JP4099911B2 - Transparent conductive film forming substrate and forming method - Google Patents

Transparent conductive film forming substrate and forming method Download PDF

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Publication number
JP4099911B2
JP4099911B2 JP28698499A JP28698499A JP4099911B2 JP 4099911 B2 JP4099911 B2 JP 4099911B2 JP 28698499 A JP28698499 A JP 28698499A JP 28698499 A JP28698499 A JP 28698499A JP 4099911 B2 JP4099911 B2 JP 4099911B2
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Japan
Prior art keywords
substrate
conductive film
transparent conductive
transparent
atmosphere
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JP28698499A
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JP2001106567A (en
Inventor
恒弘 海野
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日立電線株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a transparent conductive film forming substrate and a forming method.
[0002]
[Prior art]
Transparent conductive films made of ITO (indium-tin-oxide, indium tin oxide film), SnO 2, ZnO, and the like are used for various purposes. In particular, a liquid crystal display is used as a display for a personal computer or a television, and ITO is used as a transparent electrode for the liquid crystal.
[0003]
This liquid crystal display is expected to grow further in the future, but it requires a low price. For this reason, it is expected that a transparent conductive film substrate which is a high-cost component in a liquid crystal display will be supplied at a low cost.
[0004]
ITO is used as the transparent electrode used for the liquid crystal, but this film is formed by sputtering or vapor deposition. Since this forming apparatus is a large vacuum apparatus and the target material for sputtering is expensive, the price is not lowered.
[0005]
Here, a coating method using an organic solution of an organic compound of In and Sn is expected as an inexpensive film formation method, but is characterized by a high formation temperature.
[0006]
In addition to large liquid crystal displays, small liquid crystal displays are also widely used for personal computers and televisions. In particular, when it is used for a cellular phone or the like, it is important that the weight is light, and it is required that a film can be formed on a thin substrate or can be formed on a transparent resin or the like. When the glass substrate is thin, problems such as warping are likely to occur when it is processed at a high temperature, and it is not possible to increase the temperature with a transparent resin or the like.
[0007]
For this reason, if a transparent conductive film can be formed using the application | coating method at low temperature, it can be set as a very effective means.
[0008]
[Problems to be solved by the invention]
By the way, the method of forming a transparent conductive film by a coating method thinly applies an ITO film forming material on a transparent substrate such as glass, and performs baking after drying. When fired at a low temperature, a film with low resistance cannot be formed. Further, although heat treatment in a vacuum is used to lower the resistance, there is a problem that when the substrate fired at a low temperature is subjected to heat treatment in a vacuum, the resistance is somewhat lowered but the transparency is remarkably impaired.
[0009]
Accordingly, an object of the present invention is to provide a transparent conductive film forming substrate and a forming method capable of solving the above-described problems and forming an ITO film having a low resistivity even when the main baking temperature is low.
[0010]
[Means for Solving the Problems]
In order to achieve the above object, the transparent conductive film-formed substrate of the present invention is a coating process in which an organic solution in which an organic compound of In and Sn is dissolved in an organic solvent is coated on the transparent substrate, and the coated transparent substrate is dried. In the transparent conductive film forming substrate in which the transparent conductive film is formed by sequentially performing the drying process and the baking process for baking the dried transparent substrate, the baking process is performed in an oxygen atmosphere having an oxygen concentration of 99 % or more . After being carried out at 0 ° C. , it was carried out in a vacuum.
[0011]
In addition to the above configuration, the transparent conductive film-formed substrate of the present invention is preferably irradiated with ultraviolet rays on the transparent substrate during the firing treatment.
[0012]
The transparent conductive film-formed substrate of the present invention was coated on a transparent substrate with an organic solution prepared by dissolving an organic compound of In and Sn in an organic solvent, dried on the coated transparent substrate, and dried. In the transparent conductive film-formed substrate in which the transparent conductive film is formed by sequentially performing a baking process for baking the transparent substrate, after the baking process is performed at 180 ° C. in an oxygen atmosphere having an oxygen concentration of 99 % or more, The process is performed in a vacuum, a nitrogen atmosphere, a hydrogen atmosphere, an argon atmosphere, or a mixed gas atmosphere thereof.
[0013]
The method for forming a transparent conductive film substrate of the present invention includes a coating process for applying an organic solution in which an organic compound of In and Sn is dissolved in an organic solvent on a transparent substrate, a drying process and a drying process for drying the coated transparent substrate. In the method for forming a transparent conductive film substrate in which a transparent conductive film is formed by sequentially performing a baking process for baking the transparent substrate, the baking process was performed at 180 ° C. in an oxygen atmosphere having an oxygen concentration of 99 % or more. Thereafter, the process is performed in a vacuum, a nitrogen atmosphere, a hydrogen atmosphere, an argon atmosphere, or a mixed gas atmosphere thereof.
[0015]
According to the present invention, in the baking process when forming the ITO film, the baking process is performed in a nitrogen atmosphere, a hydrogen atmosphere, an argon atmosphere, or a mixed gas atmosphere or an oxygen atmosphere thereof, followed by a baking process in a vacuum. As a result, the resistivity of the ITO film is lowered, and the resistivity is further lowered by the combined use of ultraviolet irradiation. Further, the transparency is further improved by setting the oxygen concentration in the oxygen atmosphere to a high concentration of 50% or more.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
[0017]
FIG. 1 is a cross-sectional view showing an embodiment of a transparent conductive film-formed substrate to which the method for forming a transparent conductive film-formed substrate of the present invention is applied.
[0018]
This transparent conductive film-formed substrate is obtained by applying an organic solution in which In and Sn are dissolved in an organic solvent on the transparent substrate 1, drying the transparent substrate coated with the organic solution, and firing the dried transparent substrate. It is the board | substrate which formed the transparent conductive film 2, Comprising: After baking processing was performed in oxygen atmosphere, it was performed in the vacuum.
[0019]
The method for forming a transparent conductive film-formed substrate of the present invention includes a coating process for applying an organic solution in which an organic compound of In and Sn is dissolved in an organic solvent on a transparent substrate 1, a drying process for drying the coated transparent substrate, and A method for forming a transparent conductive film-formed substrate in which a baking treatment for sequentially baking a dried transparent substrate is performed, and after the baking treatment is performed in an oxygen atmosphere, whether in a vacuum, a nitrogen atmosphere, a hydrogen atmosphere, or an argon atmosphere. Or in a mixed gas atmosphere of these.
[0020]
By configuring the transparent conductive film-formed substrate in this manner, an ITO film having a low resistivity can be formed even if the main baking temperature is low.
[0021]
【Example】
A transparent conductive film-formed substrate as shown in FIG. 1 was produced. In addition, although a specific numerical value is given and demonstrated, it is not limited.
[0022]
The structure is such that an ITO film 2 having a thickness of 0.1 μm is formed on a 10 cm square non-alkali glass substrate 1 having a thickness of 0.2 mm.
[0023]
First, the non-alkali glass substrate 1 is washed to remove foreign matters and dirt attached to the surface. Next, after drying the non-alkali glass substrate 1, an organic solution (ITO raw material solution) in which an organic compound of In and Sn is dissolved in an organic solvent is uniformly applied. The composition ratio of Sn to In is 5%. This solution is applied to a transparent substrate and then dried at 150 ° C. Furthermore, temporary baking is performed at 300 ° C. for 1 hour in an oxygen atmosphere. These coating treatment, drying treatment and pre-baking treatment are repeated a plurality of times until the desired film thickness is obtained. Thereafter, the transparent conductive film substrate is placed in a vacuum baking apparatus (not shown), evacuated, heated to 300 ° C., and baked for 1 hour.
[0024]
When the surface resistance of the ITO film 2 formed by such a method was measured by the pow (van der Pauw) method, it was 150Ω / □ and the transparency was also good. On the other hand, although it was transparent when fired in air, the resistivity was not measurable and high. Further, when firing was further performed in vacuum after firing in air, the resistance value decreased to several tens of kΩ, but the film was blackened and transparency was impaired.
[0025]
Next, after washing the glass substrate, the ITO film material was applied and dried. Thereafter, the film was baked at 300 ° C. in oxygen. At that time, the entire substrate was irradiated with ultraviolet rays from a mercury lamp. After firing, the substrate was placed in a vacuum vessel and fired at 300 ° C. for 1 hour while being irradiated with ultraviolet rays.
[0026]
The surface resistance of this film was measured. When UV irradiation was not performed, the resistance was 150Ω / □, but the surface resistance decreased to 80Ω / □ by baking in oxygen. Furthermore, the surface resistance was reduced to 50Ω / □ by irradiating ultraviolet rays during baking in oxygen and in vacuum. The transparency was very good.
[0027]
Here, the basis of the optimum condition will be described.
[0028]
The oxygen concentration in the baking process in oxygen is important. If the firing temperature is 400 ° C. or higher even in air, a sufficient effect can be obtained. If the firing temperature is to be lowered, it is necessary to increase the oxygen concentration and lengthen the heat treatment time. If the oxygen concentration is 99% or more, the firing temperature at which the transparent conductive film is obtained can be lowered to 180 ° C.
[0029]
In the above example, a substrate with a small amount of ions such as sodium was used in this example. However, even with a substrate with a large amount of ions, first, after forming a thin film such as SiO 2 on the substrate, an ITO film was formed by the same method as described above. It may be formed.
[0030]
Further, it was confirmed that similar characteristics were obtained even when a substrate made of a transparent resin was used as the substrate. In the firing process in vacuum, the purpose is to take away excess oxygen in the ITO film and to form donor-forming oxygen vacancies, so that not only vacuum processing but also inert atmosphere gas such as nitrogen or argon or hydrogen atmosphere Some effects can be expected.
[0031]
By the way, when forming a substrate side having a low heat resistance such as a very thin substrate or a resin, or forming a transparent conductive film forming substrate for a large-sized liquid crystal display, the present invention can be used to produce a transparent conductive material with low warpage at a low temperature. A film can be formed. Therefore, the range of substrate selection can be greatly expanded. Moreover, it can be used as a transparent conductive film for not only a liquid crystal display but also other display devices such as an organic EL and a plasma display.
[0032]
As described above, according to the present invention, a low-resistance transparent conductive film can be formed by a coating method, which is an inexpensive film formation technique, even on a substrate for which an ITO film could not be formed by a coating method such as a substrate having low heat resistance. In addition, since the same conductive film can be formed at a low temperature, the specification range of the substrate to be used is widened. Since it can be formed at a lower temperature, the temperature of the firing furnace can be lowered, so that an inexpensive apparatus can be used as the firing furnace, temperature uniformity can be easily obtained, and the transparent formed substrate can be easily carried into and out of the apparatus. Become. Furthermore, less electrical energy is required to maintain the temperature, which can contribute to cost reduction and greatly contribute to environmental problems.
[0033]
【The invention's effect】
In short, according to the present invention, the following excellent effects are exhibited.
[0034]
It is possible to provide a transparent conductive film forming substrate and a forming method capable of forming an ITO film having a low resistivity even when the main baking temperature is low.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an embodiment of a transparent conductive film-formed substrate to which a method for forming a transparent conductive film-formed substrate of the present invention is applied.
[Explanation of symbols]
1 Transparent substrate (non-alkali glass substrate)
2 Transparent conductive film (ITO film)

Claims (4)

  1. A coating process for applying an organic solution obtained by dissolving In and Sn organic compounds in an organic solvent on a transparent substrate, a drying process for drying the coated transparent substrate, and a baking process for firing the dried transparent substrate are sequentially performed. In the transparent conductive film formation substrate in which the transparent conductive film is formed,
    A transparent conductive film-formed substrate, wherein the baking treatment is performed in a vacuum after being performed at 180 ° C. in an oxygen atmosphere having an oxygen concentration of 99 % or more.
  2.   The transparent conductive film forming substrate according to claim 1, wherein the transparent substrate is irradiated with ultraviolet rays during the baking treatment.
  3. A coating process for coating an organic solution in which an organic compound of In and Sn is dissolved in an organic solvent on a transparent substrate, a drying process for drying the coated transparent substrate, and a baking process for firing the dried transparent substrate are sequentially performed. In the transparent conductive film formation substrate in which the transparent conductive film is formed,
    The firing process is performed at 180 ° C. in an oxygen atmosphere having an oxygen concentration of 99 % or more, and then performed in a nitrogen atmosphere, a hydrogen atmosphere, an argon atmosphere, or a mixed gas atmosphere thereof. A transparent conductive film forming substrate.
  4. A coating process for applying an organic solution in which an organic compound of In and Sn is dissolved in an organic solvent on a transparent substrate, a drying process for drying the coated transparent substrate, and a baking process for firing the dried transparent substrate are sequentially performed. In the method of forming a transparent conductive film substrate for forming a transparent conductive film,
    The firing process is performed at 180 ° C. in an oxygen atmosphere having an oxygen concentration of 99 % or more, and then performed in a vacuum, a nitrogen atmosphere, a hydrogen atmosphere, an argon atmosphere, or a mixed gas atmosphere thereof. A method for forming a transparent conductive film-formed substrate.
JP28698499A 1999-10-07 1999-10-07 Transparent conductive film forming substrate and forming method Expired - Fee Related JP4099911B2 (en)

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Application Number Priority Date Filing Date Title
JP28698499A JP4099911B2 (en) 1999-10-07 1999-10-07 Transparent conductive film forming substrate and forming method

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JP4099911B2 true JP4099911B2 (en) 2008-06-11

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4807933B2 (en) * 2003-12-17 2011-11-02 株式会社アルバック Method for forming transparent conductive film and transparent electrode
JP4814491B2 (en) * 2004-02-24 2011-11-16 三菱マテリアル電子化成株式会社 Method for forming transparent conductive film and transparent electrode
JP5403293B2 (en) * 2009-11-05 2014-01-29 住友金属鉱山株式会社 Method for producing transparent conductive film, transparent conductive film, element using the same, transparent conductive substrate and device using the same
JP5700259B2 (en) * 2010-02-17 2015-04-15 住友金属鉱山株式会社 Method for producing transparent conductive film, transparent conductive film, element using the same, transparent conductive substrate and device using the same
KR101954551B1 (en) * 2014-12-05 2019-03-05 후지필름 가부시키가이샤 Method for manufacturing metal oxide film, metal oxide film, thin-film transistor, method for manufacturing thin-film transistor, electronic device, and ultraviolet irradiation device

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