JP5139300B2 - 紫外線および長波長励起用ケイ酸塩系蛍光体とその製造方法 - Google Patents
紫外線および長波長励起用ケイ酸塩系蛍光体とその製造方法 Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 68
- 230000005284 excitation Effects 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title 1
- 239000002243 precursor Substances 0.000 claims description 52
- 239000011701 zinc Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052788 barium Inorganic materials 0.000 claims description 22
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 150000002910 rare earth metals Chemical class 0.000 claims description 13
- 229910052712 strontium Inorganic materials 0.000 claims description 12
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000004973 liquid crystal related substance Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 15
- 238000005424 photoluminescence Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000003440 toxic substance Substances 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 231100000167 toxic agent Toxicity 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910017639 MgSi Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77342—Silicates
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Description
(Sr1-p-nBanZnp)3SiO5:Req ……化学式(2)
前記式2において、Reは希土類金属、0.03<n≦0.133、0<q<0.2であり、Si元素を1とした際のSr元素のモル比(1−p−n)×3が0.817×3〜0.92×3である。
本発明はまた、(a)基質成分としてストロンチウム前駆体、バリウム前駆体、亜鉛前駆体およびシリカ前駆体と、活性剤成分としてRe前駆体を化学量論的に混合する段階、(b)前記混合物を100〜150℃で乾燥し、蛍光体前駆体を製造する段階、および(c)前記蛍光体前駆体を、窒素と水素の体積が75〜98:2〜25の割合で混合された混合ガス雰囲気下で800〜1500℃で熱処理を行う段階を有することを特徴とし、x=0.513〜0.551、y=0.459〜0.502の色座標を有し、下記式2に表される紫外線および長波長励起用蛍光体の製造方法である。
(Sr1-p-nBanZnp)3SiO5:Req ……化学式(2)
前記式2において、Reは希土類金属、0.03<n≦0.133、0<q<0.2であり、Si元素を1とした際のSr元素のモル比(1−p−n)×3が0.817×3〜0.92×3である。
本発明は、前記紫外線および長波長励起用蛍光体は、400〜485nmの範囲の波長で発光することを特徴とする紫外線および長波長励起用蛍光体の製造方法である。
本発明は、紫外線および長波長励起用蛍光体を含む紫外線発光ダイオードである。
本発明は、紫外線および長波長励起用蛍光体を含む能動型液晶表示装置である。
また、本発明が含まれる紫外線および長波長励起用蛍光体の製造方法は、
(a)ストロンチウム前駆体、バリウム前駆体、亜鉛前駆体およびシリカ前駆体と希土類金属前駆体を化学量論的に混合する段階、
(b)前記混合物を100〜150℃で乾燥し、蛍光体前駆体を製造する段階、および
(c)前記蛍光体前駆体を、窒素と水素の体積が75〜98:2〜25の割合で混合された混合ガス雰囲気下で、800〜1500℃の温度範囲で熱処理を行う段階を有し、前記式1に表される。
炭酸ストロンチウム(2.76モル)、炭酸バリウム(0.09モル)、酸化亜鉛(0.09モル)、シリカ前駆体(1モル)、および酸化ユーロピウム(0.07モル)を化学量論的に混合し、より効果的な混合のために、アセトン溶媒10mLを使用してボールミル混合器で混合を行った。次に、前記混合物をオーブンに入れて120℃で24時間乾燥した。乾燥した混合物を高純度アルミナボートに入れて電気炉で、水素と窒素が20:80体積比である混合ガス下で24時間1200℃で熱処理を行った。このように製造された紫外線および長波長励起用蛍光体を励起させて、フォトルミネセンススペクトルを測定して、その結果を図2と図3に表し、色座標を表1に表した。
前記表1のように、バリウムと亜鉛の成分の量を変更した以外は前記実施例1と同様の方法で紫外線および長波長励起用蛍光体を製造した。前記蛍光体の色座標を表1に表す。
前記実施例1で製造した蛍光体、緑色蛍光体(Sr2SiO4:Eu)および青色蛍光体(Sr3MgSi2O8:Eu)を1:3:4の重量比で混合し、405nmの波長を有する紫外線発光ダイオードを使用して白色発光ダイオードを製造し、そのフォトルミネセンススペクトルを図7に表した(色座標:x=0.331;y=0.337、白色、CRI=90)。
バリウムを使用せずに、前記実施例1と同様の方法で蛍光体を製造した。測定したフォトルミネセンススペクトルの結果は、輝度が増加し、フォトルミネセンス帯の移動は起きず、発光効率は増加し、色座標はx=0.442、y=0.558であることを示している。
亜鉛を使用せずに、前記実施例1と同様の方法で蛍光体を製造した。測定したフォトルミネセンススペクトルの結果は、フォトルミネセンス帯は585nmに移動し、色座標はx=0.550、y=0.458であることを示している。
Sr2.93SiO5:Eu2+ 0.07蛍光体を使用して製造した発光ダイオードチップのフォトルミネセンススペクトルを測定した結果、色座標はx=0.451、y=0.552であり、演色指数は65と非常に低いことが分かる。
Claims (5)
- x=0.513〜0.551、y=0.459〜0.502の色座標を有し、下記式2に表されることを特徴とする紫外線および長波長励起用蛍光体。
(Sr1-p-nBanZnp)3SiO5:Req ……化学式(2)
前記式2において、Reは希土類金属、0.03<n≦0.133、0<q<0.2であり、Si元素を1とした際のSr元素のモル比(1−p−n)×3が0.817×3〜0.92×3である。 - (a)基質成分としてストロンチウム前駆体、バリウム前駆体、亜鉛前駆体およびシリカ前駆体と、活性剤成分としてRe前駆体を化学量論的に混合する段階、
(b)前記混合物を100〜150℃で乾燥し、蛍光体前駆体を製造する段階、および
(c)前記蛍光体前駆体を、窒素と水素の体積が75〜98:2〜25の割合で混合された混合ガス雰囲気下で800〜1500℃で熱処理を行う段階を有することを特徴とし、x=0.513〜0.551、y=0.459〜0.502の色座標を有し、下記式2に表される紫外線および長波長励起用蛍光体の製造方法。
(Sr1-p-nBanZnp)3SiO5:Req ……化学式(2)
前記式2において、Reは希土類金属、0.03<n≦0.133、0<q<0.2であり、Si元素を1とした際のSr元素のモル比(1−p−n)×3が0.817×3〜0.92×3である。 - 前記紫外線および長波長励起用蛍光体は、400〜485nmの範囲の波長で発光することを特徴とする、請求項2記載の紫外線および長波長励起用蛍光体の製造方法。
- 請求項1記載の紫外線および長波長励起用蛍光体を含む紫外線発光ダイオード。
- 請求項1記載の紫外線および長波長励起用蛍光体を含む能動型液晶表示装置。
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KR1020050088339A KR100666211B1 (ko) | 2005-09-22 | 2005-09-22 | 자외선 및 장파장 여기용 규산염계 형광체 |
KR10-2005-0088339 | 2005-09-22 | ||
PCT/KR2006/002359 WO2007035026A1 (en) | 2005-09-22 | 2006-06-20 | Silicate phosphor for uv and long-wavelength excitation and preparation method thereof |
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JP5139300B2 true JP5139300B2 (ja) | 2013-02-06 |
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US (1) | US8388863B2 (ja) |
JP (1) | JP5139300B2 (ja) |
KR (1) | KR100666211B1 (ja) |
CN (1) | CN101273108B (ja) |
DE (1) | DE112006002524T5 (ja) |
WO (1) | WO2007035026A1 (ja) |
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KR100655894B1 (ko) | 2004-05-06 | 2006-12-08 | 서울옵토디바이스주식회사 | 색온도 및 연색성이 우수한 파장변환 발광장치 |
KR100658700B1 (ko) | 2004-05-13 | 2006-12-15 | 서울옵토디바이스주식회사 | Rgb 발광소자와 형광체를 조합한 발광장치 |
KR100665299B1 (ko) | 2004-06-10 | 2007-01-04 | 서울반도체 주식회사 | 발광물질 |
KR100665298B1 (ko) | 2004-06-10 | 2007-01-04 | 서울반도체 주식회사 | 발광장치 |
US8308980B2 (en) | 2004-06-10 | 2012-11-13 | Seoul Semiconductor Co., Ltd. | Light emitting device |
JP5118837B2 (ja) * | 2005-10-25 | 2013-01-16 | インテマティックス・コーポレーション | シリケート系オレンジ色蛍光体 |
KR101258397B1 (ko) | 2005-11-11 | 2013-04-30 | 서울반도체 주식회사 | 구리 알칼리토 실리케이트 혼성 결정 형광체 |
KR101055772B1 (ko) | 2005-12-15 | 2011-08-11 | 서울반도체 주식회사 | 발광장치 |
US20070295383A1 (en) * | 2006-03-31 | 2007-12-27 | Intematix Corporation | Wavelength-converting phosphors for enhancing the efficiency of a photovoltaic device |
KR100875443B1 (ko) | 2006-03-31 | 2008-12-23 | 서울반도체 주식회사 | 발광 장치 |
KR100785492B1 (ko) * | 2006-04-17 | 2007-12-13 | 한국과학기술원 | 새로운 조성의 황색 발광 Ce3+부활 실리케이트황색형광체, 그 제조방법 및 상기 형광체를 포함하는 백색발광 다이오드 |
US7820075B2 (en) * | 2006-08-10 | 2010-10-26 | Intematix Corporation | Phosphor composition with self-adjusting chromaticity |
KR101258227B1 (ko) | 2006-08-29 | 2013-04-25 | 서울반도체 주식회사 | 발광 소자 |
CN101784636B (zh) | 2007-08-22 | 2013-06-12 | 首尔半导体株式会社 | 非化学计量四方铜碱土硅酸盐磷光体及其制备方法 |
KR101055769B1 (ko) | 2007-08-28 | 2011-08-11 | 서울반도체 주식회사 | 비화학양론적 정방정계 알칼리 토류 실리케이트 형광체를채택한 발광 장치 |
JP2009064999A (ja) * | 2007-09-07 | 2009-03-26 | He Shan Lide Electronic Enterprise Co Ltd | 低色温度光を生成する方法及びその方法を用いた光放出装置 |
KR101055762B1 (ko) | 2009-09-01 | 2011-08-11 | 서울반도체 주식회사 | 옥시오소실리케이트 발광체를 갖는 발광 물질을 채택한 발광 장치 |
DE102009030205A1 (de) | 2009-06-24 | 2010-12-30 | Litec-Lp Gmbh | Leuchtstoffe mit Eu(II)-dotierten silikatischen Luminophore |
CN102660281B (zh) * | 2012-05-28 | 2014-12-31 | 北京晶创达科技有限公司 | 一种二氧化硅包覆的橙红色荧光粉及其制备方法 |
CN110229194B (zh) * | 2019-06-27 | 2021-09-07 | 河南大学 | 一种镝离子和锑离子同时桥连的锑钨酸盐材料及其制备方法与应用 |
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US3897359A (en) | 1969-06-11 | 1975-07-29 | Matsushita Electronics Corp | Europium activated alkaline earth metal alumino silicate phosphor and method for preparing the same |
US3984587A (en) * | 1973-07-23 | 1976-10-05 | Rca Corporation | Chemical vapor deposition of luminescent films |
JPH01167394A (ja) * | 1987-12-23 | 1989-07-03 | Hitachi Ltd | 蛍光体 |
AU5396798A (en) * | 1997-03-26 | 1998-10-20 | Zhiguo Xiao | Silicate phosphor with a long afterglow and manufacturing method thereof |
KR100923804B1 (ko) | 2001-09-03 | 2009-10-27 | 파나소닉 주식회사 | 반도체발광소자, 발광장치 및 반도체발광소자의 제조방법 |
TWI285672B (en) * | 2001-12-19 | 2007-08-21 | Sumitomo Chemical Co | Method for producing silicate phosphor |
JP4225083B2 (ja) * | 2002-09-24 | 2009-02-18 | 日亜化学工業株式会社 | 蛍光体 |
JP4222059B2 (ja) * | 2002-09-24 | 2009-02-12 | 日亜化学工業株式会社 | 発光装置 |
KR100574546B1 (ko) * | 2003-03-28 | 2006-04-27 | 한국화학연구원 | 스트론튬실리케이트계 형광체, 그 제조방법 및 이를이용한 발광다이오드 |
JP2005068269A (ja) * | 2003-08-22 | 2005-03-17 | Gifu Univ | 蛍光体及びそれを応用した温度センサ |
TWI250664B (en) * | 2004-01-30 | 2006-03-01 | South Epitaxy Corp | White light LED |
JP2006012770A (ja) * | 2004-05-27 | 2006-01-12 | Hitachi Ltd | 発光装置及び該発光装置を用いた画像表示装置 |
WO2006022211A1 (ja) * | 2004-08-27 | 2006-03-02 | Konica Minolta Medical & Graphic, Inc. | 蛍光体及びプラズマディスプレイパネル |
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2005
- 2005-09-22 KR KR1020050088339A patent/KR100666211B1/ko not_active IP Right Cessation
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2006
- 2006-06-20 US US12/067,425 patent/US8388863B2/en not_active Expired - Fee Related
- 2006-06-20 CN CN2006800351228A patent/CN101273108B/zh not_active Expired - Fee Related
- 2006-06-20 JP JP2008532157A patent/JP5139300B2/ja not_active Expired - Fee Related
- 2006-06-20 WO PCT/KR2006/002359 patent/WO2007035026A1/en active Application Filing
- 2006-06-20 DE DE112006002524T patent/DE112006002524T5/de not_active Ceased
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DE112006002524T5 (de) | 2008-08-14 |
JP2009509022A (ja) | 2009-03-05 |
US8388863B2 (en) | 2013-03-05 |
CN101273108B (zh) | 2013-01-30 |
WO2007035026A1 (en) | 2007-03-29 |
US20100224830A1 (en) | 2010-09-09 |
KR100666211B1 (ko) | 2007-01-09 |
CN101273108A (zh) | 2008-09-24 |
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