JP5068946B2 - 太陽電池用透明導電性基板およびその製造方法 - Google Patents
太陽電池用透明導電性基板およびその製造方法 Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 157
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 73
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 45
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 40
- 238000002834 transmittance Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 description 61
- 239000010408 film Substances 0.000 description 58
- 239000011521 glass Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 21
- 229910021417 amorphous silicon Inorganic materials 0.000 description 19
- 239000002585 base Substances 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 13
- 239000011737 fluorine Substances 0.000 description 13
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 12
- 229910001887 tin oxide Inorganic materials 0.000 description 12
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910021419 crystalline silicon Inorganic materials 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 239000005368 silicate glass Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000006018 Li-aluminosilicate Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000005385 borate glass Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- NRVRMANRRKBYEK-UHFFFAOYSA-N methane;dihydroiodide Chemical compound C.I.I NRVRMANRRKBYEK-UHFFFAOYSA-N 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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Description
また、特許文献2では、光電変換層のうち、結晶シリコン系薄膜層での光電変換効率に着目して、透明導電性基板のヘイズ率を6.5%以下に規定した光電変換装置が提案されている。
・シート抵抗が小さい。
・光透過率が高い。
・ヘイズ率が高い。
・透明導電性基板全体について見た場合にヘイズ率のばらつきが少ない。
ここで、ヘイズ率とは拡散透過光量を全透過光量で除した値である。ヘイズ率が高いと、光が通過する際の散乱が大きくなるため、太陽電池の光電変換層内の光路長が長くなる。したがって、ヘイズ率を高くすることができれば、光電変換層での光吸収率が高くなり、太陽電池の光電変換効率が優れたものになる。
また、特開平6−316442号公報では、3層膜について、透過率が高く、視認性を高めたタッチパネル用の導電膜が記載されている。しかし、タッチパネル用の導電膜は、視認性を高めるために上記導電膜の厚みが0.01〜0.02μmと本発明と比べて薄い。そのためヘイズ率は1%以下であり、太陽電池用として用いた場合、光電変換効率を向上させることができない問題がある。
図1に示すように、本発明の太陽電池用透明導電性基板1は、基体2上に、TiO2層3、SiO2層4およびSnO2層5が、該基体2側からこの順に積層して形成されている。以下、各層について説明する。
これらの中でも、透光性、機械的強度、耐熱性に優れ、かつコスト面でも優れることからガラス製の基体2が好ましい。基体2をなすガラス材料としては、無色透明なソーダライムシリケートガラス、アルミノシリケートガラス、ボレートガラス、リチウムアルミノシリケートガラス、石英ガラス、ホウ珪酸ガラス、無アルカリガラス、および、その他の各種ガラスから選択することができる。
SiO2層4についても、TiO2層3およびSnO2層5との界面が実質的に平坦であることが好ましい。SiO2層4の界面が実質的に平坦であれば、その上に積層されるSnO2層5の結晶が面内均一に成長し、結果的に太陽電池用透明導電性基板1を基板全体として見た場合のC光源ヘイズ率のばらつきを抑制することができる。SiO2層4は、その上にSnO2層5を形成する前の表面を原子間力顕微鏡(AFM)で測定した際の算術平均粗さ(Ra)が1nm以下であることが好ましく、より好ましくは0.6nm以下である。
さらに、本発明の太陽電池用透明導電性基板は、光透過率、特に400〜1200nmの波長領域の光透過率に優れている。具体的には、400nm〜1200nmの波長領域の平均光透過率が80%以上であることが好ましい。平均光透過率は83%以上であることがより好ましく、86%以上であることがさらに好ましい。
本発明の太陽電池用透明導電性基板は、ヘイズ率が高く、基板全体について見た場合にヘイズ率のばらつきが少なく、かつ光透過率、特に400〜1200nmの波長域の光透過率が高いため、タンデム型太陽電池に使用した場合に、光電変換効率をさらに向上させることができる。
[参考例1]
1.太陽電池用透明導電性基板の製造
基体としてソーダライムシリケートガラス製の基体(30cm×40cm×4mm)を用意し、十分に洗浄を行った後、該基体上に5nmの層厚のTiO2層、32nmの層厚のSiO2層、および0.5μmの層厚のフッ素がドープされたSnO2層を該基体側からこの順に形成させた。
得られた太陽電池用透明導電性基板について、以下の物性評価を実施した。結果を表1に示した。
層厚(TiO 2 層、SiO 2 層、SnO 2 層)
TiO2層およびSiO2層については、それぞれ各層を形成した後、触針式表面粗さ計(DEKTAK3030、アルバック製)により測定した。SnO2層については、全層を形成した後、一部のSnO2層にのみマスクをかぶせて、HCl:Znでエッチングをして段差を作り、その段差を上記の表面粗さ計により測定して得た。
SnO2層中のフッ素濃度は、SnO2層を亜鉛を含む塩酸中で溶解した後、ガスクロマトグラフィーにより定量分析を行うことで求めた。なお、表1におけるフッ素濃度は、SnO2に対するmol%である。
基板全面に分布する10箇所において、C光源ヘイズ率を基板の長手方向に10mm間隔でヘイズメータ(TC−H III、東京電色製)で測定した。得られたヘイズ率の平均値を、基板のC光源ヘイズ率とした。また、得られたヘイズ率の最大値と最小値の差を求め、これを基板全体におけるC光源ヘイズ率のばらつきとした。
波長400nm〜1200nmでの分光透過率の平均値を積分球を用いた分光光度計(U−3410自記分光光度計、日立製)によって測定し、ヘイズによる透過率の測定値の低下を公知の方法(導電膜表面の凹凸による透過率測定値の低下を防止するために、導電膜の凹凸面と石英ガラス基板とを合わせ、これらの間に二ヨウ化メタン(CH2I2)を挟みこみ透過率を測定する測定方法)(Jpn.J.Appl.Phys.27(1988)2053、Asahi Grass Res.Res.Rep.127(1987)13等に記載)で補正し、平均光透過率を算出した。
シート抵抗は、4端子法で測定した。得られた基板を約3cm角に切り出し、切り出した基板の対向する2辺に、長さ3cmの一対の電極を電極間距離が3cmとなるように平行に取り付けた。次に、テスターで電極間の抵抗(シート抵抗)を測定した。
走査電子顕微鏡(SEM)(JSM−820、日本電子製)を用いてSnO2層表面の凹凸の高低差を測定し、ランダムに採取した10個の凹凸の高低差の平均を求めた。この結果を用いて、凹凸形状の均一性を以下の基準で評価した。
凹凸形状の高低差のばらつきが±10%超:不均一であり凸部の大きさは大きくばらついている。
凹凸の高低差のばらつきが±10%以内:比較的均一であった。
凹凸の高低差のばらつきが±5%以内:均一であった。
参考例1と同様の手順で、TiO2層、SiO2層およびSnO2層の層厚、ならびにフッ素濃度を表1に示す値に変えて太陽電池用透明導電性基板を製造して、物性評価を実施した。結果を表1に示した。
SiO2層およびSnO2層の層厚ならびにフッ素濃度を表1に示す値に変えて、かつガラス製の基体上にTiO2層を形成することなしに、参考例1と同様の手順で太陽電池用透明導電性基板を製造して、物性評価を実施した。結果を表1に示した。
比較例1〜3と同様に、SiO2層およびSnO2層の層厚ならびにフッ素濃度を表1に示す値とし、ガラス製の基体上にTiO2層を形成することなしに、太陽電池用透明導電性基板を製造した。但し、SnO2層を形成する際に、基体の移動方向に対して上流側と下流側とで、四塩化錫と水との混合比(上流側、下流側ともに、四塩化錫:水=1:100)を変えずに原料ガス(四塩化錫、水およびフッ化水素含有)を基体表面に吹き付けた。
TiO2層およびSnO2層の層厚ならびにフッ素濃度を表1に示す値に変えて、かつSiO2層を形成することなしに、参考例1と同様の手順で太陽電池用透明導電性基板を製造して、物性評価を実施した。結果を表1に示した。
2:基体
3:TiO2層
4:SiO2層
5:SnO2層
6:第1の光電変換層(アモルファスシリコン)
7:第2の光電変換層(結晶性シリコン)
8:裏面電極層
10:太陽電池(タンデム構造)
Claims (5)
- 基体上に、TiO2層、SiO2層およびSnO2層が前記基体側からこの順に形成されており、
前記TiO2層は、層厚が12nmであり、
前記TiO2層の算術平均粗さ(Ra)が1nm以下であり、
前記SiO2層は、層厚が32nmであり、
前記SiO2層の算術平均粗さ(Ra)が1nm以下であり、
前記SnO2層の層厚は、0.7μmであり、
前記SnO2層の表面に凹凸が形成されており、前記凹凸は、高低差が0.25μmであって、かつ、該凹凸の高低差のばらつきが±5%以内であり、
前記凹凸における凸部間のピッチは0.3〜0.45μmであり、
C光源ヘイズ率が25%であり、
基板全面に分布する10箇所において、C光源ヘイズ率を基板の長手方向に10mm間隔でヘイズメータで測定した際に、ヘイズ率の測定値における最大値と、最小値との差が3%以下であり、
400〜1200nmの波長領域の平均光透過率が89%であることを特徴とする太陽電池用透明導電性基板。 - 前記SnO 2 層は、導電電子密度が5×10 19 〜4×10 20 cm -3 である請求項1に記載の太陽電池用透明導電性基板。
- 前記SnO 2 層は、シート抵抗が10Ω/□である請求項1または2に記載の太陽電池用透明導電性基板。
- 請求項1〜3のいずれかに記載の太陽電池用透明導電性基板を用いた太陽電池。
- 請求項1〜3のいずれかに記載の太陽電池用透明導電性基板を用いたタンデム構造の太陽電池。
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EP3105193B1 (en) * | 2014-02-11 | 2020-08-12 | Pilkington Group Limited | Coated glass article and display assembly made therewith |
WO2016075435A1 (en) * | 2014-11-12 | 2016-05-19 | Pilkington Group Limited | Coated glass article, display assembly made therewith and method of making a display assembly |
WO2016132131A1 (en) | 2015-02-19 | 2016-08-25 | Pilkington Group Limited | A chemical vapour deposition process for depositing an iron doped tin oxide coating and a coated glass article formed thereby |
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Also Published As
Publication number | Publication date |
---|---|
EP1624494A1 (en) | 2006-02-08 |
WO2004102677A1 (ja) | 2004-11-25 |
JPWO2004102677A1 (ja) | 2006-07-13 |
US20060065299A1 (en) | 2006-03-30 |
JP5088435B2 (ja) | 2012-12-05 |
EP1624494A4 (en) | 2007-10-10 |
JP2011181975A (ja) | 2011-09-15 |
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