishing rate is extremely low. is doing.
以上のように、ポリアルキレンイミンを含むことで、被研磨物であるシリコンウエハの表面を親水化するとともに研磨レートを低下させないシリコンウエハ研磨用組成物を実現できる。さらに、仕上げ段階より前の段階において本発明のシリコンウエハ研磨用組成物を使用することで効果が顕著になる。 As described above, by including polyalkyleneimine, it is possible to realize a silicon wafer polishing composition that hydrophilizes the surface of a silicon wafer that is an object to be polished and does not decrease the polishing rate. Furthermore, the effect becomes remarkable by using the silicon wafer polishing composition of the present invention in the stage before the finishing stage.
Claims (4)
仕上げ段階より前の段階で、請求項１〜３のいずれか１つに記載のシリコンウエハ研磨用組成物を用いてシリコンウエハの研磨を行うことを特徴とするシリコンウエハの研磨方法。 In a method for polishing a silicon wafer that performs multiple stages of polishing,
At the stage before more finishing stage, the polishing method for a silicon wafer and performing the polishing of the silicon wafer using a silicon wafer polishing composition according to any one of claims 1 to 3.
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| US6676718B2 (en) * | 2001-01-12 | 2004-01-13 | Rodel Holdings, Inc. | Polishing of semiconductor substrates |
| US6685757B2 (en) * | 2002-02-21 | 2004-02-03 | Rodel Holdings, Inc. | Polishing composition |
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| JPH08113772A (en) * | 1994-10-18 | 1996-05-07 | Asahi Denka Kogyo Kk | Silicon wafer abrasive composition and composition for silicon wafer abrasive |
| JPH10168431A (en) * | 1996-12-09 | 1998-06-23 | Internatl Business Mach Corp <Ibm> | Polishing step and slurry for flattening |
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