JP5583097B2 - 透明電極積層体 - Google Patents
透明電極積層体 Download PDFInfo
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- JP5583097B2 JP5583097B2 JP2011211012A JP2011211012A JP5583097B2 JP 5583097 B2 JP5583097 B2 JP 5583097B2 JP 2011211012 A JP2011211012 A JP 2011211012A JP 2011211012 A JP2011211012 A JP 2011211012A JP 5583097 B2 JP5583097 B2 JP 5583097B2
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- 239000010410 layer Substances 0.000 claims description 76
- 229910052751 metal Inorganic materials 0.000 claims description 71
- 239000002184 metal Substances 0.000 claims description 71
- 239000002070 nanowire Substances 0.000 claims description 70
- 239000000758 substrate Substances 0.000 claims description 60
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 48
- 239000002042 Silver nanowire Substances 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 238000002834 transmittance Methods 0.000 claims description 31
- 229910021389 graphene Inorganic materials 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000000411 transmission spectrum Methods 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 238000002835 absorbance Methods 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000002356 single layer Substances 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 8
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- LPSWFOCTMJQJIS-UHFFFAOYSA-N sulfanium;hydroxide Chemical compound [OH-].[SH3+] LPSWFOCTMJQJIS-UHFFFAOYSA-N 0.000 description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 229910010272 inorganic material Inorganic materials 0.000 description 3
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- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000001755 magnetron sputter deposition Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 2
- 229940056910 silver sulfide Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
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- 229920002799 BoPET Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical class O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
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- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical class [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
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- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
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- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
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- H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic System
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- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
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Description
透明基板11として厚さ0.4mmのガラス基板を用いて、図1に示す構成の透明電極積層体を作製する。電極層13の材料としては、平均直径115nmの銀ナノワイヤーのメタノール分散液を用いる。分散液中における銀ナノワイヤーの濃度は、0.3質量%程度である。銀ナノワイヤーは、Seashell Technology社製の、平均直径115nmのものを用いる。
硫黄蒸気で処理しない以外は実施例1と同様にして、本比較例の透明電極積層体を作製する。本比較例の透明電極積層体の写真を図6に示す。白濁が確認されており、光散乱が大きいことがわかる。得られた透明電極積層体は、スペキュラー透過率が73%(550nm)であり、表面抵抗は6Ω/□である。
透明基板11としてポリメチルメタクリレート(PMMA)基板を用いて、図3に示す構成の透明電極積層体を作製する。電極層13の材料としては、平均直径60nmの銀ナノワイヤーのメタノール分散液を用いる。分散液中における銀ナノワイヤーの濃度は、0.3質量%程度である。ここでの銀ナノワイヤーは、Seashell Technology社製のものである。
硫黄蒸気で処理しない以外は実施例2と同様にして、本比較例の透明電極積層体を作製する。得られた透明電極積層体は、スペキュラー透過率が92%(550nm)であり、表面抵抗は30Ω/□であるものの、比較例1の場合と同程度の白濁が確認される。したがって、本比較例の透明電極積層体は、光散乱は抑制されていない。
透明基板11として厚さ0.5mmのガラス基板を用いて、図1に示す構成の透明電極積層体を作製する。電極層13の材料としては、平均直径90nmの銅ナノワイヤーのメタノール分散液を用いる。分散液中における銅ナノワイヤーの濃度は、0.2質量%程度である。銅ナノワイヤーは、特開2004−263318号公報に基いて作製する。
硫黄蒸気で処理しない以外は実施例3と同様にして、本比較例の透明電極積層体を作製する。本比較例の透明電極積層体は、スペキュラー透過率が60%(550nm)であり、表面抵抗は30Ω/□であるものの、比較例1と同程度の白濁が生じて光散乱が大きい。
実施例1と同様にして、銀ナノワイヤーの三次元網目構造をガラス基板上に形成する。銀ナノワイヤーの三次元網目構造が形成されたガラス基板をUVオゾン洗浄装置に収容し、UVを照射しつつ、銀ナノワイヤーをオゾン蒸気と10分間反応させる。ここで用いるUV光源は低圧水銀灯であり、オゾン蒸気は空気中の酸素の反応により発生させる。銀ナノワイヤー表面の一部が酸化して、本実施例の透明電極積層体が得られる。透明電極積層体における電極層の厚さは、200nm程度である。
実施例1と同様にして、銀ナノワイヤーの三次元網目構造をガラス基板上に形成する。銀ナノワイヤーの三次元網目構造が形成されたガラス基板をガラス製反応容器に収容し、室温下、銀ナノワイヤーを塩素・窒素の混合ガスと10分間反応させる。銀ナノワイヤー表面の一部が塩化して、本実施例の透明電極積層体が得られる。透明電極積層体における電極層の厚さは、200nm程度である。
まず、Cu箔を下地触媒層として用いて、窒素置換された単層グラフェンをCVD法により作製する。反応ガスとして、アンモニア、メタン、水素、およびアルゴンの(15:60:65:200ccm)混合ガスを用い、1000℃で5分間のCVDを行なう。得られるグラフェンのほとんどは単層グラフェンであるが、条件によっては、一部に二層またはこれ以上の多層のグラフェンも生成する。
実施例1と同様の銀ナノワイヤーのメタノール分散液を用意し、以下のような手法により銀ナノワイヤーの表面の一部を硫化させる。まず、硫化鉄に希硫酸を反応させて、発生する硫化水素ガスを純水に溶解させ硫化水素水を得る。メススリンダーを用いて、硫化水素水を銀ナノワイヤーのメタノール分散液に加え、オイルバスにより分散液の温度を40℃に高めて反応させる。5分後、銀ナノワイヤーの表面の一部が硫化して反応生成物(硫化銀)が生じる。
実施例3と同様の銅ナノワイヤーのメタノール分散液を用意し、以下のような手法により銅ナノワイヤーの表面の一部を硫化させる。まず、硫化鉄に希硫酸を反応させて、発生する硫化水素ガスを純水に溶解させ硫化水素水を得る。メスシリンダーを用いて、硫化水素水を銅ナノワイヤーのメタノール分散液に加え、オイルバスにより分散液の温度を40℃に高めて反応させる。3分後、銅ナノワイヤーの表面の一部が硫化して反応生成物(硫化銅)が生じる。
12…反応抑制層; 13…電極層; 21…金属ナノワイヤー
22…三次元網目構造; 23…反応生成物; 24…空隙。
Claims (5)
- 透明基板と、
前記透明基板上に形成された光透過性の電極層とを具備し、
前記電極層は、直径が20nm以上200nm以下の銀ナノワイヤーの三次元網目構造を含み、それぞれの銀ナノワイヤーは表面の一部に、硫化物、酸化物、およびハロゲン化物から選択される反応生成物を有し、スペキュラー透過スペクトルにおいて320nm近傍の透過率極大ピークと350nm近傍の透過率極小ピークとの吸光度比が2.5以下であることを特徴とする透明電極積層体。 - 透明基板と、
前記透明基板上に形成された光透過性の電極層とを具備し、
前記電極層は、直径が20nm以上200nm以下の銀または銅からなる金属ナノワイヤーの三次元網目構造を含み、それぞれの金属ナノワイヤーは表面の一部に、前記金属ナノワイヤーを構成する金属のハロゲン化物を有することを特徴とする透明電極積層体。 - 前記ハロゲン化物は塩化物であることを特徴とする請求項2に記載の透明電極積層体。
- 前記電極層は、前記三次元網目構造の少なくとも一方の面に設けられた単層グラフェンおよび/または多層グラフェンを含有するカーボン層をさらに具備することを特徴とする請求項1及至3記載のいずれか1項に記載の透明電極積層体。
- 前記単層グラフェンおよび/または多層グラフェンは窒素がドーピングされていることを特徴とする請求項4に記載の透明電極積層体。
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