JPS63314715A - Manufacture of transparent electrically conductive film - Google Patents
Manufacture of transparent electrically conductive filmInfo
- Publication number
- JPS63314715A JPS63314715A JP15192287A JP15192287A JPS63314715A JP S63314715 A JPS63314715 A JP S63314715A JP 15192287 A JP15192287 A JP 15192287A JP 15192287 A JP15192287 A JP 15192287A JP S63314715 A JPS63314715 A JP S63314715A
- Authority
- JP
- Japan
- Prior art keywords
- film
- conductive film
- electrically conductive
- resistance
- air
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 230000000903 blocking effect Effects 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 9
- 239000011521 glass Substances 0.000 abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract description 4
- 229910052738 indium Inorganic materials 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 2
- 238000005245 sintering Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 150000002894 organic compounds Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000000053 physical method Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- ARHIRDSNQLUBHR-UHFFFAOYSA-K 2-ethylhexanoate;indium(3+) Chemical compound [In+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O ARHIRDSNQLUBHR-UHFFFAOYSA-K 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical group 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は各種表示デバイス用電極材料、発熱体、熱線反
射材料などの目的に使用される透明導電膜の製造方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing transparent conductive films used for various purposes such as electrode materials for display devices, heating elements, and heat ray reflecting materials.
従来の技術
従来よシ、透明導電膜は各種表示デバイス用電極、発熱
体、熱線反射材料などの目的に使用されてきた。BACKGROUND OF THE INVENTION Conventionally, transparent conductive films have been used for purposes such as electrodes for various display devices, heating elements, and heat ray reflective materials.
従来のこれら透明導電膜は主として蒸着、スパッタ等の
物理的手法により製造されてきたが、装置コストや生産
性等の向上を目的として金属を含有した有機化合物の熱
分解による製造方法の研究も広く行なわれている。Conventionally, these transparent conductive films have been mainly manufactured using physical methods such as vapor deposition and sputtering, but research has also been widely conducted on manufacturing methods using thermal decomposition of organic compounds containing metals, with the aim of improving equipment costs and productivity. It is being done.
発明が解決しようとする問題点
しかしながら、金属を含有した有機化合物の熱分解によ
る製造方法においては生成した透明導電膜の導電性が蒸
着、スパッタ等の物理的手法のよるものに比して劣るも
のであった。Problems to be Solved by the Invention However, the conductivity of the produced transparent conductive film is inferior to that produced by physical methods such as vapor deposition and sputtering in the manufacturing method by thermal decomposition of organic compounds containing metals. Met.
それ故に、本発明の目的は金属を含有した有機化合物の
熱分解による製造方法における利点を維持しつつ、物理
的手法により得られる透明導電膜により近い導電性を有
する透明導電膜の製造方法を提供することである。Therefore, an object of the present invention is to provide a method for producing a transparent conductive film having conductivity closer to that obtained by a physical method while maintaining the advantages of the production method by thermal decomposition of an organic compound containing a metal. It is to be.
問題点を解決するだめの手段
本発明においては上記、金属を含有した有機化合物の熱
分解による透明導電膜の製造方法における問題を解決す
るための手段として、熱分解、焼結の完了した透明導電
膜に空気中で、または空気との接触を遮断した状態で可
視光線ないしは赤外線を照射して抵抗値の調節をするこ
とを特徴とする。すなわち、上記電磁波の照射により透
明導電膜の抵抗値が製造直後よりも著しく低下し、物理
的手法により製造されたものにより近い抵抗値の透明導
電膜が得られる。Means for Solving the Problems In the present invention, as a means for solving the problems in the above-mentioned method for manufacturing a transparent conductive film by thermal decomposition of an organic compound containing a metal, a transparent conductive film that has been thermally decomposed and sintered is used. It is characterized by adjusting the resistance value by irradiating the film with visible light or infrared rays in the air or with the film blocked from contact with air. That is, by irradiating the electromagnetic waves, the resistance value of the transparent conductive film is significantly lower than that immediately after production, and a transparent conductive film having a resistance value closer to that produced by a physical method can be obtained.
従来よシ、例えば特公昭６０−１９８１０号公報に記載
されているごとく、金属含有有機化合物の熱分解におい
て紫外線により有機化合物の結合を切断して熱分解を補
助しようとする考えはあり、かつ現在、主として使用さ
れている酸化インジウムや酸化スズ等は光導電性を有す
るゆえに紫外線の照射により抵抗値を低下させようとす
る試みは良く行なわれているが、実際には紫外線照射に
よる抵抗値低下は一時的なものであって永続性は少ない
。Conventionally, as described in Japanese Patent Publication No. Sho 60-19810, there has been an idea to assist the thermal decomposition of metal-containing organic compounds by breaking the bonds of the organic compounds with ultraviolet rays. Since indium oxide and tin oxide, which are mainly used, have photoconductivity, attempts are often made to lower the resistance value by irradiating ultraviolet rays, but in reality, the resistance value does not decrease by irradiating ultraviolet rays. It is temporary and has little permanence.
本発明者らは従来全く知られていなかった可視光線から
赤外線の波長領域での照射が抵抗値低下に効果のあるこ
とを見いだし、本発明に至ったものである。The present inventors have discovered that irradiation in the wavelength range from visible light to infrared rays, which was completely unknown in the past, is effective in lowering the resistance value, which led to the present invention.
上記電磁波を透明導電膜に照射する雰囲気としては通常
の空気中でも良いが、空気を遮断して照射すると更に良
好な結果が得られる。The atmosphere in which the transparent conductive film is irradiated with the electromagnetic waves may be normal air, but even better results can be obtained if the electromagnetic waves are irradiated with the air blocked.
上記、照射時の空気遮断条件としては特に厳しい条件は
不要であって、実施例で示す通り、プラスチックスフィ
ルム、紙、ガラス板、セラミックス板、金属板などで透
明導電膜表面を覆うだけで十分な効果があるため、大量
生産にも十分に対応できる有用な手段と言える。As mentioned above, there is no need for particularly severe air blocking conditions during irradiation, and as shown in the examples, it is sufficient to cover the surface of the transparent conductive film with a plastic film, paper, glass plate, ceramic plate, metal plate, etc. Because of its effectiveness, it can be said to be a useful method that can be used in mass production.
本発明にかかる抵抗値低下処理をした透明導電膜は処理
後もプラスチックスフィルム製の袋に保存する程度の簡
単な保管条件で抵抗値の増加もなく安定なものである。The transparent conductive film subjected to the resistance value lowering treatment according to the present invention remains stable without any increase in resistance value even after treatment under simple storage conditions such as storing in a plastic film bag.
作用
金属を含有した有機化合物の熱分解により製造した透明
導電膜に空気中で、または空気との接触を遮断した状態
で可視光線ないしは赤外線を照射することにより、透明
導電膜の抵抗値が低下する。By irradiating a transparent conductive film produced by thermal decomposition of an organic compound containing a working metal with visible light or infrared rays in the air or in a state where contact with air is blocked, the resistance value of the transparent conductive film decreases. .
本発明にかかる処理による抵抗値低下の機構としては、
熱分解により生じた酸化物超微粒子の表面に強く吸着さ
れた酸素原子またはイオンが可視光線または赤外線の照
射による熱振動によシ脱着されるものと推定される。The mechanism of resistance value reduction due to the treatment according to the present invention is as follows:
It is presumed that oxygen atoms or ions strongly adsorbed on the surface of ultrafine oxide particles produced by thermal decomposition are desorbed by thermal vibrations caused by visible light or infrared ray irradiation.
透明導電膜に吸着された酸素量および、脱着後の酸素含
有量は実施例に述べるごとく還元ガス中における熱分析
や、ラザフォード後方散乱の測定により実測することが
できる。The amount of oxygen adsorbed on the transparent conductive film and the oxygen content after desorption can be measured by thermal analysis in reducing gas or measurement of Rutherford backscattering, as described in Examples.
実施例 以下、実施例によυ説明する。Example This will be explained below using examples.
実施例１
２−エチルへキサン酸インジウムに６モルチの２−エチ
ルヘキサン酸スズを添加し、石油系溶剤に溶解してイン
キを製造した。本インキをガラス板上に印刷してのち、
５３０℃で焼成して透明導電膜を製造した。Example 1 An ink was prepared by adding 6 mol of tin 2-ethylhexanoate to indium 2-ethylhexanoate and dissolving it in a petroleum solvent. After printing this ink on a glass plate,
A transparent conductive film was manufactured by firing at 530°C.
本透明導電膜に直接、または透明導電膜を有する側のガ
ラス面上に各種材料を載せて１０Ｃｍの距離よりハロゲ
ンランプを照射した結果を下記の表１に示す。なお、表
１中で耐熱性の不十分な材料の場合およびセラミックス
、金属板のごとき不透明な材料の場合は透明導電膜の反
対側のガラス面よシ照射した。Table 1 below shows the results of irradiating various materials directly on the transparent conductive film or on the glass surface on the side having the transparent conductive film from a distance of 10 cm with a halogen lamp. In Table 1, in the case of materials with insufficient heat resistance and in the case of opaque materials such as ceramics and metal plates, the glass surface opposite to the transparent conductive film was irradiated.
表 １
続いて、表１においてポリイミドフィルムラ介して照射
したサンプルと、焼成したままのサンプルの２種につい
て還元ガス中の熱重量分析とラザフォード後方散乱の測
定を行なった。Table 1 Next, in Table 1, thermogravimetric analysis in reducing gas and measurement of Rutherford backscattering were performed on two types of samples: the sample irradiated through the polyimide film layer and the as-fired sample.
この結果、どちらの測定においても照射サンプルにおい
てはインジウム１原子当り１．５個の酸素原子が観測さ
れだのに対し、焼成したままのサンプルにおいてはイン
ジウム１原子当り２個の酸素原子が観測された。As a result, in both measurements, 1.5 oxygen atoms per indium atom were observed in the irradiated sample, whereas 2 oxygen atoms were observed per indium atom in the as-fired sample. Ta.
この結果より、金属化合物の熱分解時に過剰に吸着され
た酸素原子が本発明にかかる処理によシ脱着して化合物
本来の抵抗値にまで低下するものと推察された。From this result, it was inferred that the oxygen atoms excessively adsorbed during the thermal decomposition of the metal compound were desorbed by the treatment according to the present invention, and the resistance value was reduced to the original resistance value of the compound.
発明の効果
以上実施例および比較例から判るごとく、本発明にかか
る透明導電膜の製造方法は極めて簡単な方法で熱分解透
明導電膜の抵抗値を低下でき、その抵抗値も従来の物理
的手法によるものと同等のものであり、産業上の効果は
大である。Effects of the Invention As can be seen from the Examples and Comparative Examples, the method for producing a transparent conductive film according to the present invention can reduce the resistance value of a pyrolyzed transparent conductive film in an extremely simple manner, and the resistance value can also be lowered by conventional physical methods. It is equivalent to that of the above method, and the industrial effect is great.
Claims (2)
を行う透明導電膜の製造方法。(1) A method for producing a transparent conductive film in which the resistance value is adjusted by irradiating visible light or infrared rays.
赤外線を照射して抵抗値の調節を行う特許請求の範囲第
１項に記載の透明導電膜の製造方法。(2) The method for manufacturing a transparent conductive film according to claim 1, wherein the resistance value is adjusted by irradiating visible light or infrared rays while blocking contact with air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151922A JP2589696B2 (en) | 1987-06-18 | 1987-06-18 | Method for producing transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151922A JP2589696B2 (en) | 1987-06-18 | 1987-06-18 | Method for producing transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63314715A true JPS63314715A (en) | 1988-12-22 |
| JP2589696B2 JP2589696B2 (en) | 1997-03-12 |
Family
ID=15529131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62151922A Expired - Fee Related JP2589696B2 (en) | 1987-06-18 | 1987-06-18 | Method for producing transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2589696B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0634376A1 (en) * | 1993-07-15 | 1995-01-18 | Saint-Gobain Vitrage | Process for treating a thin oxide layer |
| JP2005353505A (en) * | 2004-06-14 | 2005-12-22 | Nippon Soda Co Ltd | Manufacturing method of indium oxide membrane |
| JP2013538675A (en) * | 2010-07-26 | 2013-10-17 | デ，ロシェモント，エル．，ピエール | Liquid phase chemical deposition apparatus and process and product thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6116417A (en) * | 1984-07-02 | 1986-01-24 | 松下電器産業株式会社 | Apparatus for producing transparent conductive film |
-
1987
- 1987-06-18 JP JP62151922A patent/JP2589696B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6116417A (en) * | 1984-07-02 | 1986-01-24 | 松下電器産業株式会社 | Apparatus for producing transparent conductive film |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0634376A1 (en) * | 1993-07-15 | 1995-01-18 | Saint-Gobain Vitrage | Process for treating a thin oxide layer |
| JP2005353505A (en) * | 2004-06-14 | 2005-12-22 | Nippon Soda Co Ltd | Manufacturing method of indium oxide membrane |
| JP4705340B2 (en) * | 2004-06-14 | 2011-06-22 | 日本曹達株式会社 | Method for producing indium oxide film |
| JP2013538675A (en) * | 2010-07-26 | 2013-10-17 | デ，ロシェモント，エル．，ピエール | Liquid phase chemical deposition apparatus and process and product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2589696B2 (en) | 1997-03-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |