JP3194012B2 - Ultraviolet transparent electric conductor - Google Patents
Ultraviolet transparent electric conductorInfo
- Publication number
- JP3194012B2 JP3194012B2 JP08523199A JP8523199A JP3194012B2 JP 3194012 B2 JP3194012 B2 JP 3194012B2 JP 08523199 A JP08523199 A JP 08523199A JP 8523199 A JP8523199 A JP 8523199A JP 3194012 B2 JP3194012 B2 JP 3194012B2
- Authority
- JP
- Japan
- Prior art keywords
- electric conductor
- ultraviolet
- present
- transparent electric
- thin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004020 conductor Substances 0.000 title description 13
- 239000000463 material Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000002950 deficient Effects 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- -1 tin-substituted indium oxide Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、3〜4eVの領域の紫
外光を透過させることができるとともに、高い電気伝導
性を有する酸化物材料からなる紫外光透明電気伝導体に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet transparent electric conductor made of an oxide material having a high electric conductivity and capable of transmitting ultraviolet light in a range of 3 to 4 eV.
【０００２】[0002]
【従来の技術】従来、透明伝導性薄膜材料としては、酸
化インジウム、二酸化スズ、酸化亜鉛などが広く用いら
れている。これらの材料は、いずれも可視域の光子エネ
ルギー(1.6-3.2eV)にほぼ一致する光透過領域を有して
おり、その電気伝導度の典型値は、103Scm-1である。し
かしながら、これらの材料では、紫外光(3-4eV)の透過
率が低いという問題点がある。2. Description of the Related Art Conventionally, indium oxide, tin dioxide, zinc oxide and the like have been widely used as transparent conductive thin film materials. Each of these materials has a light transmission region substantially matching the photon energy (1.6-3.2 eV) in the visible region, and a typical value of the electric conductivity is 10 3 Scm −1 . However, these materials have a problem that the transmittance of ultraviolet light (3-4 eV) is low.
【０００３】透過波長の短波長化を図るために、酸化イ
ンジウムにスズを大量に導入したスズ置換酸化インジウ
ムが、使用されている。しかしながら、この材料におい
ても、透過領域の上限は、3.5eV程度にとどまってい
る。[0003] In order to shorten the transmission wavelength, tin-substituted indium oxide obtained by introducing a large amount of tin into indium oxide is used. However, also in this material, the upper limit of the transmission region is about 3.5 eV.
【０００４】[0004]
【発明が解決しようとする課題】従って、本発明は、紫
外光域にまで透過領域を広げた透明伝導性材料を提供す
ることを主な目的とする。SUMMARY OF THE INVENTION Accordingly, it is a main object of the present invention to provide a transparent conductive material whose transmission region is extended to an ultraviolet region.
【０００５】[0005]
【課題を解決するための手段】本発明者は、上記の様な
技術の現状に鑑みて研究を進めた結果、特定の組成式で
示される金属酸化物薄膜が、3〜4eVの領域の紫外光を透
過させることができるとともに、高い電気伝導性を有し
ていることを見出した。Means for Solving the Problems The present inventor has conducted research in view of the current state of the art as described above. They have found that they can transmit light and have high electrical conductivity.
【０００６】すなわち、本発明は、下記の紫外光透明電
気伝導体を提供するものである： １．組成式RMoO3 （１） (RはCa、SrおよびBaの少なくとも１種である)で示され
るペロブスカイト型結晶構造材料からなる紫外光透明電
気伝導性体。 ２．組成式NaxWO3 （２） (0.3≦x≦1である)で示されるNaサイト欠損ペロブスカ
イト型結晶構造材料からなる紫外光透明電気伝導性体。That is, the present invention provides the following ultraviolet light transparent electric conductor: An ultraviolet light transparent electric conductor comprising a perovskite-type crystal structure material represented by a composition formula RMoO 3 (1) (R is at least one of Ca, Sr and Ba). 2. An ultraviolet-light transparent electric conductor comprising a Na-site-deficient perovskite-type crystal structure material represented by a composition formula of Na x WO 3 (2) (where 0.3 ≦ x ≦ 1).
【０００７】[0007]
【発明の実施の形態】本発明による紫外光透明電気伝導
体は、組成式RMoO3により示されるペロブスカイト型結
晶構造材料ならび組成式NaxWO3により示されるNaサイト
欠損ペロブスカイト型結晶構造材料からなる。BEST MODE FOR CARRYING OUT THE INVENTION The transparent ultraviolet light conductor according to the present invention comprises a perovskite-type crystal structure material represented by a composition formula RMoO 3 and a Na-site-deficient perovskite-type crystal structure material represented by a composition formula Na x WO 3. .
【０００８】組成式RMoO3(1)で示される本発明材料にお
いて、Rは、Ca、SrおよびBaの少なくとも１種であり、
その結晶構造は、ペロブスカイト型である。In the material of the present invention represented by the composition formula RMoO 3 (1), R is at least one of Ca, Sr and Ba;
Its crystal structure is a perovskite type.
【０００９】また、組成式NaxWO3(2)で示される本発明
材料においても、その結晶構造は、Naサイト欠損ペロブ
スカイト型である。Further, also in the material of the present invention represented by the composition formula Na x WO 3 (2), the crystal structure is a Na site-deficient perovskite type.
【００１０】上記組成式(1)および(2)で示されるペロブ
スカイト型結晶構造材料またはNaサイト欠損ペロブスカ
イト型結晶構造材料の製造方法は、特に制限されず、目
的とする用途乃至形態に応じて、公知の高周波マグネト
ロンスパッタリング法、真空蒸着法などにより適宜製造
することができる。製造条件の相違に関わりなく、上記
の組成と結晶構造とを有する限り、本発明の紫外光透明
電気伝導体が得られる。The method for producing the perovskite-type crystal structure material or the Na-site-deficient perovskite-type crystal structure material represented by the above-mentioned composition formulas (1) and (2) is not particularly limited, and may be selected according to the intended use or form. It can be appropriately manufactured by a known high-frequency magnetron sputtering method, vacuum evaporation method, or the like. Irrespective of the difference in the manufacturing conditions, the ultraviolet transparent electric conductor of the present invention can be obtained as long as it has the above composition and crystal structure.
【００１１】より具体的に、例えば、高周波マグネトロ
ンスパッタリング法によりSrMoO3からなる本発明の紫外
光透明電気伝導性体を製造する場合の条件の一例は、下
記表１の通りである。More specifically, for example, the conditions for producing the ultraviolet transparent electric conductor of the present invention comprising SrMoO 3 by high frequency magnetron sputtering are shown in Table 1 below.
【００１２】[0012]
【表１】 [Table 1]
【００１３】また、高周波マグネトロンスパッタリング
法によりNaxWO3からなる本発明の紫外光透明電気伝導性
体を製造する場合の条件の一例は、下記表２の通りであ
る。Table 2 below shows an example of conditions for producing the ultraviolet transparent electric conductor of the present invention comprising Na x WO 3 by a high-frequency magnetron sputtering method.
【００１４】[0014]
【表２】 [Table 2]
【００１５】さらに、真空蒸着法によりNaxWO3からなる
本発明の紫外光透明電気伝導性体を製造する場合の条件
の一例は、下記表３の通りである。Further, an example of the conditions for producing the ultraviolet light transparent electric conductor of the present invention comprising Na x WO 3 by a vacuum evaporation method is shown in Table 3 below.
【００１６】[0016]
【表３】 [Table 3]
【００１７】本発明による紫外光透過可能な透明伝導性
酸化物材料は、注入電子の濃度調整により、2〜4eVの領
域内で光透過領域を制御することができ、電気伝導度
は、約1E+4Scm-1にも達する。The transparent conductive oxide material capable of transmitting ultraviolet light according to the present invention can control the light transmission region within the range of 2 to 4 eV by adjusting the concentration of injected electrons, and has an electric conductivity of about 1E. It reaches + 4Scm -1 .
【００１８】[0018]
【発明の効果】本発明による紫外光透明電気伝導材料薄
膜は、添加イオンの量により、電気伝導度のみならず、
光透過波長領域を制御することができる。特に、その電
気伝導度は、従来の透明伝導度材料に比して、約1E+4Sc
m-1と大きいので、より薄い膜厚での実用化が可能とな
る。According to the ultraviolet transparent electroconductive material thin film of the present invention, not only the electrical conductivity but also the
The light transmission wavelength region can be controlled. In particular, its electrical conductivity is about 1E + 4Sc compared to conventional transparent conductive materials.
Since it is as large as m- 1 , practical use with a thinner film thickness is possible.
【００１９】従って、本発明による紫外光透明電気伝導
材料は、液晶ディスプレイ、光電効果を利用する太陽電
池、光伝導セルなどの窓材、光学バンドパスフィルタな
どとして有用である。Therefore, the ultraviolet transparent electric conductive material according to the present invention is useful as a liquid crystal display, a window material such as a solar cell utilizing a photoelectric effect, a photoconductive cell, and an optical bandpass filter.
【００２０】[0020]
【実施例】以下に実施例を示し、本発明の特徴とすると
ころをより一層明確にする。 実施例１ 高周波マグネトロンスパッタリング法により、シリカガ
ラス基板上にRサイト欠損ペロブスカイト型構造材料と
してNaxWO3薄膜を形成させた。高周波マグネトロンスパ
ッタリング法による薄膜形成条件は、前記表１に示すと
おりであった。EXAMPLES Examples are shown below to further clarify the features of the present invention. Example 1 A Na x WO 3 thin film was formed as an R-site-deficient perovskite structure material on a silica glass substrate by a high-frequency magnetron sputtering method. The conditions for forming the thin film by the high-frequency magnetron sputtering method were as shown in Table 1 above.
【００２１】得られた薄膜(0.15〜0.25μm)について、
分光光度計により光吸収を測定し、直流４端子法により
電気伝導度を測定した。測定は、いずれも室温で行っ
た。光吸収の測定結果を図１に示し、電気伝導度の測定
結果を図２に示す。With respect to the obtained thin film (0.15-0.25 μm),
The light absorption was measured by a spectrophotometer, and the electric conductivity was measured by a DC four-terminal method. All measurements were performed at room temperature. FIG. 1 shows the measurement result of the light absorption, and FIG. 2 shows the measurement result of the electric conductivity.
【００２２】図１から明らかな通り、NaxWO3に大量に電
子を注入することにより、可視域から紫外域にかけて、
約1eVの幅で103〜104cm-1という低い吸収係数を示す。
すなわち、Na添加量によりキャリア濃度を制御すること
により、約2〜4eVの光子エネルギー範囲内で透過領域の
位置を制御することができる。例えば、Na0.9WO3薄膜に
おいて、電子注入を行った場合には、約4eVまで透過領
域が平行移動している。As is clear from FIG. 1, by injecting a large amount of electrons into Na x WO 3 , from the visible region to the ultraviolet region,
It exhibits a low absorption coefficient of 10 3 to 10 4 cm −1 with a width of about 1 eV.
That is, by controlling the carrier concentration by the amount of added Na, the position of the transmission region can be controlled within the photon energy range of about 2 to 4 eV. For example, when electron injection is performed on a Na 0.9 WO 3 thin film, the transmissive region moves parallel to about 4 eV.
【００２３】また、Na添加量の増大にほぼ比例して、電
気伝導度が増大し、Na0.9WO3薄膜においては、6E+4Scm
-1にも達している。 実施例２ 実施例１の手法に準じて、ペロブスカイト型構造を有す
る材料として、シリカガラス基板上にそれぞれCaMoO3、
SrMoO3およびBaMoO3の薄膜を形成させた。In addition, the electric conductivity increases almost in proportion to the increase in the amount of added Na, and in the Na 0.9 WO 3 thin film, 6E + 4 Scm
It has reached -1 . Example 2 According to the method of Example 1, as a material having a perovskite structure, CaMoO 3 ,
SrMoO 3 and BaMoO 3 thin films were formed.
【００２４】得られたSrMoO3薄膜(約0.25μm)につい
て、分光光度計により光吸収を測定し、直流４端子法に
より電気伝導度を測定した。測定は、いずれも室温で行
った。With respect to the obtained SrMoO 3 thin film (about 0.25 μm), light absorption was measured by a spectrophotometer, and electric conductivity was measured by a DC four-terminal method. All measurements were performed at room temperature.
【００２５】得られたSrMoO3薄膜は、図３から明らかな
通り、2.1〜3.5eVの光子エネルギー域に光透過領域を有
しており、電気伝導度は、8E+3Scm-1であった。As is clear from FIG. 3, the obtained SrMoO 3 thin film has a light transmission region in a photon energy region of 2.1 to 3.5 eV, and has an electric conductivity of 8E + 3 Scm −1 .
【００２６】また、これらの薄膜は、硝酸水溶液に容易
に溶解するので、用途に応じてエッチングに供すること
ができる。Further, since these thin films are easily dissolved in a nitric acid aqueous solution, they can be subjected to etching depending on the application.
【図１】実施例１で得られたNaxWO3薄膜において、光吸
収スペクトルにおよぼすNa量の影響を示すグラフであ
る。FIG. 1 is a graph showing the influence of the amount of Na on the light absorption spectrum of the Na x WO 3 thin film obtained in Example 1.
【図２】実施例１で得られたNaxWO3薄膜において、電気
伝導度におよぼすNa量の影響を示すグラフである。FIG. 2 is a graph showing the effect of the amount of Na on electric conductivity in the Na x WO 3 thin film obtained in Example 1.
【図３】実施例２で得られたSrMoO3薄膜による光吸収ス
ペクトルを示すグラフである。FIG. 3 is a graph showing a light absorption spectrum of a SrMoO 3 thin film obtained in Example 2.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 早川 惇二 大阪府池田市緑丘１丁目８番31号 工業 技術院大阪工業技術研究所内 (72)発明者 西井 準治 大阪府池田市緑丘１丁目８番31号 工業 技術院大阪工業技術研究所内 審査官 大工原 大二 (56)参考文献 Ｅｌｅｃｔｒｏｃｈｉｍ．Ａｃｔａ, 22，751−759（1977) 日本化学会編「ペロブスカイト関連化 合物−機能の宝庫［季刊 化学総説 Ｎ ｏ．32］」（1997年７月10日）学会出版 センターｐ178−181 (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 39/00 C01G 41/00 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Junji Hayakawa 1-8-31 Midorioka, Ikeda-shi, Osaka Inside the Industrial Research Institute, Osaka Institute of Technology (72) Junji Nishii 1-8-8 Midorioka, Ikeda-shi, Osaka No. 31 Examiner, Osaka Institute of Technology, Industrial Technology Institute Daiji Daikohara (56) Reference Electrochim. Acta, 22, 751-759 (1977) The Chemical Society of Japan, edited by the Chemical Society of Japan, “Perovskite-Related Compounds—A Treasury of Functions [Quarterly Review of Chemistry No. 32]” (July 10, 1997), Gakkai Shuppan Center, p178-181 (58 ) Field surveyed (Int. Cl. 7 , DB name) C01G 39/00 C01G 41/00 CA (STN)
Claims (1)
光透明電気伝導材料。1. An ultraviolet transparent electroconductive material comprising a perovskite type crystal structure material represented by a composition formula RMoO 3 (1) (R is at least one of Ca, Sr and Ba).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08523199A JP3194012B2 (en) | 1999-03-29 | 1999-03-29 | Ultraviolet transparent electric conductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08523199A JP3194012B2 (en) | 1999-03-29 | 1999-03-29 | Ultraviolet transparent electric conductor |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000386379A Division JP2001253716A (en) | 2000-12-20 | 2000-12-20 | Ultraviolet transparent electric conductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000281346A JP2000281346A (en) | 2000-10-10 |
| JP3194012B2 true JP3194012B2 (en) | 2001-07-30 |
Family
ID=13852801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08523199A Expired - Lifetime JP3194012B2 (en) | 1999-03-29 | 1999-03-29 | Ultraviolet transparent electric conductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3194012B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9659681B2 (en) | 2013-11-01 | 2017-05-23 | Samsung Electronics Co., Ltd. | Transparent conductive thin film |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100786855B1 (en) * | 2001-08-24 | 2007-12-20 | 삼성에스디아이 주식회사 | Solar cell using ferroelectric |
| US20150153478A1 (en) | 2007-04-18 | 2015-06-04 | Sumitomo Metal Mining Co., Ltd. | Electroconductive particle, visible light transmitting particle-dispersed electrical conductor and manufacturing method thereof, transparent electroconductive thin film and manufacturing method thereof, transparent electroconductive article that uses the same, and infrared-shielding article |
| EP1801815B1 (en) | 2004-08-31 | 2020-01-01 | Sumitomo Metal Mining Co., Ltd. | Infrared-shielding article and method for producing it |
| CN101023498B (en) * | 2004-08-31 | 2012-02-29 | 住友金属矿山株式会社 | Conductive particle, visible light transmissive particle dispersed conductor, method for producing same, transparent conductive thin film, method for producing same, transparent conductive article using same, infrared shield article |
| JP4552940B2 (en) * | 2004-10-01 | 2010-09-29 | 株式会社村田製作所 | Hybrid lens using translucent ceramic |
| US10629321B2 (en) | 2014-04-09 | 2020-04-21 | Cornell University | Misfit p-type transparent conductive oxide (TCO) films, methods and applications |
| CN109928751A (en) * | 2019-03-21 | 2019-06-25 | 中国科学院宁波材料技术与工程研究所 | A kind of SrMoO3The preparation method of ceramic target |
-
1999
- 1999-03-29 JP JP08523199A patent/JP3194012B2/en not_active Expired - Lifetime
Non-Patent Citations (2)
| Title |
|---|
| Ｅｌｅｃｔｒｏｃｈｉｍ．Ａｃｔａ，２２，７５１−７５９（１９７７） |
| 日本化学会編「ペロブスカイト関連化合物−機能の宝庫［季刊 化学総説 Ｎｏ．３２］」（１９９７年７月１０日）学会出版センターｐ１７８−１８１ |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9659681B2 (en) | 2013-11-01 | 2017-05-23 | Samsung Electronics Co., Ltd. | Transparent conductive thin film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000281346A (en) | 2000-10-10 |
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