JPH08241626A - Transparent conductive film and method and use of transparent conductive film using the same - Google Patents

Abstract

(57) [Summary] [Structure] A material for a transparent conductive film containing antimony in tin oxide, at least one of Group VIII metal oxides other than Fe, Co and Ni, and an organic solvent. [Effect] The material for the transparent conductive film is 1
The resistivity can be reduced by a digit or more, and a large-area transparent conductive film can be easily formed. Further, the transparent conductive film has excellent characteristics as a transparent electrode of a liquid crystal display device and an antistatic film on the display surface of a cathode ray tube.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for a transparent conductive film containing tin oxide as a main component, a method for producing a transparent conductive film using the same, and its use.

[0002]

2. Description of the Related Art ITO (indium tin oxide), ATO (antimony tin oxide), etc. are known as materials for transparent conductive films, and are used as transparent electrodes for liquid crystal display elements, electrodes for solar cells, or antistatic films for cathode ray tubes. It is used for etc.

As the performance of electronic equipment is improved, the transparent conductive film is required to have low resistivity and high transparency, and further, a film capable of forming a low resistivity film at low temperature is required.

There are various methods for manufacturing these transparent conductive films, but they are roughly classified into a physical film forming method and a chemical film forming method. Since the resistivity of the film is greatly affected by the manufacturing method, it is important to select it depending on the application of the conductive film.

An ATO film formed by a physical film forming method is disclosed in JP-A 2-7.
As seen in Japanese Patent No. 2549, a low resistivity film is formed at a relatively low temperature by a magnetron sputtering method. On the other hand, in the chemical film forming method, as shown in Japanese Patent Laid-Open No. 220505/1985, a cobalt, nickel, cerium compound or the like is added to ATO to form a low-resistivity and high-strength film. .

[0006]

There are still some problems in the above-mentioned conventional technique. The magnetron sputtering method has the drawbacks that the material itself is damaged because it is exposed to plasma during the process, the composition ratio is difficult to control, and a large-scale vacuum device is required, and large-area coating is difficult.

Further, the film obtained by adding cobalt, nickel and cerium compounds to ATO found in Japanese Patent Laid-Open No. 60-220505 promotes crystallization of ATO using the added cobalt, nickel and cerium compounds as a sintering aid. This is a technique for producing a low resistance film. However, the effect of the above additives is small, and the resistivity is (1.8 to 2.0) × 10 ⁻² Ω · cm,
(8.7-9.4) × 10 ^-3 Ω · cm
In addition, heat treatment is required at a temperature higher than 500 ° C.

An object of the present invention is to solve the above problems and to satisfy the advantages of both, that is, a low resistance film can be obtained without requiring heat treatment at high temperature (above 500 ° C.),
It is an object of the present invention to provide a transparent conductive film material that can be formed into a large area device with a simple device and a method for producing a transparent conductive film using the same.

Another object of the present invention is to use the transparent conductive film having a low resistivity, and specifically to provide a liquid crystal display device or a cathode ray tube having an outer transparent conductive film.

[0010]

According to the present invention, 2 to 15% by weight (preferably 5 to 12%, more preferably 8 to 11%) in terms of antimony oxide and Fe, Co and Ni are excluded.
A transparent conductive film for a screen display device, characterized in that at least one of Group II metal oxides is 0.1 to 5% by weight in terms of those metal oxides and 80% by weight or more in terms of tin oxide. .

The present invention converts the antimony oxide into 2-1.
5% by weight, at least one kind of added amount is 0.1 to 2% by weight in terms of Group VIII metal oxide excluding Fe, Co and Ni, and 83% by weight or more in terms of tin oxide. And in the transparent conductive film.

The present invention is 83% by weight in terms of tin oxide.
The above tin alkoxide or metal salt, 2 to 15% by weight of antimony oxide alkoxide or metal salt, and Group VIII metal salt excluding Fe, Co, and Ni are converted to oxides of the metal. After being dissolved or uniformly dispersed in 0.1 to 2% by weight of an organic solvent, hydrolysis,
A method for producing a transparent conductive film, which comprises a reaction step of carrying out a polymerization reaction, a film forming step of applying the reactant on an insulating substrate to form a film, and a baking step of drying and baking the film.

The present invention is 83% by weight in terms of tin oxide.
The above tin alkoxide or metal salt, 2 to 15% by weight of antimony oxide alkoxide or metal salt, and Group VIII metal salt excluding Fe, Co, and Ni are converted to oxides of the metal. After dissolving or uniformly dispersing 0.1 to 2% by weight in an organic solvent, hydrolysis,
A reaction step of forming a prepolymer for carrying out a polymerization reaction, a film forming step of coating the reaction product on an insulating substrate to form a film, and a bonding of the metal atom of the alkoxide or metal salt with an organic group in the solution. The method for producing a transparent conductive film is characterized by comprising a firing step of irradiating an electromagnetic wave having a specific wavelength necessary for destroying, and drying and firing.

The present invention is 83% by weight in terms of tin oxide.
The above tin alkoxide or metal salt, 2 to 15% by weight of antimony oxide alkoxide or metal salt, and Group VIII metal salt excluding Fe, Co, and Ni are converted to oxides of the metal. After dissolving or uniformly dispersing 0.1 to 2% by weight in an organic solvent, hydrolysis,
A reaction step of forming a prepolymer for carrying out a polymerization reaction, a film forming step of applying the reaction product onto an insulating substrate to form a film, and an organometallic compound on the transparent conductive film formed by a baking step of drying and baking the film. Characterized in that it comprises a step of laminating a thin layer of silica by irradiating an electromagnetic wave having a specific wavelength necessary for breaking a bond between a metal atom of the organometallic compound and an organic group to a solution consisting of And a method for producing a transparent conductive film.

The present invention converts the antimony oxide to 2 to
A transparent conductive film, comprising: forming a tin oxide layer of 85% by weight or more in terms of tin oxide containing 15% by weight, and then laminating a Group VIII metal oxide layer excluding Fe, Co, and Ni.

According to the present invention, a pair of electrodes are arranged between a pair of transparent substrates so as to face each other, and an alignment means for aligning liquid crystals is provided on the electrode formation surface, and a liquid crystal layer is sandwiched between the substrates. The electrodes are connected to an external driving means for driving a liquid crystal layer, a pair of polarizing plates are arranged above and below the substrate, and a transparent film having an antistatic film is provided on the screen side of the polarizing plates. In a liquid crystal display device having a substrate, at least one of the electrode and the antistatic film is 2 to 15% by weight in terms of antimony oxide, and VI, excluding Fe, Co, and Ni.
A transparent conductive film having 0.1 to 5% by weight in terms of these oxides of at least one type II group metal oxide and 80% by weight or more in terms of tin oxide is formed. It is in a liquid crystal display device. According to the present invention, tin oxide is converted into antimony oxide on the outer surface of the display surface of the cathode ray tube.
.About.15% by weight, and at least one kind of Group VIII metal oxides other than Fe, Co and Ni is converted into oxides of 0.1.
% To 5% by weight, and a transparent conductive film composed of 80% by weight or more of tin oxide in terms of tin oxide is provided, and a thin layer of silica is laminated on the surface of the transparent conductive film. CRT.

The present invention converts the antimony oxide into 2-1.
5% by weight, at least one of Group VIII metal oxides excluding Fe, Co, and Ni is converted into those metal oxides of 0.1 to
A material for a transparent conductive film, comprising a solution of an organic compound of 2% by weight and 83% by weight or more in terms of tin oxide.

The present invention excludes 83% by weight or more of tin alkoxide or metal salt calculated as tin oxide, 2 to 15% by weight of antimony oxide alkoxide or metal salt calculated as antimony oxide, and Fe, Co, Ni. A material for a transparent conductive film, characterized in that 0.1 to 2% by weight of a group VIII metal salt converted to an oxide of the metal is dissolved or uniformly dispersed in an organic solvent.

In the above, VI excluding Fe, Co and Ni
Group II transition metal oxides include Ir ₂ O ₃ , RuO ₂ , and Rh ₂ O.
₃ , PtO, PdO, OsO ₂ , and one or more of them are added.

The metal oxide is present as fine particles on tin oxide-antimony. The particle size of the fine particles is preferably 5 nm or less.

As the alkoxide of tin, which is the raw material of tin, for example, any of ethoxide, propoxide, isopropoxide, butoxide, isobutoxide and the like may be used. As the tin salt, for example, chloride, bromide, iodide or the like can be used, but SnCl ₄ is preferable.

As for antimony, alkoxides, chlorides, bromides, iodides and the like can be used as in the above case, and alkoxides or chlorides are preferable.

Fluoride can also be used. In this case, fluorine is added to tin oxide. When fluorine is added, hydrogen fluoride or an organic fluorine compound can be used.

As the organic solvent, one which can dissolve or uniformly disperse the raw materials to be used is selected and used.
If the organic solvent and the above-mentioned tin and antimony raw materials react to form no precipitate, it can be used. Examples of the organic solvent include alcohol-based, glycol-based,
Solvents such as hexane and cyclohexane are used.

Next, the group VIII metals other than Fe, Co and Ni are dissolved in the above organic solvent and added. It is also possible to add it in an organic solvent after dissolving it in water, and chloride, nitrate, ammonia salt or the like can be used.

The transparent conductive film of the present invention can be applied to an antistatic film such as a cathode ray tube by laminating an insulating film such as silica. As the silica raw material, a silica sol solution prepared by dissolving silicon alkoxide in an organic solvent and adding water and an acid is used. The silica sol solution is preferably prepared by adding ethyl silicate to one or more of ethanol, propanol, isopropanol, butanol and isobutanol, and adding nitric acid or hydrochloric acid.

To obtain the transparent conductive film of the present invention, F
It may be a laminate of a Group VIII metal oxide film excluding e, Co, and Ni and a film in which antimony is added to tin oxide.

The material for transparent conductive film of the present invention can be applied by a method capable of uniform coating such as spin coating, spray coating, and pulling method on an insulating substrate.

The above coating film is dried in a constant temperature bath and then baked at a predetermined temperature (preferably 300 to 500 ° C.). The calcination can be performed by a known method such as blowing hot air or irradiating infrared rays.

In the reaction step of carrying out hydrolysis and polymerization reaction, it is effective to add water to the raw material solution and stir at 100 ° C. or lower. The reaction time is not particularly limited, but when an alkoxide is used as a raw material, the hydrolysis rate is high, and thus heating is not particularly required.

[0031]

[Function] The transparent conductive film material mainly composed of tin oxide is 4
It is an n-type semiconductor in which conduction electrons are generated by adding pentavalent antimony or fluorine to valent tin.

In the case of an n-type semiconductor, if an acceptor level exists at a grain boundary or surface, conduction electrons are trapped in the acceptor level and are negatively charged. Therefore, the energy of electrons becomes high near the surface and near the grain boundaries to form a bank layer. Since this bank layer has a high electron potential, it strongly adsorbs a gas having a strong electron affinity, particularly oxygen. When the electron affinity gas is adsorbed, the gas removes electrons from the bulk and becomes anion, so that the surface and the grain boundary bank layer are further heightened, and as a result, the resistivity is increased.

In the present invention, the group VIII metal oxide fine particles are dispersed on a transparent conductive film material mainly composed of tin oxide. The group VIII metal oxide having a high electronegativity can keep the surface and the grain boundary bank layer low, and maintain a low resistivity.

The electrons and holes generated in the semiconductor recombine or are trapped by the adsorbed gas and disappear. But,
When the Group VIII metal oxide is present on the surface and near the grain boundaries, it attracts holes and separates charges, and at the same time, adsorbs anionized gas with a strong electron affinity to combine with holes and desorb the adsorbed gas. It is possible to separate them and keep the surface and the grain boundary bank layer low. That is, the above VI present on tin oxide
The group II metal fine particles act as a microelectrode.

When the film thickness is relatively thin, the above VIII
A similar effect can be obtained by stacking fine particles of a group metal oxide.

In addition, in the case of a material such as ruthenium which becomes a resistor among the above Group VIII metal oxides, if it is added more than necessary, the resistance value of ruthenium acts, resulting in an increase in resistivity. If the amount added is further increased, the particle size of the fine particles dispersed on the material for the transparent conductive film is increased, the surface area of the metal oxide is decreased, and the active sites used for the reaction with adsorbed oxygen are decreased. Therefore, VIII
It is necessary to adjust the addition amount of the group metal oxide appropriately.

Another point of the present invention is to use light energy instead of heat energy in the sol-gel method of forming a coating film of a metal alkoxide sol and converting it into an inorganic film by heat energy. That is, the antireflection film and the antistatic film formed by curing by light irradiation are provided on the panel surface of the cathode ray tube panel surface liquid crystal display device or the like. Usually, the sol-gel method is based on a hydrolysis reaction and a condensation reaction in a solution using a metal alkoxide as a raw material, an inorganic polymer precursor is generated in the solution, and then this solution is formed into a film and heat-treated to form an oxide thin film. Is what you get. In the present invention, in this sol-gel reaction, energy necessary for breaking the metal-alkoxy group bond can be applied by irradiation with light such as ultraviolet rays to complete the sol-gel reaction. Further, after forming a film of this solution, light having a shorter wavelength than that for generating ozone is irradiated to obtain an oxide thin film having a uniform stoichiometric ratio at low temperature. The use of this method makes it possible to obtain a dense thin film at a lower temperature than conventional methods, and is therefore the most suitable method for producing a liquid crystal display device and a cathode ray tube surface-treated film. Further, in the present invention, heating may be used in combination with ultraviolet light irradiation. The heating temperature in this case is lower than before, for example, 100 ° C. or lower is sufficient for the silica film, and heating for a short time (about 10 to 15 minutes) is further required.
In the case of a TO film, the temperature may be 150 to 300 ° C., so there is almost no effect of heat on the inside of the cathode ray tube. Therefore, the emission characteristics of the electron gun of the cathode ray tube are not adversely affected, and thermal distortion of the entire cathode ray tube can be avoided. In addition, the occurrence of film peeling due to heat treatment can be eliminated. Also, since the processing time can be shortened at low temperature, the manufacturing cost and equipment cost can be expected to be significantly reduced.
In particular, in the case of heating, according to the present method, since the low temperature is sufficient, the heating rise temperature can be made faster than before. For example, in the conventional method, since the heat treatment is performed at 160 ° C., the heating temperature rise is very slow at 5 ° C./min. According to this method, since the heating temperature may be 100 ° C. or lower, the heating temperature rise can be doubled or faster.

A further advantage of the present invention is that it is possible to form a particularly flea glare film having a uniform stoichiometric ratio at a low temperature, so that the structural defects of SiO _{2 in} the film are significantly larger than those of the conventional one. It can be reduced. When heat treatment (150 to 180 ° C. or higher) at a high temperature by a usual method, SiO ₂ structural defects (E ′ center, etc.) are generated in the film, so that when the light in the visible light range hits, fluorescence is emitted to this whole area. Like In the case of a color cathode ray tube, this fluorescence impairs the sharpness of the three primary colors of red, blue, and green, which is a serious problem when developing a high-definition cathode ray tube. According to the present invention, since a film having extremely few structural defects can be obtained, R, G,
B emission gives a film that does not substantially fluoresce. Therefore, in the non-luminous film according to the present invention, the colors of R, G, and B emitted from the inside of the CRT can be clearly transmitted from the screen to the viewer. On the other hand, the film produced by the conventional method continues to emit fluorescence for several hours when irradiated with light in the visible light region. For this reason, the CRT surface becomes unclear. When the emission spectrum emitted from the fluorescent substance of the cathode ray tube is measured, the B and G spectra of the conventional film-formed one are considerably broad because of the overlap of the extra fluorescence. However, in the case where the film of the present invention is formed, the full width at half maximum of the spectrum is 80 because there is no extra fluorescence.
It becomes narrower than nm, which leads to improvement of color purity.

Since this structural defect is a defect in the SiO ₂ network structure, it has a great influence on the mechanical strength and water resistance of the film. The strength and water resistance of the membrane are
The non-glare film, which is an antireflection film, is a particularly important element because it is formed on the outermost surface of the cathode ray tube panel. Since the SiO ₂ film according to the present invention has few structural defects, the strength and water resistance of the film are improved. The structural defect of the film and its quantification can be measured by electron spin resonance spectrum (ESR). The amount of Si defects estimated by ESR is 10 ¹⁰ to 10 ¹⁴ defects / cm ³ .

[0040]

【Example】

Example 1 Tin chloride propanol (C ₃ H ₇ OH)
Dissolved in isopropoxyantimony (C ₃ H ₇ OH) ₃ Sb
Was added, and the mixture was heated and stirred at 80 ° C. for 2 hours to obtain a raw material solution.
Further, ruthenium acetylacetate was added, and a raw material solution was similarly prepared by heating and stirring at 80 ° C. for 2 hours.

2000 g of the above raw material solution was placed on a glass substrate.
After spin coating at rpm, 300-500 ° C in air
And a tin oxide (SnO ₂ ) thin film added with 10 wt% of antimony oxide (Sb ₂ O ₅ ) and a tin oxide thin film added with 10 wt% of Sb ₂ O ₅ and 1 wt% of RuO ₂ were prepared. . The relationship between the firing temperature and the room temperature resistivity of these films is shown in FIG.

By adding Ru, the resistivity can be reduced to 0.1 Ωcm or less, and the film with Ru added can lower the resistivity by about one digit as compared with the film without addition. Further, when the ultraviolet / visible absorption spectra of the produced films were measured, all the films exhibited a transmittance of 95% by weight or more in the visible light region (particularly, a wavelength of 300 to 850 nm).

Example 2 FIG. 2 shows the resistivity when the amount of ruthenium oxide (RuO ₂ ) added in the raw material solution of Example 1 was changed.

When the addition amount is 5% by weight or less, the resistivity can be made smaller than that in the case where no addition is made, but when it exceeds 5% by weight, the resistivity becomes higher than in the case where no addition is made. In particular,
If 0.1 to 3% by weight is not added, the resistivity becomes small and
Lower resistivities of 1 to 2% by weight and even 0.15 to 1% by weight are obtained, and a resistivity of 1000 μΩcm or less is obtained.

When the obtained film is observed by TEM,
It was found that fine particles of ruthenium oxide were deposited. The size of these ruthenium oxide fine particles increases with the addition amount of Ru. The relationship between the particle size of Ru and the resistivity is shown in FIG. 3. The smaller the particle size, the lower the resistivity, which is considered to be due to the catalytic action of Ru. When the particle size of Ru becomes large, the resistivity of ruthenium oxide itself affects the resistivity of the conductive film, so the particle size is preferably 5 nm or less. Therefore, it is preferably 3.5 nm or less.

Example 3 Ruthenium acetylacetate was dissolved in ethanol, and this was placed on a glass substrate in an amount of 20.
Spin coating was performed at 00 rpm, drying and baking at 500 ° C. were performed to obtain a ruthenium oxide film. A solution prepared by dissolving tin chloride and isopropoxyantimony in propanol was spin-coated in the same manner to form a film, and ruthenium oxide-
An ATO (Sb 10% by weight) laminated film was produced. When the resistivity of the film at room temperature was measured, it showed about half the resistivity of the ATO single-phase film.

Example 4 Tin chloride and isobutoxy antimony were dissolved in propanol, and a propanol solution of isopropoxy antimony was added so that the tin concentration was 0.3 mol / l and the molar ratio of tin and antimony was 10%. , ATO film raw material solution was prepared.

Cobalt nitrate, nickel nitrate, iron nitrate, rhodium nitrate, iridium nitrate, palladium chloride, and ruthenium chloride were added to the above raw material solution so that the respective oxides became 0.2% by weight, and the mixture was added at 80 ° C. for 10 hours. The mixture was heated and stirred to obtain an ATO film raw material coating liquid to which the metal oxide was added.

Next, each of the raw material coating liquids was spin-coated on a quartz substrate at 1000 rpm for 60 seconds, and the coating was performed at 60 ° C. for 2 seconds.
After drying for 0 minutes, calcination in air at 400 ° C for 20 minutes AT
An O film was produced.

The resistance of the prepared film and the film strength by an eraser test were measured. In the eraser test, the eraser was rubbed under a load of 1 kg, the resistance value was measured, and this operation was repeated until the resistance value changed, and the eraser was rubbed and evaluated. Table 1 shows the respective results.

[0051]

[Table 1]

When iron, cobalt and nickel are added, the resistance value of the ATO film is slightly reduced, whereas the resistance value of the ATO film of the present invention to which ruthenium, rhodium and platinum are added is as follows. It fell to about 1/10.

Regarding the film strength, no change was observed in the resistance value of all the manufactured films even after the sand eraser eraser test was performed 200 times or more, and the film strength is sufficient as an antistatic film. In addition, reduction treatment with hydrogen or the like is not necessary after manufacturing.

From the above results, VI excluding Co, Ni and Fe
An excellent transparent conductive film having a low resistance value can be obtained by adding the group II metal oxide.

Example 5 An example in which the transparent conductive film of the present invention is applied to a liquid crystal display device will be shown.

FIG. 4 is a partial cutaway view of the liquid crystal display device 1 manufactured according to the present invention. The liquid crystal display device 1 has a polarizing plate 2, a color filter 3, and a glass plate 4, and a liquid crystal layer 7 is sandwiched by two sets of strip-shaped transparent electrodes, that is, a counter electrode 5 and a pixel electrode 6, which are orthogonal to each other. A liquid crystal cell is formed at each intersection of those electrodes.

On the polarizing plate 2 of the liquid crystal display device 1,
On the glass substrate 8 serving as a surface protection plate, the antireflection film 9 for reflection is formed.
have. The anti-reflection film 9 was produced by the following process.

The ruthenium acetylacetate-added solution prepared in Example 1 was dropped on the glass substrate 8 serving as a surface protective film, spin-coated at 500 rpm, and then at 250 ° C. for 1 hour.
Ru-added ATO that becomes a transparent antistatic film after heat treatment for 5 minutes
A film 10 was obtained. The film composition consisted of 10 wt% antimony oxide, 0.2 wt% ruthenium oxide, and the balance SnO.

Next, a silica sol solution consisting of ethyl silicate, nitric acid, propanol, and water was dropped on the Ru-added ATO film, spin-coated at 500 rpm, and heated at 160 ° C. for 20 minutes.
After heat treatment for a minute, a silica film 11 to be a reflection film was formed on the Ru-added ATO film, and a glass substrate 8 to be a surface protection plate with a reflection antistatic film 9 was prepared.

When the liquid crystal display device 1 was manufactured, the liquid crystal display device 1 was manufactured after the glass substrate 8 serving as the surface protection plate with the antireflection film 9 was manufactured in advance.

A part of the glass substrate 8 serving as a surface protective plate with the antireflection film 9 was cut and the reflectance and the surface resistance value were measured. The reflectance at 560 nm was 0.6%. Was 5.2 × 10 ⁵ Ω / □. From this,
It was found that the film had excellent antistatic properties against reflection, and a high-performance liquid crystal display device could be produced.

The Ru-added ATO film serves as an antistatic film.

[Embodiment 6] An example in which the transparent conductive film of the present invention is applied as a surface treatment film for a cathode ray tube is shown.

FIG. 6 is a partially cutaway side view showing the cathode ray tube 12 manufactured according to the present invention. This CRT 1
2 has an airtight glass envelope 13 whose inside is exhausted. The envelope 13 has a neck 14 and a cone 15 continuous from the neck 14. Further, the envelope 13 has a cone 15 and a face plate 16 sealed with frit glass. A metal tension band 17 is provided on the outer periphery of the side wall of the face plate 16 to prevent explosion.
Has been consolidated. An electron gun 18 that emits an electron beam is arranged on the neck 14. On the inner surface of the face plate 16, a phosphor screen composed of a striped phosphor layer that emits red, green, and blue light emitted from the electron gun 18 and a striped black absorption layer disposed between the phosphor layers. 19 are provided.

Face plate 1 of this cathode ray tube 12
The outer surface of 6 is provided with a reflection antistatic film 20,
The reflection of extraneous light is suppressed, the face plate 16 is prevented from being charged, and the adhesion of dust is suppressed. Further, the reflection antistatic film 20 is composed of a Ru-added ATO film 21 and a silica film 22 which are antistatic films as shown in an enlarged view of a portion A of FIG.

The antistatic antireflection film 20 was produced as follows.

The raw material solution prepared in Example 2 containing 10% by weight of antimony oxide and 0.2% by weight of ruthenium oxide was dropped on the face plate 16 to obtain 500 to 200%.
Spin coating was performed at 0 rpm and heat treatment was performed at 350 ° C. for 20 minutes to prepare a Ru-added ATO film.

Next, a silica sol solution consisting of ethyl silicate, nitric acid, water and propanol was further spray-coated thereon, followed by heat treatment at 160 ° C. for 20 minutes, and Ru added A
A silica film serving as an antireflection film was formed on the TO film, and a cathode ray tube having the antireflection film 20 made of a transparent conductive film on the face plate 16 was manufactured.

When the Braun tube 12 is manufactured, the antireflection film 20 is formed on the face plate 16 in advance, and then the Braun tube 12 is manufactured.

A part of the face plate 16 of the manufactured cathode ray tube 12 was cut and the reflectance and surface resistance were measured. The reflectance at 560 nm was 0.1 to 0.3%, and the surface resistance was 7. It was 0.6 × 10 ³ Ω / □. Thus, it was possible to obtain a film having an excellent antireflection property. Furthermore, since the resistance value of the Ru-added ATO film 21 is low, it is possible to suppress the leaking electromagnetic wave, and it is possible to manufacture a high-performance cathode ray tube.

An example of forming the above-mentioned silica film by the following another method will be shown.

Tetraethoxysilane, water, ethanol,
Nitric acid was mixed at a molar ratio of 1: 12: 45: 0.25 to prepare a raw material solution. Immediately after making this solution,
The face of the cathode ray tube was spray coated. 254 nm (10 m
W / cm ² ), then 184 nm (1 mW / cm ² ) of light
Irradiate for 0 minutes. In the display screen of this cathode ray tube, unnecessary emission of the non-glare film due to the emission of the phosphors (R, G, B) does not occur, so that a cathode ray tube with extremely high color and color tone can be manufactured. The fluorescent substance (R,
The emission spectrum of G and B) has a narrower half-value width than that of the conventional light emission spectrum, and thus the color purity is improved. In addition, since the surface is made of a film with an antireflection function having unevenness with a height of 0.2 to 0.3 μm and a width of about 30 μm, a high-precision cathode ray tube with a reflectance of 1% or less and little reflection is produced. We were able to. Next, the properties of the antireflection film produced in this example and the antireflection film produced only by the conventional heat treatment were compared. As the emission spectrum of the non-glare film when the film heat-treated at 160 ° C. is irradiated with visible light of 490 nm, it has a peak at around 530 nm and shows a wide emission spectrum over the entire visible light region. Since this light emission covers the entire visible light region, the screen is in a state where green-white light emission occurs. Moreover, this emission intensity continues for a considerably long time. Further, this light emission overlaps the spectra of the R, G, and B light emission of the phosphors of the color CRT, which causes the blurring of the image. On the other hand, such light emission is not observed in the film produced by light irradiation. Therefore, it becomes possible to manufacture a high-definition CRT. It is known that this light emission is due to the defect structure of the film, and ESR confirmed the presence of the E'center. The amount was 10 ²⁷ pieces / cm ³ . On the other hand, its existence is not confirmed in the light irradiation film. Next, as the absorption spectrum of the film, the heat-treated film has absorption in the ultraviolet region, and its absorption intensity rises from around 200 nm. This absorption is said to be absorption based on the structural defect of SiO _{2, and} the structural defect of the heat-treated film is also estimated from the absorption spectrum. On the other hand, in the light-treated film, such absorption is not observed. Instead of the above-mentioned silica film, a silica film containing Sb and Sn oxide was similarly formed by the following method.

Tetraethoxysilane, water, ethanol,
Nitric acid was mixed at a molar ratio of 1: 12: 45: 0.25 and fine particles of tin oxide (Sb / Sn = 5 mol%) containing antimony oxide with a diameter of 0.1 μm or less were added to tetraethoxysilane. And added in equal amounts to uniformly disperse them into a raw material solution. The surface of the cathode ray tube was spray-coated with this solution to form a film. 254 nm (10 mW / cm ² ) while heating this film at 90 ° C., then 184 nm
The light of (1 mW / cm ² ) was irradiated for 10 minutes. The produced film is in a state where fine particles of tin oxide containing conductive antimony oxide are uniformly dispersed in the SiO ₂ matrix. The surface resistance of this film was 10 ⁹ Ω / □. The antistatic / antireflective film produced by this method showed good performance without any adverse effect on the inside of the cathode ray tube due to high heat treatment, which has been a problem in the past. After switching on of the cathode ray tube, the induction voltage observed on the outermost surface of the panel after being turned on attenuates the induction voltage by only 5 minutes after the induction voltage becomes 0 if the anti-reflection film only contains tin oxide. In contrast to the above requirements, it was confirmed that the film with the film of this example had an induced voltage of 0 within a few seconds, and the antireflection was good.

The Ru-added ATO film formed by the sol-gel method of this embodiment was formed only by the heat treatment method. However, this film was subjected to electromagnetic waves having a specific wavelength as in the case of forming the silica film. The subsequent heat treatment temperature is 400 ° C. or less, preferably by irradiating and applying as a solution of the prepolymer, and further by irradiating the prepolymer film with an electromagnetic wave having a specific wavelength to generate ozone and oxidize an organic substance. Can be performed at a temperature of 200 to 350 ° C. As a result, the C content of the film was 0.0
It can be reduced to 1 to 5 atom%. Ultraviolet rays, 325 nm wavelength He-Cd laser light, 249 nm Kr laser light, 193 nm A as electromagnetic waves of a specific wavelength.
r-F laser light or the like can be used.

[0075]

According to the present invention, Co, Ni and Fe are excluded
Surface adsorbed species such as oxygen can be removed by adding a specific content of Group VIII metal oxide, and the resistivity of tin oxide film can be compared with conventional materials without reducing treatment such as hydrogen treatment. It can be lowered by one digit or more, and a large-area transparent conductive film can be easily formed.

Further, the transparent conductive film according to the present invention has excellent characteristics as a transparent electrode of a liquid crystal display device and an antistatic film on the display surface of a cathode ray tube.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the firing temperature and the resistivity of a ruthenium-added tin oxide film and a non-added tin oxide film.

FIG. 2 is a graph showing the relationship between the amount of ruthenium oxide added and the resistivity of a tin oxide film.

FIG. 3 is a graph showing the relationship between the ruthenium oxide particle size and the resistivity of a tin oxide film.

FIG. 4 is a sectional view of a liquid crystal display device using the transparent conductive film of the present invention.

5 is an enlarged view of part B in FIG.

FIG. 6 is a partial cross-sectional view of a cathode ray tube using the transparent conductive film of the present invention.

FIG. 7 is an enlarged view of part A in FIG.

[Explanation of symbols]

2 ... Polarizing plate, 3 ... Color filter, 4 ... Glass plate, 5 ...
Counter electrode, 6 ... Pixel electrode, 7 ... Liquid crystal layer, 8 ... Glass substrate, 9, 20 ... Antireflection film, 13 ... Envelope, 18 ...
Electron gun, 21 ... ATO film, 22 ... Silica film.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number for FI Technical indication C01G 55/00 C01G 55/00 G09F 9/30 335 7426-5H G09F 9/30 335E H01B 13/00 503 H01B 13/00 503B H01J 29/88 H01J 29/88 // C09K 3/16 101 C09K 3/16 101A 101C (72) Inventor Tomoji Oishi 7-1, Omika-cho, Hitachi City, Ibaraki Hitachi Hitachi Research Laboratory (72) Inventor Ken Takahashi 7-1 Omika-cho, Hitachi City, Ibaraki Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Masahiro Nishizawa 3300 Hayano, Mobara-shi, Chiba Hitachi Manufacturing Co., Ltd. Electronic Device Division

Claims (12)

[Claims] 1. 2 to 15% by weight in terms of antimony oxide,
At least one of Group VIII metal oxides other than Fe, Co and Ni is 0.1 to 5% by weight in terms of those metal oxides and 80% by weight or more in terms of tin oxide. Transparent conductive film for equipment. 2. 2 to 15% by weight in terms of antimony oxide,
Transparent conductive material characterized in that the addition amount of at least one of the group VIII metal oxides excluding Fe, Co and Ni is 0.1 to 2% by weight and that of tin oxide is 83% by weight or more. film. 3. The transparent conductive film according to claim 1, wherein the Group VIII metal oxide is fine particles of 5 nm or less. 4. Excluding 83% by weight or more of tin alkoxide or metal salt in terms of tin oxide, 2 to 15% by weight of antimony oxide in terms of antimony alkoxide or metal salt, and Fe, Co, Ni. A reaction step of dissolving or uniformly dispersing 0.1 to 2% by weight of a Group VIII metal salt in the form of an oxide of the metal in an organic solvent, and then carrying out hydrolysis and polymerization reactions. The reaction product is placed on an insulating substrate. A method for producing a transparent conductive film, which comprises a film forming step of applying and forming a film, and a baking step of drying and baking the film. 5. Excluding 83% by weight or more of tin alkoxide or metal salt in terms of tin oxide, 2 to 15% by weight of antimony oxide in terms of antimony alkoxide or metal salt, and Fe, Co, Ni. A reaction step of dissolving or uniformly dispersing 0.1 to 2% by weight of a Group VIII metal salt in the form of an oxide of the metal in an organic solvent, and then carrying out hydrolysis and polymerization reactions. The reaction product is placed on an insulating substrate. A method for producing a transparent conductive film, which comprises laminating a thin layer of silica on a transparent conductive film formed by a film forming process of applying to form a film and a baking process of drying and baking the film. 6. Excluding 83% by weight or more of tin alkoxide or metal salt in terms of tin oxide, 2 to 15% by weight of antimony oxide in terms of antimony alkoxide or metal salt, and Fe, Co, Ni. A reaction step of forming a prepolymer for carrying out hydrolysis and polymerization reaction after dissolving or uniformly dispersing 0.1 to 2% by weight of a Group VIII metal salt in the form of an oxide of the metal in an organic solvent, and the reaction product. Film-forming step of coating on an insulating substrate to form a film, and irradiating the solution with an electromagnetic wave having a specific wavelength necessary for breaking the bond between the metal atom of the alkoxide or metal salt and an organic group The method for producing a transparent conductive film is characterized by comprising a baking step of drying, baking and baking. 7. Excluding 83% by weight or more of tin alkoxide or metal salt in terms of tin oxide, 2 to 15% by weight of antimony oxide in terms of antimony alkoxide or metal salt, and Fe, Co, Ni. A reaction step of forming a prepolymer for carrying out hydrolysis and polymerization reaction after dissolving or uniformly dispersing 0.1 to 2% by weight of a Group VIII metal salt in the form of an oxide of the metal in an organic solvent. A film-forming process of forming a film by coating on an insulating substrate, a solution of an organometallic compound formed on a transparent conductive film formed by a baking process of drying and baking the film, and a metal atom and an organic group of the organometallic compound A method for producing a transparent conductive film, which comprises a step of irradiating with an electromagnetic wave having a specific wavelength necessary for breaking the bond of the above, applying the same, and laminating a thin layer of silica. 8. 2 to 15% by weight in terms of antimony oxide
A transparent conductive film, comprising: forming a tin oxide layer of 85% by weight or more in terms of tin oxide containing, and laminating a Group VIII metal oxide layer excluding Fe, Co, and Ni. 9. A pair of electrodes are arranged to face each other between a pair of transparent substrates, an alignment means for aligning liquid crystals is provided on the electrode formation surface, and a liquid crystal layer is sandwiched between the substrates. The electrodes are connected to an external driving means for driving the liquid crystal layer, a pair of polarizing plates are arranged above and below the substrate, and a transparent substrate having an antistatic film is provided on the screen side of the polarizing plates. In the liquid crystal display device having the above, at least one of the electrode and the antistatic film is 2 to 15% by weight in terms of antimony oxide, and at least one of Group VIII metal oxides other than Fe, Co and Ni is added to these oxides. A liquid crystal display device, wherein a transparent conductive film having a conversion of 0.1 to 5% by weight and a conversion to tin oxide of 80% by weight or more is formed. 10. On the outer surface of the display surface of the cathode ray tube, tin oxide and antimony oxide are 2 to 15% by weight, and Fe and C are added.
A transparent conductive film comprising at least 80% by weight of tin oxide in terms of tin oxide, containing 0.1 to 5% by weight of those oxides of at least one type of Group VIII metal oxide excluding o and Ni. A cathode ray tube having a thin layer of silica laminated on the surface of the transparent conductive film. 11. An antimony oxide in an amount of 2 to 15% by weight, at least one of Group VIII metal oxides other than Fe, Co and Ni in an amount of 0.1 to 2% by weight and a tin oxide. A material for transparent conductive film, comprising a solution of an organic compound of 83% by weight or more. 12. A VIII group excluding Fe, Co and Ni, and 83% by weight or more of tin alkoxide or metal salt converted to tin oxide, 2 to 15% by weight of antimony oxide alkoxide or metal salt converted to antimony oxide. A material for a transparent conductive film, characterized in that 0.1 to 2% by weight of a metal salt in terms of oxide is dissolved or uniformly dispersed in an organic solvent.