JP3079262B2 - Transparent conductive thin film and method for producing the same - Google Patents
Transparent conductive thin film and method for producing the sameInfo
- Publication number
- JP3079262B2 JP3079262B2 JP11026139A JP2613999A JP3079262B2 JP 3079262 B2 JP3079262 B2 JP 3079262B2 JP 11026139 A JP11026139 A JP 11026139A JP 2613999 A JP2613999 A JP 2613999A JP 3079262 B2 JP3079262 B2 JP 3079262B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- transparent conductive
- conductive thin
- temperature
- lanio
- 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
- 239000010409 thin film Substances 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000000758 substrate Substances 0.000 claims description 31
- 241000877463 Lanio Species 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 238000002834 transmittance Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 150000002603 lanthanum Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 description 30
- 239000000919 ceramic Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
- Laminated Bodies (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electrodes Of Semiconductors (AREA)
- Conductive Materials (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規な透明導電性
薄膜及びその製造方法に関する。さらに詳しくは、本発
明は、常温から高温までの広い温度範囲において、良好
な導電性を有するとともに、広い波長領域の光に対して
均等な透光性を有し、機能性薄膜として種々の用途に有
用な透明導電性薄膜、及びこのものを効率よく製造する
方法に関するものである。The present invention relates to a novel transparent conductive thin film and a method for producing the same. More specifically, the present invention has good conductivity in a wide temperature range from room temperature to high temperature, has uniform light transmittance to light in a wide wavelength range, and has various uses as a functional thin film. The present invention relates to a transparent conductive thin film useful for the above, and a method for efficiently producing the same.
【０００２】[0002]
【従来の技術】従来、透明導電性薄膜として、ＩＴＯ
（Ｉｎｄｉｕｍ ａｎｄ ｔｉｎ ｏｘｉｄｅｓ、Ｉｎ
２Ｏ３とＳｎＯ２との混合体）薄膜が実用化され、電子
デバイスや光学デバイスの電極として用いられている。
しかしながら、この薄膜は、耐熱性に劣り、５００℃以
上の温度では機能しない上、光の透過性についても選択
的透過現象がみられ、３４０〜８００ｎｍの波長領域で
は、特に光の吸収により５００ｎｍ付近の透光性が低い
などの欠点を有している。これまで、高温領域におい
て、良好な導電性と透光性を有する薄膜は知られていな
いのが実状である。2. Description of the Related Art Conventionally, ITO has been used as a transparent conductive thin film.
(Indium and tin oxides, In
Mixtures of 2 O 3 and SnO 2 ) thin films have been put to practical use and used as electrodes for electronic devices and optical devices.
However, this thin film is inferior in heat resistance, does not function at a temperature of 500 ° C. or more, and has a selective transmission phenomenon with respect to light transmittance. In the wavelength region of 340 to 800 nm, especially around 500 nm due to light absorption. Has a drawback such as low light transmittance. Until now, there is no known thin film having good conductivity and light-transmitting properties in a high-temperature region.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、常温から高温までの広い温度範囲におい
て、良好な導電性を有するとともに、広い波長領域の光
に対して均一の透光性を有し、機能性薄膜として種々の
用途に有用な新規な透明導電性薄膜を提供することを目
的としてなされたものである。Under such circumstances, the present invention has good conductivity in a wide temperature range from room temperature to high temperature and has a uniform property with respect to light in a wide wavelength range. The object of the present invention is to provide a novel transparent conductive thin film which has a light transmitting property and is useful as a functional thin film for various uses.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、透明導電
性薄膜について鋭意研究を重ねた結果、ペロブスカイト
型構造を有するＬａＮｉＯ３薄膜は、良好な導電性を有
し、膜厚を変えることにより、広い波長領域にわたって
透光率を調整することができること、そして、この透明
導電性薄膜は、ランタン塩とニッケル塩と有機バインダ
ーを溶解させてなる水性塗布液を基材上に塗布し、酸素
雰囲気下、特定の温度で焼成し、この際膜厚が所定の範
囲になるように調整することにより製造しうることを見
出し、この知見に基づいて本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies on the transparent conductive thin film, the present inventors have found that a LaNiO 3 thin film having a perovskite structure has good conductivity and that the thickness thereof can be changed. Thus, the light transmittance can be adjusted over a wide wavelength range, and this transparent conductive thin film is formed by applying an aqueous coating solution obtained by dissolving a lanthanum salt, a nickel salt, and an organic binder onto a base material, It has been found that it can be manufactured by baking at a specific temperature in an atmosphere and adjusting the film thickness at this time to be within a predetermined range, and based on this finding, the present invention has been completed.
【０００５】すなわち、本発明は、ＬａＮｉＯ３の組成
を有するペロブスカイト型構造の金属酸化物からなり、
２０〜８００℃の温度における体積抵抗率が２×１０
−５Ω・ｍ以下、又は表面抵抗が３００Ω／□以下であ
ることを特徴とする透明導電性薄膜を提供するものであ
る。前記透明導電性薄膜は、本発明に従えば、ランタン
塩とニッケル塩と水溶性有機バインダーを溶解させた水
溶液からなる塗布液を調製したのち、基材上に該塗布液
を塗布し、次いで酸素雰囲気中において、５００〜８０
０℃の温度で焼成し、２０〜８００℃の温度における体
積抵抗率が２×１０−５Ω・ｍ以下、又は表面抵抗が３
００Ω／□以下になるように調整された膜厚のＬａＮｉ
Ｏ３の組成を有するペロブスカイト型構造の金属酸化物
からなる薄膜を形成させることにより、製造することが
できる。That is, the present invention comprises a metal oxide having a perovskite structure having a composition of LaNiO 3 ,
Volume resistivity at a temperature of 20 to 800 ° C. is 2 × 10
The present invention provides a transparent conductive thin film characterized by having a surface resistance of −5 Ω · m or less or a surface resistance of 300 Ω / □ or less. According to the present invention, the transparent conductive thin film is prepared by preparing a coating solution composed of an aqueous solution in which a lanthanum salt, a nickel salt and a water-soluble organic binder are dissolved, and then coating the coating solution on a substrate, and then applying oxygen. 500-80 in the atmosphere
It is fired at a temperature of 0 ° C. and has a volume resistivity of 2 × 10 −5 Ω · m or less or a surface resistance of 3 at a temperature of 20 to 800 ° C.
LaNi with a film thickness adjusted to be less than 00Ω / □
It can be manufactured by forming a thin film made of a metal oxide having a perovskite structure having a composition of O 3 .
【０００６】[0006]
【発明の実施の形態】本発明の透明導電性薄膜は、Ｌａ
ＮｉＯ３で表わされ、かつペロブスカイト型構造を有す
る金属酸化物からなるものであるが、このペロブスカイ
ト型構造とは、ＣａＴｉＯ３（灰チタン石）で代表され
るＡＢＯ３の組成をもつ化合物にみられる、立方晶系若
しくはそれが少し歪んだ正方晶系、斜方晶系、単斜晶
系、六方晶系の結晶構造を意味する。本発明の透明導電
性薄膜は、従来のＩＴＯ薄膜と異なり、室温（２０℃）
から８００℃の高温に至る温度範囲において、体積抵抗
率が２×１０−５Ω・ｍ以下、又は表面抵抗が３００Ω
／□以下という優れた導電性を示す。そして、本発明の
透明導電性薄膜においては、膜厚により、導電性及び透
光性を調整することができ、かつ、透光性については、
３００〜８００ｎｍの波長域において、実質上同一の透
光率とすることができる。また、膜厚を変えることによ
り、該透光率を１〜９５％の範囲で調整することができ
る。BEST MODE FOR CARRYING OUT THE INVENTION The transparent conductive thin film of the present invention is La
It is composed of a metal oxide represented by NiO 3 and having a perovskite structure. This perovskite structure refers to a compound having the composition of ABO 3 represented by CaTiO 3 (perovskite). Cubic, or a slightly distorted tetragonal, orthorhombic, monoclinic, or hexagonal crystal structure. The transparent conductive thin film of the present invention differs from the conventional ITO thin film at room temperature (20 ° C.).
In the temperature range from to a high temperature of 800 ° C., the volume resistivity is 2 × 10 −5 Ω · m or less, or the surface resistance is 300 Ω.
/ Excellent conductivity of not more than / □. And, in the transparent conductive thin film of the present invention, the conductivity and the light transmission can be adjusted by the film thickness, and the light transmission is
In the wavelength range of 300 to 800 nm, substantially the same light transmittance can be obtained. The light transmittance can be adjusted in the range of 1 to 95% by changing the film thickness.
【０００７】本発明方法により、前記の透明導電性薄膜
を製造するには、まずＬａＮｉＯ３膜形成用の塗布液を
調製する必要がある。この塗布液は、例えば水溶性のラ
ンタン塩とニッケル塩と有機バインダーを水媒体に溶解
させることにより調製される。この際用いる水溶性のラ
ンタン塩及びニッケル塩としては、水溶性のものであれ
ばよく特に制限はないが、酢酸塩及び硝酸塩が好適であ
る。また、このランタン塩とニッケル塩は、実質上化学
量論的量用いるのが好ましい。一方、有機バインダーと
しては、水溶性であって、塗膜形成能を有するものであ
ればよく、特に制限されず、例えばポリビニルアルコー
ル、ポリビニルピロリドン、カルボキシメチルセルロー
スなどを用いることができる。In order to produce the above-mentioned transparent conductive thin film by the method of the present invention, it is necessary to first prepare a coating liquid for forming a LaNiO 3 film. This coating solution is prepared, for example, by dissolving a water-soluble lanthanum salt, a nickel salt, and an organic binder in an aqueous medium. The water-soluble lanthanum salt and nickel salt used at this time are not particularly limited as long as they are water-soluble, but acetates and nitrates are preferred. Preferably, the lanthanum salt and the nickel salt are used in substantially stoichiometric amounts. On the other hand, the organic binder is not particularly limited as long as it is water-soluble and has a coating film forming ability, and for example, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose and the like can be used.
【０００８】この塗布液中のランタン塩とニッケル塩の
含有量は、所望のＬａＮｉＯ３膜の厚さに応じて適宜調
整されるが、一般には、ＬａＮｉＯ３換算で０．０５〜
５．０モル％、好ましくは０．１〜１．０モル％濃度に
なるように調整するのが有利である。この濃度が０．０
５モル％未満ではペロブスカイト型構造になりにくく、
所望の導電性を有する薄膜が得られにくいし、５．０モ
ル％を超えるとコーティングした塗膜が剥れやすくな
り、基材に対して十分な機械的付着強度を有する薄膜が
得られにくい。[0008] The content of lanthanum and nickel salts of the coating solution is suitably adjusted depending on the thickness of the desired LaNiO 3 film, typically, 0.05 in LaNiO 3 terms
It is advantageous to adjust the concentration to 5.0 mol%, preferably 0.1 to 1.0 mol%. This concentration is 0.0
If it is less than 5 mol%, it is difficult to form a perovskite structure,
It is difficult to obtain a thin film having the desired conductivity, and if it exceeds 5.0 mol%, the coated film tends to peel off, and it is difficult to obtain a thin film having sufficient mechanical adhesion strength to the substrate.
【０００９】次いで、このようにして調製した塗布液を
適当な基材上に、スピンコーティング法やディップコー
ティング法などの公知の方法によりコーティングし、塗
膜を形成させる。基材としては、塗布液に浸されず、か
つ焼成温度に耐えるものであればよく、特に制限され
ず、様々なものを用いることができる。このような基材
としては、例えばガラス、石英、Ｓｉ単結晶、Ａｌ２Ｏ
３単結晶、ＳｉＣセラミックス、Ａｌ２Ｏ３セラミック
ス、Ｓｉ３Ｎ４セラミックス、ステンレス鋼などからな
る基材を挙げることができる。また、コーティングは、
所望する膜厚によっては、複数回繰り返し行ってもよ
い。Next, the coating solution thus prepared is coated on a suitable substrate by a known method such as a spin coating method or a dip coating method to form a coating film. The substrate is not particularly limited as long as it is not immersed in the coating liquid and withstands the firing temperature, and various substrates can be used. As such a substrate, for example, glass, quartz, Si single crystal, Al 2 O
Substrates made of three single crystals, SiC ceramics, Al 2 O 3 ceramics, Si 3 N 4 ceramics, stainless steel, and the like can be given. Also, the coating
Depending on the desired film thickness, it may be repeated plural times.
【００１０】次に、このようにして基材上に設けられた
塗膜を、酸素雰囲気中において、５００〜８００℃の範
囲の温度において焼成する。この焼成温度が５００℃未
満ではペロブスカイト型構造が形成されず、所望の導電
性を有する薄膜が得られないし、８００℃を超えると基
材との反応が起こり、薄膜の導電性が低下する。また、
酸素雰囲気としては、酸素を含むガスであればよく特に
制限はないが、通常、空気が用いられる。焼成時間は、
焼成温度により左右され、一概に定めることはできない
が、一般的には１０〜６０分間程度で十分である。この
ようにして、ペロブスカイト型構造を有するＬａＮｉＯ
３からなる透明導電性薄膜が効率よく得られる。Next, the coating film thus formed on the substrate is fired in an oxygen atmosphere at a temperature in the range of 500 to 800 ° C. If the firing temperature is lower than 500 ° C., a perovskite structure is not formed, and a thin film having desired conductivity cannot be obtained. If the firing temperature exceeds 800 ° C., a reaction with the base material occurs, and the conductivity of the thin film decreases. Also,
The oxygen atmosphere is not particularly limited as long as it is a gas containing oxygen, but air is usually used. The firing time is
Although it depends on the firing temperature and cannot be unconditionally determined, generally about 10 to 60 minutes is sufficient. Thus, LaNiO having a perovskite structure is obtained.
3 can be efficiently obtained.
【００１１】[0011]
【発明の効果】本発明によれば、ペロブスカイト型構造
を有するＬａＮｉＯ３からなる透明導電性薄膜を効率よ
く製造することができる。この本発明の透明導電性薄膜
は、室温から８００℃程度の高温に至るまで、良好な導
電性を有するとともに、３００〜８００ｎｍの広い波長
領域の光に対して、実質上同一の透光率を示し、かつ膜
厚により、該透光率を１〜９５％の範囲で連続的に調整
しうるという利点がある。したがって、本発明の透明導
電性薄膜は、機能性薄膜として、例えば太陽電池や高温
電子デバイス、高温光学デバイスなどの電極として有用
である上、可視光領域の均一光フィルターとしての応用
などが期待できる。According to the present invention, a transparent conductive thin film made of LaNiO 3 having a perovskite structure can be efficiently produced. The transparent conductive thin film of the present invention has good conductivity from room temperature to a high temperature of about 800 ° C., and has substantially the same light transmittance for light in a wide wavelength range of 300 to 800 nm. There is an advantage that the light transmittance can be continuously adjusted within the range of 1 to 95% depending on the film thickness. Therefore, the transparent conductive thin film of the present invention is useful as a functional thin film, for example, as an electrode of a solar cell, a high-temperature electronic device, a high-temperature optical device, and can be expected to be applied as a uniform light filter in a visible light region. .
【００１２】[0012]
【実施例】次に、本発明を実施例によりさらに詳細に説
明するが、本発明は、これらの例によってなんら限定さ
れるものではない。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００１３】実施例１ 酢酸ランタン及び硝酸ニッケルを、それぞれ純水に溶解
させてなる２種の水溶液を均質に混合したのち、これに
有機バインダーとしてポリビニルアルコールを、酢酸ラ
ンタンと硝酸ニッケルの合計重量に対し、０．０１倍量
添加し、さらに、水溶液のＬａＮｉＯ３換算濃度が０．
１モル％になるように調整することにより、塗布液を調
製した。次に、石英基板上に、上記塗布液を回転数２０
００ｒｐｍにて、１回のコーティングで焼成後の膜厚が
１５ｎｍになるようにスピンコーティングしたのち、空
気中にて５００℃で１時間焼成し、膜厚１５ｎｍのペロ
ブスカイト型構造のＬａＮｉＯ３膜を形成した。さら
に、上記と同様のスピンコーティングを繰り返し行い、
各種膜厚のペロブスカイト型構造のＬａＮｉＯ３膜を形
成した。Example 1 Two kinds of aqueous solutions each prepared by dissolving lanthanum acetate and nickel nitrate in pure water were mixed homogeneously, and then polyvinyl alcohol was added as an organic binder to the total weight of lanthanum acetate and nickel nitrate. On the other hand, a 0.01-fold amount was added, and the LaNiO 3 conversion concentration of the aqueous solution was 0.1.
The coating liquid was prepared by adjusting to 1 mol%. Next, the above-mentioned coating solution was applied on a quartz substrate at a rotation speed of 20
After spin-coating at 00 rpm with a single coating so that the film thickness after firing becomes 15 nm, it is fired in air at 500 ° C. for 1 hour to form a LaNiO 3 film having a perovskite structure with a film thickness of 15 nm. did. Furthermore, the same spin coating as above is repeated,
LaNiO 3 films having a perovskite structure having various thicknesses were formed.
【００１４】膜厚１５〜３００ｎｍのＬａＮｉＯ３膜に
ついて、各温度における体積抵抗率と表面抵抗を測定す
ると共に、各膜厚のＬａＮｉＯ３膜について、各波長に
おける透光率を測定した。図１に、膜厚２００ｎｍのＬ
ａＮｉＯ３膜における温度と表面抵抗との関係をグラフ
として示す。表面抵抗は、室温（２０℃）から８００℃
まで３００Ω／□以下であり、また体積抵抗率は２×１
０−５Ω・ｍ以下であった。図２に、各膜厚のＬａＮｉ
Ｏ３膜における波長と透光率との関係をグラフとして示
す。３４０〜８００ｎｍの広い波長領域の光に対し、均
一な透光率を有することが分かる。図３に、ＬａＮｉＯ
３膜における波長６００ｎｍの光に対する透光率との関
係を実線でグラフとして示す。ＬａＮｉＯ３膜の膜厚を
調整することにより、透光率を１０〜９０％程度の範囲
で連続的に調整しうることが分かる。With respect to the LaNiO 3 film having a thickness of 15 to 300 nm, the volume resistivity and the surface resistance at each temperature were measured, and the transmittance of the LaNiO 3 film having each thickness was measured at each wavelength. FIG. 1 shows a 200 nm thick L
The graph shows the relationship between the temperature and the surface resistance of the aNiO 3 film. Surface resistance from room temperature (20 ° C) to 800 ° C
Up to 300Ω / □ and the volume resistivity is 2 × 1
0 −5 Ω · m or less. FIG. 2 shows LaNi of each film thickness.
The graph shows the relationship between the wavelength and the light transmittance of the O 3 film. It can be seen that it has a uniform light transmittance for light in a wide wavelength range of 340 to 800 nm. FIG. 3 shows the LaNiO
The relationship between the transmittance of the three films and the light having a wavelength of 600 nm is shown by a solid line as a graph. It can be seen that the light transmittance can be continuously adjusted in the range of about 10 to 90% by adjusting the thickness of the LaNiO 3 film.
【００１５】実施例２ 実施例１において、石英基板の代わりにガラス基板、Ｓ
ｉ単結晶基板、Ａｌ２Ｏ３単結晶基板、ＳｉＣセラミッ
クス基板、Ａｌ２Ｏ３セラミックス基板、Ｓｉ ３Ｎ４セ
ラミックス基板及びステンレス鋼基板をそれぞれ用いた
以外は、実施例１と同様な操作を行った。Ｓｉ単結晶基
板、Ａｌ２Ｏ３単結晶基板、ＳｉＣセラミックス基板、
Ａｌ２Ｏ ３セラミックス基板、Ｓｉ３Ｎ４セラミックス
基板及びステンレス鋼基板の場合は、図１と同様な結果
が得られた。また、ガラス基板については、軟化点が低
いため、７００℃までは同様な結果が得られたが、７０
０℃を超えるとガラスとの反応により導電率が高くなっ
た。図３に、ガラス基板上に設けられたＬａＮｉＯ３膜
における膜厚と波長６００ｎｍの光に対する透光率との
関係を破線でグラフとして示す。ガラス基板について
も、石英基板と同様な結果が得られた。Example 2 In Example 1, a glass substrate was used instead of the quartz substrate.
i single crystal substrate, Al2O3Single crystal substrate, SiC ceramic
Substrate, Al2O3Ceramic substrate, Si 3N4C
Lamix substrate and stainless steel substrate were used respectively.
Except for the above, the same operation as in Example 1 was performed. Si single crystal base
Plate, Al2O3Single crystal substrate, SiC ceramic substrate,
Al2O 3Ceramic substrate, Si3N4Ceramics
In the case of a substrate and a stainless steel substrate, the results are the same as in Fig. 1.
was gotten. For glass substrates, the softening point is low.
Therefore, similar results were obtained up to 700 ° C.
If the temperature exceeds 0 ° C, the conductivity with the glass increases due to the reaction with the glass.
Was. FIG. 3 shows LaNiO provided on a glass substrate.3film
Between the film thickness and the transmittance for light having a wavelength of 600 nm
The relationship is shown as a graph with a dashed line. About glass substrate
Also, the same result as that of the quartz substrate was obtained.
【図１】 石英基板上に形成した本発明のＬａＮｉＯ３
膜における温度と表面抵抗との関係を示すグラフ。FIG. 1 shows a LaNiO 3 of the present invention formed on a quartz substrate.
4 is a graph showing the relationship between temperature and surface resistance of a film.
【図２】 石英基板上に形成した本発明のＬａＮｉＯ３
膜の各膜厚における波長との透光率との関係を示すグラ
フ。FIG. 2 LaNiO 3 of the present invention formed on a quartz substrate
7 is a graph showing the relationship between wavelength and light transmittance at each film thickness of the film.
【図３】 石英基板上及びガラス基板上にそれぞれ形成
した本発明のＬａＮｉＯ３膜における膜厚と透光率との
関係を示すグラフ。FIG. 3 is a graph showing the relationship between the film thickness and the light transmittance of the LaNiO 3 film of the present invention formed on a quartz substrate and a glass substrate, respectively.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０１Ｌ 21/288 Ｈ０１Ｌ 21/288 Ｚ // Ｂ３２Ｂ 9/00 Ｂ３２Ｂ 9/00 Ａ (72)発明者 秋山 守人 佐賀県鳥栖市宿町字野々下807番地１ 九州工業技術研究所内 (56)参考文献 特開 平７−133189（ＪＰ，Ａ) 特開 平４−254419（ＪＰ，Ａ) 特開 平７−315847（ＪＰ，Ａ) 特開 平５−286702（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 53/00 H01B 1/08 H01L 21/28 301 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI H01L 21/288 H01L 21/288 Z // B32B 9/00 B32B 9/00 A (72) Inventor Morito Akiyama Tosu City, Saga Prefecture 807 Nonoshita, Sukumachi, Kyushu Industrial Research Institute (56) References JP-A-7-133189 (JP, A) JP-A-4-254419 (JP, A) JP-A-7-315847 (JP, A) JP-A-5-286702 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C01G 53/00 H01B 1/08 H01L 21/28 301
Claims (4)
イト型構造の金属酸化物からなり、２０〜８００℃の温
度における体積抵抗率が２×１０−５Ω・ｍ以下、又は
表面抵抗が３００Ω／□以下であることを特徴とする透
明導電性薄膜。1. A metal oxide having a perovskite structure having a composition of LaNiO 3 and having a volume resistivity at a temperature of 20 to 800 ° C. of 2 × 10 −5 Ω · m or less, or a surface resistance of 300 Ω / □ or less. A transparent conductive thin film characterized by the following.
１〜９５％の範囲に調整された実質上同一の透光率を有
する請求項１記載の透明導電性薄膜。2. In the wavelength range of 300 to 800 nm,
The transparent conductive thin film according to claim 1, having substantially the same light transmittance adjusted to a range of 1 to 95%.
インダーを溶解させた水溶液からなる塗布液を調製した
のち、基材上に該塗布液を塗布し、次いで酸素雰囲気中
において、５００〜８００℃の温度で焼成し、２０〜８
００℃の温度における体積抵抗率が２×１０−５Ω・ｍ
以下、又は表面抵抗が３００Ω／□以下になるように調
整された膜厚のＬａＮｉＯ３の組成を有するペロブスカ
イト型構造の金属酸化物からなる薄膜を形成させること
を特徴とする透明導電性薄膜の製造方法。3. A coating solution comprising an aqueous solution in which a lanthanum salt, a nickel salt, and a water-soluble organic binder are dissolved, and then the coating solution is applied on a substrate, and then at 500 to 800 ° C. in an oxygen atmosphere. Baking at a temperature of 20-8
Volume resistivity at a temperature of 00 ° C. is 2 × 10 −5 Ω · m
Producing a thin film of a metal oxide having a perovskite structure having a composition of LaNiO 3 having a thickness adjusted so as to have a surface resistance of 300 Ω / □ or less. Method.
５〜５．０モル％のものである請求項３記載の透明導電
性薄膜の製造方法。4. A coating liquid having a LaNiO 3 conversion concentration of 0.0
The method for producing a transparent conductive thin film according to claim 3, wherein the amount is 5 to 5.0 mol%.
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|---|---|---|---|
| JP11026139A JP3079262B2 (en) | 1999-02-03 | 1999-02-03 | Transparent conductive thin film and method for producing the same |
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| JP3079262B2 true JP3079262B2 (en) | 2000-08-21 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2767613A2 (en) | 2013-02-13 | 2014-08-20 | Mitsubishi Materials Corporation | LaNiO3 thin film-forming composition and method of forming LaNiO3 thin film using the same |
| WO2015056587A1 (en) | 2013-10-15 | 2015-04-23 | 三菱マテリアル株式会社 | Lanio3 thin-film-forming composition, and method for forming lanio3 thin-film in which said composition is used |
| US9659681B2 (en) | 2013-11-01 | 2017-05-23 | Samsung Electronics Co., Ltd. | Transparent conductive thin film |
| CN109269662A (en) * | 2018-09-19 | 2019-01-25 | 北京科技大学 | Rare-earth Ni-base perovskite oxide thermistor material applied to infrared acquisition |
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| KR100576849B1 (en) * | 2003-09-19 | 2006-05-10 | 삼성전기주식회사 | Light emitting device and manufacturing method |
| US7083869B2 (en) * | 2004-03-23 | 2006-08-01 | Fujitsu Limited | Methods of forming LaNiO3 conductive layers, ferro-electric devices with LaNiO3 layers, and precursor formation solutions |
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1999
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2767613A2 (en) | 2013-02-13 | 2014-08-20 | Mitsubishi Materials Corporation | LaNiO3 thin film-forming composition and method of forming LaNiO3 thin film using the same |
| US9412485B2 (en) | 2013-02-13 | 2016-08-09 | Mitsubishi Materials Corporation | LaNiO3 thin film-forming composition and method of forming LaNiO3 thin film using the same |
| WO2015056587A1 (en) | 2013-10-15 | 2015-04-23 | 三菱マテリアル株式会社 | Lanio3 thin-film-forming composition, and method for forming lanio3 thin-film in which said composition is used |
| JP2015099914A (en) * | 2013-10-15 | 2015-05-28 | 三菱マテリアル株式会社 | Composition for lanthanum nickel oxide thin film formation, and method for forming lanthanum nickel oxide thin film by use thereof |
| KR101640728B1 (en) | 2013-10-15 | 2016-07-18 | 미쓰비시 마테리알 가부시키가이샤 | Lanio3 thin-film-forming composition, and method for forming lanio3 thin-film in which said composition is used |
| US9659681B2 (en) | 2013-11-01 | 2017-05-23 | Samsung Electronics Co., Ltd. | Transparent conductive thin film |
| CN109269662A (en) * | 2018-09-19 | 2019-01-25 | 北京科技大学 | Rare-earth Ni-base perovskite oxide thermistor material applied to infrared acquisition |
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| Publication number | Publication date |
|---|---|
| JP2000226216A (en) | 2000-08-15 |
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