JP2009080924A - スパッタリングターゲット、光情報記録媒体用薄膜及びその製造方法 - Google Patents
スパッタリングターゲット、光情報記録媒体用薄膜及びその製造方法 Download PDFInfo
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- JP2009080924A JP2009080924A JP2008258075A JP2008258075A JP2009080924A JP 2009080924 A JP2009080924 A JP 2009080924A JP 2008258075 A JP2008258075 A JP 2008258075A JP 2008258075 A JP2008258075 A JP 2008258075A JP 2009080924 A JP2009080924 A JP 2009080924A
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- Prior art keywords
- sputtering
- target
- sputtering target
- thin film
- film
- Prior art date
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 28
- 230000003287 optical effect Effects 0.000 title claims description 35
- 239000010409 thin film Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 title description 4
- 230000008569 process Effects 0.000 title description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000004544 sputter deposition Methods 0.000 claims abstract description 42
- 239000011787 zinc oxide Substances 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229910052738 indium Inorganic materials 0.000 claims description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 17
- 239000000758 substrate Substances 0.000 abstract description 10
- 239000000428 dust Substances 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000000151 deposition Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 48
- 229910004298 SiO 2 Inorganic materials 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
- 230000001681 protective effect Effects 0.000 description 15
- 230000008859 change Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000011241 protective layer Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005245 sintering Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 238000001552 radio frequency sputter deposition Methods 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 240000002329 Inga feuillei Species 0.000 description 1
- XIJLVRPEVKZWKG-UHFFFAOYSA-N [Si](O)(O)(O)O.[S-2].[Zn+2] Chemical compound [Si](O)(O)(O)O.[S-2].[Zn+2] XIJLVRPEVKZWKG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008642 heat stress Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract
【解決手段】A、Bは其々異なる3価以上の陽性元素であり、その価数を其々Ka、Kbとしたとき、AXBYO(KaX+KbY)/2(ZnO)m、1<m、X≦m、0<Y≦0.9、X+Y=2を満たす酸化亜鉛を主成分とした化合物を含有し、かつ相対密度が80%以上であることを特徴とするスパッタリングターゲットに関する。
【選択図】なし
Description
上記の相変化は数百nm〜数μm程度の径に絞ったレーザー光の照射によって行なわれる。この場合、例えば1μmのレーザービームが10m/sの線速度で通過するとき、光ディスクのある点に光が照射される時間は100nsであり、この時間内で上記相変化と反射率の検出を行う必要がある。
このようなことから相変化光ディスクは、Ge−Sb−Te系等の記録薄膜層の両側を硫化亜鉛−ケイ酸化物(ZnS・SiO2)系の高融点誘電体の保護層で挟み、さらにアルミニウム合金反射膜を設けた四層構造となっている。
このように、高融点誘電体の保護層は昇温と冷却による熱の繰返しストレスに対して耐性をもち、さらにこれらの熱影響が反射膜や他の箇所に影響を及ぼさないようにし、かつそれ自体も薄く、低反射率でかつ変質しない強靭さが必要である。この意味において誘電体保護層は重要な役割を有する。
この反射層も保護層材であるZnS−SiO2と接するように配置されているが、ZnS−SiO2からの硫黄成分の拡散により、純Ag又はAg合金反射層材料が腐食劣化して、光情報記録媒体の反射率等への特性劣化を引き起こす要因となっていた。
上記の問題を解決するために、保護層材ZnS−SiO2と同特性で、ZnSを含まない材料が求められている。また、SiO2は、成膜レートの低下や異常放電も生じ易いことから、添加しない方が望ましい。
このようなことから、ZnSとSiO2を含まないZnOベースのホモロガス化合物を主成分とする材料の適用が考えられた(非特許文献2参照)。
このように、保護層材ZnS−SiO2を酸化物系の主成分の材料へと置き換えることで硫黄成分の影響の低減又はそれを消失させることにより、光情報記録媒体の特性改善及び生産性向上が期待された。
このような低密度のターゲットは、スパッタリングによって膜を形成する際に、アーキングを発生し易く、それが起因となってスパッタ時に発生するパーティクル(発塵)やノジュールが発生し、成膜の均一性及び品質が低下するだけでなく、生産性も劣るという問題があった。
1.A、Bは其々異なる3価以上の陽性元素であり、その価数を其々Ka、Kbとしたとき、AXBYO(KaX+KbY)/2(ZnO)m、1<m、X≦m、0<Y≦0.9、X+Y=2を満たす酸化亜鉛を主成分とした化合物を含有し、かつ相対密度が80%以上であることを特徴とするスパッタリングターゲット
2.相対密度が90%以上であることを特徴とする上記1記載のスパッタリングターゲット
3.Aがインジウムであることを特徴とする上記1又は2記載のスパッタリングターゲット
4.ターゲット内における亜鉛以外の、陽性元素のばらつきの範囲が0.5%以内であることを特徴とする上記1〜3のいずれかに記載のスパッタリングターゲット
5.ターゲット内における密度のばらつきの範囲が3%以内であることを特徴とする上記1〜4のいずれかに記載のスパッタリングターゲット、を提供する。
6.上記1〜5のいずれかに記載のスパッタリング用ターゲットを使用して形成された光情報記録媒体用薄膜
7.反射層或いは記録層と隣接して使用されることを特徴とする上記6記載の光情報記録媒体用薄膜
8.上記1〜5のいずれかに記載のスパッタリング用ターゲットを使用して直流スパッタで薄膜を形成することを特徴とする光情報記録媒体用薄膜の製造方法、を提供する。
さらに、高密度ターゲットは、スパッタ時に発生するパーティクル(発塵)やノジュールを低減し、品質のばらつきが少なく量産性を向上させることができ、また保護膜としての特性も損なわずに、該ターゲットを使用して酸化亜鉛を主成分とする相変化型光ディスク保護膜を形成した光記録媒体を得ることができるという著しい効果を有する。
本発明の酸化亜鉛を主成分とした高密度ターゲットは、異常放電の防止、成膜レートの向上及び安定に優れる。
特に、A元素であるインジウムが有効である。また、本発明の上記酸化亜鉛を主成分とした化合物は、他のホモロガス化合物InGa(MgO)等をさらに含ませることができる。
これによって、膜厚及び特性の均一性に優れた光情報記録媒体用薄膜が得られる。この保護膜は、反射層或いは記録層と隣接させて使用することができる。
また、DCスパッタリング装置は価格が安く、制御が容易であり、電力の消費量も少なくて済むという利点がある。さらに、屈折率が高い添加物と組み合わせると、通常のZnS−SiO2(2.0〜2.1)より大きくすることができ、保護膜自体の膜厚を薄くすることも可能となるため、生産性向上、基板加熱防止効果を発揮できる。
本発明のスパッタリング用ターゲットの製造に際しては、平均粒径が5μm以下である各構成元素の酸化物粉末を常圧焼結又は高温加圧焼結することによって製造する。これによって、結晶粒が微細均一で、高密度のターゲットを製造することができる。
4N相当で5μm以下のIn2O3粉と4N相当で1μm以下のAl2O3粉と4N相当で平均粒径5μm以下のZnO粉を用意し、In1.2Al0.8O3(ZnO)3となるように調合して、湿式混合し、乾燥後、1100°Cで仮焼した。仮焼後、平均粒径1μm相当まで湿式微粉砕して、乾燥した粉を成型に充填し、冷間加圧成形した後、温度1400°Cで常圧焼結を行いターゲットとした。このターゲットの相対密度は98%であった。
実施例1のターゲットの化学組成、相対密度、非晶質性、透過率、屈折率を表1に示す。
表1に示すように、本発明の範囲内で成分組成を変え、実施例1と同等の平均粒径の原料粉を使用し、同様に仮焼、粉砕、常圧焼結を行い、さらにターゲットに加工し、そのターゲットを使用してスパッタリングを実施した。
この場合の、ターゲットの組成、ターゲットの相対密度、非晶質性、透過率、屈折率を表1に示す。表1に示すように、本発明の条件に含まれるターゲットは相対密度が80%以上であり、非晶質性が良好に保たれ、透過率、屈折率も良好であることが分る。
4N相当で5μm以下のIn2O3粉と4N相当で1μm以下のAl2O3粉と4N相当で平均粒径5μm以下のZnO粉を用意し、In1.3Al0.7O3(ZnO)0.8となるように調合して、湿式混合し、乾燥後、1100°Cで仮焼した。仮焼後、平均粒径1μm相当まで湿式微粉砕して、乾燥した粉を成型に充填し、冷間加圧成形した後、温度1400°Cで常圧焼結を行いターゲットとした。このターゲットの相対密度は92%であった。
また、成膜サンプルのアニール処理(600°C×30min、Arフロー)後のXRD測定を行った。2θ=20〜60°の範囲の未成膜ガラス基板に対する最大ピーク強度比は8.3であり、非晶質安定性が得られなかった。
比較例1のターゲットの化学組成、相対密度、非晶質性、透過率、屈折率、組成のばらつき、密度のばらつきを表1に示す。
表1に示すように、成分組成を変え(ZnOが本発明の範囲から逸脱している)、比較例1と同等の平均粒径の原料粉を使用し、同様に仮焼、粉砕、常圧焼結を行い、さらにターゲットに加工し、そのターゲットを用いてスパッタリングを実施した。
この場合の、ターゲットの組成、ターゲットの相対密度、非晶質性、透過率、屈折率を表1に示す。表1に示すように、本発明の条件該のターゲットは相対密度が80%以上であるが、特定の結晶ピークが見られ、非晶質安定性が得られなかった。また、透過率は比較例3において著しく悪くなり、屈折率も増加する傾向にあった。
さらに、高密度ターゲットは、スパッタ時に発生するパーティクル(発塵)やノジュールを低減し、品質のばらつきが少なく量産性を向上させることができ、また保護膜としての特性も損なわずに、該ターゲットを使用して酸化亜鉛を主成分とする相変化型光ディスク保護膜を形成した光記録媒体を得ることができるという著しい効果を有する。
したがって、光情報記録媒体用薄膜(特に保護膜としての使用)、同薄膜の製造及び同薄膜製造用ターゲットとして有用である。
特に、A元素であるインジウムが有効である。また、本発明の上記酸化亜鉛を主成分とした化合物は、他のホモロガス化合物InGaO 3 (MgO)等をさらに含ませることができる。
Claims (8)
- A、Bは其々異なる3価以上の陽性元素であり、その価数を其々Ka、Kbとしたとき、AXBYO(KaX+KbY)/2(ZnO)m、1<m、X≦m、0<Y≦0.9、X+Y=2、を満たす酸化亜鉛を主成分とした化合物を含有し、かつ相対密度が80%以上であることを特徴とするスパッタリングターゲット。
- 相対密度が90%以上であることを特徴とする請求項1記載のスパッタリングターゲット。
- Aがインジウムであることを特徴とする請求項1又は請求項2記載のスパッタリングターゲット。
- ターゲット内における亜鉛以外の、陽性元素のばらつきの範囲が0.5%以内であることを特徴とする請求項1〜請求項3のいずれかに記載のスパッタリングターゲット。
- ターゲット内における密度のばらつきの範囲が3%以内であることを特徴とする請求項1〜請求項4のいずれかに記載のスパッタリングターゲット。
- 請求項1〜請求項5のいずれかに記載のスパッタリング用ターゲットを使用して形成された光情報記録媒体用薄膜。
- 反射層或いは記録層と隣接して使用されることを特徴とする請求項6記載の光情報記録媒体用薄膜。
- 請求項1〜請求項5のいずれかに記載のスパッタリング用ターゲットを使用して直流スパッタで薄膜を形成することを特徴とする光情報記録媒体用薄膜の製造方法。
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|---|---|---|---|---|
| EP2237339A2 (en) | 2009-03-30 | 2010-10-06 | TDK Corporation | Electrode for photoelectric conversion elements, manufacturing method of the same, and dye-sensitized solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2237339A2 (en) | 2009-03-30 | 2010-10-06 | TDK Corporation | Electrode for photoelectric conversion elements, manufacturing method of the same, and dye-sensitized solar cell |
| JP2013177676A (ja) * | 2012-02-06 | 2013-09-09 | Mitsubishi Materials Corp | 酸化物スパッタリングターゲット及び光記録媒体用保護膜 |
| WO2014038204A1 (ja) * | 2012-09-07 | 2014-03-13 | 出光興産株式会社 | スパッタリングターゲット |
| JP2014051714A (ja) * | 2012-09-07 | 2014-03-20 | Idemitsu Kosan Co Ltd | スパッタリングターゲット |
| JP2014099493A (ja) * | 2012-11-14 | 2014-05-29 | Idemitsu Kosan Co Ltd | スパッタリングターゲット、酸化物半導体薄膜及びそれらの製造方法 |
| CN104704138A (zh) * | 2012-11-14 | 2015-06-10 | 出光兴产株式会社 | 溅射靶、氧化物半导体薄膜及它们的制造方法 |
| US11443943B2 (en) | 2012-11-14 | 2022-09-13 | Idemitsu Kosam Co., Ltd. | Sputtering target, oxide semiconductor thin film, and method for producing these |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4699504B2 (ja) | 2011-06-15 |
| US7718095B2 (en) | 2010-05-18 |
| US20060147740A1 (en) | 2006-07-06 |
| WO2004079038A1 (ja) | 2004-09-16 |
| US7635440B2 (en) | 2009-12-22 |
| KR20050106473A (ko) | 2005-11-09 |
| TWI304446B (ja) | 2008-12-21 |
| JPWO2004079038A1 (ja) | 2006-06-08 |
| US7897068B2 (en) | 2011-03-01 |
| CN1756857A (zh) | 2006-04-05 |
| TW200417619A (en) | 2004-09-16 |
| JP4965540B2 (ja) | 2012-07-04 |
| CN1756857B (zh) | 2010-09-29 |
| US20100167000A1 (en) | 2010-07-01 |
| CN101650955B (zh) | 2011-08-24 |
| US7892457B2 (en) | 2011-02-22 |
| US20100240521A1 (en) | 2010-09-23 |
| US20080299415A1 (en) | 2008-12-04 |
| JP2009062618A (ja) | 2009-03-26 |
| KR100753328B1 (ko) | 2007-08-29 |
| CN101650955A (zh) | 2010-02-17 |
| JP4611198B2 (ja) | 2011-01-12 |
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