JP2001288466A - Fluorescent material and method of its manufacture and color filter and its method of manufacture and color display unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorescent material or a color filter excellent in optical character, heat resistance, and toxicity and not inhibiting irradiation of an ultra-violet ray to a photoresist, and a color display unit good in luminance chromaticity and excellent in luminance and contrast. SOLUTION: In this fluorescent material, a coating film 2 being an oxide matrix dispersed with a gold minute particle, is formed as a thin film on the surface of a red, etc., fluorescent particle 1. This fluorescent material can be obtained by mixing the fluorescent particles in a gold colloid dispersion, stirring, then taking out, drying, and sintering the precipitated fluorescent particles. This color filter has filter layers formed inside a panel 3, and at least one color filter layer is a thin film of the oxide matrix dispersed with the gold minute particle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor, a color filter, a method of manufacturing the same, and a color cathode ray tube, a field emission display (FED), and a plasma display panel (PD) having the same.
P).

[0002]

2. Description of the Related Art Generally, on the inner surface of a face panel of a color display device such as a color cathode ray tube, phosphor layers of respective colors of blue, green and red are formed in a dot or stripe pattern. The phosphor layer emits light of each color by colliding with an electron beam or the like, thereby displaying an image.

Conventionally, for the purpose of improving the luminance, contrast, and emission chromaticity of such a color display device, the surface of the phosphor particles is coated with pigment particles of each color that transmits light of the same color as the emission color. Coating) or a method in which a color filter composed of a pigment layer of each color that transmits light of the same color as the emission color of the phosphor layer is provided between the phosphor layer and the face panel.

[0004] Organic and inorganic pigments can be used as such pigments for phosphor coating and color filter formation. However, due to the optical properties, heat resistance, and toxicity of the pigments, they are used. The pigments that can be used were limited. That is, organic pigments have good optical properties but poor heat resistance, and thus cannot be used in color display devices such as cathode ray tubes, which require a heat treatment step. Among inorganic pigments, cadmium pigments have good optical properties and heat resistance, but cannot be used because they have toxicity.

Therefore, as a pigment for a phosphor coating and a pigment for a color filter of a color display device, there is no choice but to use red iron oxide (Fe ₂ O ₃ ) which is slightly inferior in optical characteristics but has excellent heat resistance and is non-toxic. .

[0006]

However, Bengala,
Due to the optical characteristic of having a large absorption of wavelengths in the ultraviolet region, the amount of exposure of the photoresist in the phosphor layer forming step and the like has been reduced due to coating on the phosphor surface and installation of a color filter. That is,
In the formation of a phosphor layer by photolithography, a sufficient amount of ultraviolet light applied to the photoresist is absorbed by the phosphor coating film and the color filter, including redwood, which absorb part of the ultraviolet light that is irradiated to cure the photoresist. There was a problem that irradiation was not performed.

Therefore, a phosphor coating material and a color filter material which are excellent in optical properties, heat resistance and non-toxicity and which do not hinder the irradiation of a photoresist with ultraviolet rays when forming a phosphor layer, have been conventionally used. It has been demanded.

In the case of using a pigment such as red iron oxide, an insulating phosphor coating film or a color filter is provided between the phosphor layer and the black matrix (BM). It is electrically insulated.
As a result, the phosphor layer is likely to be charged and the problem that the luminance of the display device is reduced has occurred. The present invention has been made to solve these problems, and has been made in order to solve the above-mentioned problems. A phosphor or color filter that does not hinder the irradiation of the photoresist with ultraviolet light during the formation of the phosphor layer, etc. It is an object to provide a color display device having excellent display characteristics such as contrast.

[0009]

According to a first aspect of the present invention, there is provided:
A phosphor which is disposed in a layer inside a panel of a color display device, and has a thin film containing fine gold particles on the surface of phosphor main body particles.

In a second aspect of the present invention, the phosphor main body particles are added to a coating solution containing fine gold particles and mixed.
A method for producing a phosphor, characterized in that a thin film containing the gold fine particles is formed on the surface of the phosphor main body particles by drying and firing.

According to a third aspect of the present invention, there is provided a color filter in which a plurality of color filter layers are arranged in a predetermined pattern on the inner surface of a translucent panel, wherein at least one color filter layer has a gold layer in an oxide matrix. It is a thin film in which fine particles are dispersed and contained.

In a fourth aspect of the present invention, a coating liquid containing gold fine particles and an alkoxysilane or a metal alkoxide is applied to a light-transmitting panel, and then dried and fired, so that the oxide matrix is formed. Forming a thin film containing gold fine particles dispersed and contained therein.

According to a fifth aspect of the present invention, there is provided a light-transmitting panel, a light-absorbing layer disposed on an inner surface of the panel, and a light-absorbing layer disposed on a back side opposite to the panel with respect to the light-absorbing layer. A phosphor layer, wherein the phosphor layer includes the phosphor according to the first aspect.

Further, a sixth aspect of the present invention is directed to a light-transmitting panel, a light-absorbing layer and a color filter provided on an inner surface of the panel, respectively, and a side opposite to the panel with respect to the color filter. And a phosphor layer disposed on the back side of the color filter, wherein the color filter is the color filter according to the third aspect.

In the first aspect of the present invention, since the phosphor main body particles have a thin film containing fine gold particles on the surface thereof,
A phosphor excellent in optical properties, heat resistance and non-toxicity can be obtained. In the case of the gold fine particles alone, the particles are aggregated or grow by drying and blackened, but in the present invention, the gold fine particles are uniformly dispersed in a matrix of an oxide such as silica in a thin film. In addition, the particle size of the fine gold particles is kept fine, and the selective absorption of visible light is maintained without blackening.

In the phosphor coated with such a thin film, as shown in a second embodiment, particles of the phosphor main body are added and mixed to a coating liquid containing fine gold particles having a controlled particle diameter. It can be easily formed by post-drying and firing.

In the third aspect of the present invention, since the filter layer of at least one color is a thin film in which fine gold particles are dispersed and contained in an oxide matrix, it is excellent in optical properties, heat resistance and non-toxicity. A color filter can be obtained.

And such a color filter is
As shown in the fourth embodiment, a coating liquid containing gold fine particles having a controlled particle diameter and an alkoxysilane is applied onto a translucent panel, dried, and then baked in a heat treatment step. , Can be formed.

In the coated phosphor and color filter of the present invention, the fine gold particles dispersed and contained in the coating thin film and the filter thin film are smaller than those of redwood which has been conventionally used as a red pigment.
It has an optical characteristic that absorption of light in an ultraviolet region is extremely small. Therefore, the irradiation of the photoresist with ultraviolet rays during the formation of the phosphor layer or the like is not hindered, and the photoresist can be irradiated with a sufficient amount of ultraviolet rays.

Further, by selecting a metal oxide (oxide semiconductor) having a low electric resistance value as the oxide constituting the matrix of the gold fine particle dispersion, a metal oxide (oxide semiconductor) having a low electric resistance value is sufficient for a phosphor coating film containing gold fine particles or a color filter. Conductivity can be imparted. As a result, the phosphor layer and B
An electrical connection with M can be made, and a decrease in luminance due to charging of the phosphor layer can be prevented.

[0021]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 shows a first embodiment of the present invention.
FIG. 2 is a cross-sectional view illustrating a schematic configuration of a phosphor whose entire surface is coated with a coating film. FIG. 2 illustrates a schematic configuration of a phosphor in which a part of the surface is coated with a coating film according to a second embodiment. FIG.

In these figures, reference numeral 1 denotes a phosphor particle as a main body, on which a coating film 2 in which fine gold particles are dispersed and contained in an oxide matrix is provided.
It is formed in a thin film shape covering the entire surface or a part thereof. Hereinafter, a coating film in which fine gold particles (gold colloid) are dispersed and contained in an oxide matrix is referred to as a gold colloid-dispersed oxide matrix coating film.

As the phosphors, those which emit red light include Y ₂ O ₃ : Eu, Y ₂ O ₂ S: Eu, (Y, G
d) BO ₃ : Eu, YBO ₃ : Eu or the like can be used. By adjusting the particle size of the gold fine particles,
Since a coating film having optical characteristics other than red can be obtained, the phosphor that can be used is not limited to red.

It is desirable that the particle size of the fine gold particles is 2.5 to 35.0 nm. More preferably, the particle size range is 10.
0 to 30.0 nm, and the most preferred range is 1 to 30.0 nm.
0.0 to 25.0 nm.

A matrix in which such fine gold particles are dispersed and contained.
The oxides that make up the trix are transparent to visible light.
It is preferable to use a clear oxide. Such a transparent
As the light oxide, silica (SiO₂), Aluminum oxide
Um (Al₂O₃), Cerium oxide (Ce)₂O₃),acid
Indium (In)₂O₃), Lanthanum oxide (La₂O
₃), Tin oxide (SnO)₂), Tantalum oxide (Ta)
O_x), Zinc oxide (ZnO) ₂), Titanium oxide (Ti
O₂), Yttrium oxide (Y₂O₃), Zirconium oxide
Um (ZrO₂), Tin (Sn) doped oxide oxide
Oxide doped with indium and antimony (Sb)
And tin oxide doped with aluminum (Al)
Can be mentioned.

Also, 1 × 10^-FiveΩ · m or less electrical resistivity
It is also possible to use an oxide (semiconductor) having
You. As such an oxide semiconductor, indium oxide
(In ₂O₃), Tin oxide (SnO)₂), Ruthenium oxide
(RuO_x), Rhenium oxide (ReO)_x), Zinc oxide
(ZnO), germanium oxide (GeO)₂), Copper oxide
(Cu₂O), silver oxide (Ag)₂O), vanadium oxide
(V₂O₅), Titanium oxide (TiO)₂), Oxidized tongue
Ten (WO_x) And the like.

In the gold colloid-dispersed oxide matrix coating film 2, the ratio of the fine gold particles to the oxide matrix is 1.0 to 8.0% by mole relative to SiO ₂ .
It is desirable that A more preferable ratio is 1.5 to
6.0%, and the most desirable ratio is 1.5 to 4.5%.
It is. The ratio of the gold fine particles to the oxide semiconductor is desirably 0.1 to 8.0% by mole.

The method for producing the phosphor coated with the gold colloid-dispersed oxide matrix coating film 2 is described below.
It is shown below.

First, a coating solution (colloidal gold dispersion) is prepared.

That is, a solution of chloroauric acid obtained by adding an acid to a solution of tetrachloroauric acid (III) tetrahydrate (HAuCl ₄ .4H ₂ O) dissolved in an organic solvent is converted into an oxide. After being added to the solution of the matrix forming material, the mixture is refluxed at 40 ° C. for about 2 hours and hydrolyzed to obtain a gold colloid dispersion. At this time, as the solvent, methanol,
An alcohol solvent such as ethanol or isopropyl alcohol, a cellosolve solvent, or a ketone solvent such as methyl ethyl ketone can be used. As the acid to be added to the solution of tetrachloroauric acid (III) tetrahydrate, an inorganic acid such as hydrochloric acid or nitric acid or an organic acid such as acetic acid can be used. Further, as a material for forming the oxide matrix, alkoxides of silicon such as tetraethoxysilane and tetramethoxysilane, and alkoxides containing a metal constituting the oxide semiconductor such as titanium tetraethoxide and tin tetraethoxide described above. Can be used.

The phosphor particles are mixed into the gold colloid dispersion liquid prepared in this way, and the mixture is stirred. The precipitated phosphor particles are taken out, dried and fired to obtain a gold colloid dispersed oxide matrix coating film. Can be obtained.

Next, a color filter according to a third embodiment of the present invention will be described.

FIG. 3 is a sectional view showing a schematic configuration of a color filter for a cathode ray tube according to a third embodiment of the present invention.

In the drawing, reference numeral 3 denotes a face panel glass panel. On the inner surface of the panel 3, a light absorbing layer 4 and a color filter 5 formed as a black matrix are provided, respectively. , Blue, green, and red phosphor layers 6 are formed in a dot or stripe pattern. The color filters 5 are regularly arranged and formed in holes of a predetermined shape (for example, circular dot shape) of the light absorption layer 4 so that the filter layers of each color transmit light of the same color as the emission color of the phosphor layer 6. Have been. In the color filter 5, at least one color filter layer is a thin film in which gold fine particles are dispersed in an oxide matrix (hereinafter, referred to as a gold colloid-dispersed oxide matrix thin film).

Here, the particle size of the fine gold particles is 2.5 to 3
It is desirable to set it to 5.0 nm. A more preferred range of the particle size is 10.0 to 30.0 nm, and an even more preferred range is 10.0 to 25.0 nm.

A matrix in which such fine gold particles are dispersed and contained.
The oxides that make up the trix are transparent to visible light.
It is preferable to use a clear oxide. Such a transparent
As the light oxide, silica (SiO₂), Aluminum oxide
Um (Al₂O₃), Cerium oxide (Ce)₂O₃),acid
Indium (In)₂O₃), Lanthanum oxide (La₂O
₃), Tin oxide (SnO)₂), Tantalum oxide (Ta)
O_x), Zinc oxide (ZnO) ₂), Titanium oxide (Ti
O₂), Yttrium oxide (Y₂O₃), Zirconium oxide
Um (ZrO₂), Tin (Sn) doped oxide oxide
Oxide doped with indium and antimony (Sb)
And tin oxide doped with aluminum (Al)
Can be mentioned.

Also, 1 × 10^-FiveΩ · m or less electrical resistivity
It is also possible to use an oxide (semiconductor) having
You. As such an oxide semiconductor, indium oxide
(In ₂O₃), Tin oxide (SnO)₂), Ruthenium oxide
(RuO_x), Rhenium oxide (ReO)_x), Zinc oxide
(ZnO), germanium oxide (GeO)₂), Copper oxide
(Cu₂O), silver oxide (Ag)₂O), vanadium oxide
(V₂O₅), Titanium oxide (TiO)₂), Oxidized tongue
Ten (WO_x) And the like.

In the gold colloid-dispersed oxide matrix thin film 2, the ratio of the fine gold particles to the oxide matrix is Si
The molar ratio of O ₂ is desirably 1.0 to 8.0%. A more desirable ratio is 1.5 to 6.0%, and a most desirable ratio is 1.5 to 4.5%. The ratio of the gold fine particles to the oxide semiconductor is as follows:
It is desirable that the molar ratio be 0.1 to 8.0%.

In order to produce such a filter layer (colloidal gold-dispersed oxide matrix thin film), the coating solution (colloidal gold dispersion) prepared by the above-mentioned method is applied by a spin coating method or a dip coating method. It is possible to adopt a method of applying on a panel, drying and firing. Further, patterning can be performed by a known photolithography method. That is, a coating solution is prepared by adding a photosensitive component appropriately selected to the colloidal gold dispersion, the coating solution is applied to a panel, dried, exposed to a predetermined position through a shadow mask, and developed. Thereby, a patterned filter layer can be formed. Patterning can also be performed by a two-layer photolithography method in which a photoresist coating film is separately laminated and formed.

Next, a color cathode ray tube, a field emission display (FED), and a plasma display panel (PDP) will be described with reference to the drawings as examples of a color display device having such a phosphor coating film and a color filter. explain.

As shown in FIGS. 4A and 4B, the color cathode ray tube has a glass panel 7 which is a translucent panel, a funnel 8 and an envelope 9 composed of a neck 9. A phosphor screen 10 is provided on the inner surface of the panel 7, and a shadow mask 11 is disposed inside the panel 7 so as to face the phosphor screen 10. On the other hand, an electron gun 13 for emitting an electron beam 12 is provided in the neck 9 of the envelope. The electron beam 1 emitted from the electron gun 13 is provided inside the funnel 8.
An inner shield 14 that shields the electron beam 2 from an external magnetic field is disposed, and a deflecting device 15 that deflects the electron beam 12 by a generated magnetic field is disposed outside the funnel 8.
The phosphor screen 10 is composed of a light absorbing layer 16 formed in a matrix and phosphor layers 17 of each color regularly arranged and formed in the holes thereof. A color filter 19 having a filter layer 18 of a color corresponding to the emission color of the phosphor layer 17 is provided between them.

In a field emission display (FED) as a second example of the color display device of the present invention, as shown in FIG. 5, a substrate 20 on the electron emission side and a substrate 21 on the light emission side are parallel to each other. The vacuum envelope 22 is formed so as to be opposed. In the substrate 20 on the electron emission side, a silicon dioxide film 25 having a large number of cavities 24 is formed on a silicon substrate 23, on which a gate electrode 26 made of molybdenum or niobium is formed. On the internal silicon substrate 23, a cone-shaped electron-emitting device 27 made of molybdenum is formed. In the light emitting side substrate 21,
On the surface of the glass panel 28 facing the electron-emitting device 27,
A phosphor screen 10 composed of a light absorbing layer and a phosphor layer of each color is formed, and a color filter (not shown) corresponding to the emission color of the phosphor layer is provided between the phosphor layer and the glass panel 28. .) Is provided. Further, in order to support the load applied to the silicon substrate 23 by the weight of the glass panel 28 and the like and the atmospheric pressure, a support member 29 is provided between the substrate 20 on the electron emission side and the substrate 21 on the light emission side. .

Further, in an AC type PDP which is a third example of the color display device of the present invention, as shown in FIG.
The rear substrate 30 and the front substrate 31 are arranged in parallel and opposed to each other, and both are held at a fixed interval by a plurality of cell barriers 32 arranged on the rear glass substrate 30a. . In the front substrate 31, the light absorbing layer 16 and the color filter 19 are formed on the inner surface of the glass substrate 31a.
Is disposed thereon, and a transparent electrode 33 serving as a sustain electrode is provided thereon.
And a metal electrode 34 serving as a bus electrode. Further, a dielectric layer 36 is formed so as to cover the composite electrode 35, and a protective layer 37 is further formed thereon. On the other hand, the address electrodes 38 are arranged on the front surface of the rear glass substrate 30a so as to be orthogonal to the composite electrodes 35.
Are formed between the cell barriers 32, and the phosphor layer 17 is provided so as to cover the address electrodes 38.

Next, the characteristics of the gold colloid-dispersed oxide matrix thin film used as the coating film of the phosphor or the filter layer of the color filter in the first to third embodiments will be described with reference to the drawings. I do.

First, the light transmittance spectrum of a gold colloid-dispersed oxide matrix thin film is measured by changing the particle size of gold fine particles (colloid), and the bottom wavelength (wavelength at which the absorption rate is maximum) of this spectrum is determined. Was. The particle size of the colloidal gold and the colloidal gold-dispersed silica (SiO
₂ ) The relationship with the optical characteristics (maximum absorption wavelength) of the matrix thin film is shown in FIG.

From this graph, it can be seen that as the particle size of the gold colloid becomes smaller, the spectrum bottom wavelength (the maximum absorption wavelength) shifts to the shorter wavelength side, and the color of the obtained thin film becomes more red (pink). If it is smaller than 2.5 nm, the bottom wavelength of the spectrum is significantly shorter, so that it was confirmed that the obtained thin film was yellowish and the coloring power was insufficient. Further, it was confirmed that as the particle size of the gold colloid was larger, the spectral bottom wavelength shifted to the longer wavelength side, and the color of the obtained thin film became blue-violet.

Next, in a color display device having such a color filter of a colloidal gold-dispersed silica matrix thin film, the chromaticity characteristics of red emission were measured by changing the particle size of the gold colloid. FIG. 8 shows the characteristics of the red filter layer formed by using the red iron oxide pigment.

From the chromaticity diagram shown in FIG. 8, when the particle size of the gold colloid is increased up to the particle size of 25.0 nm, the y value of the emission chromaticity decreases and the x value increases, and the chromaticity characteristic of red is reduced. It was confirmed that it improved. However, when the particle size of the colloidal gold was further increased beyond 25.0 nm, it was confirmed that the y value of the chromaticity increased and the x value decreased, and the chromaticity characteristics deteriorated.

From the measurement results shown in FIGS. 7 and 8, it is desirable that the particle size of the gold colloid is 2.5 to 35.0 nm, more preferably 10.0 to 30.0 nm, and most preferably. It was found to be 10.0 to 25.0 nm. That is, from the graph shown in FIG. 7, a coloring effect is recognized in the obtained thin film, and the particle size range of gold colloid usable as a color filter is 2.5 to 35.0 nm. When it was 10.0 to 30.0 nm, it was found that it could be used as a red filter. Also, from the graph shown in FIG. 8, the particle size range of the gold colloid having the effect of improving the chromaticity characteristics of red emission is 1
It was found to be 0.0-25.0 nm.

In preparing a colloidal gold dispersion,
FIG. 9 shows the relationship between the molar ratio of tetrachloroaurate (III) tetrahydrate and tetraethoxysilane (TEOS) and the particle size of the obtained gold colloid. In order to obtain a colloidal gold having a particle size in the above range, the molar ratio of tetrachloroauric acid (III) tetrahydrate to TEOS is desirably 1.0 to 8.0%, and more desirably. It was confirmed from this graph that is between 1.5 and 6.0%, and most preferably between 1.5 and 4.5%. Note that tetrachloroaurate (III) tetrahydrate and TE
Since the molar ratio with OS is the molar ratio between the fine gold particles and silica (SiO ₂ ) in the film formed as it is, the fine SiO ₂ particles in the gold colloid dispersed oxide matrix thin film
_The ratio (molar ratio) to 2 is also 1.0 to 1.0 as described above.
It is preferably 8.0%, more preferably 1.5%.
To 6.0%, and most preferably 1.5 to 4.5%.

FIG. 10 shows the spectral transmittance spectrum of such a gold colloid-dispersed oxide (for example, silica) matrix thin film together with the transmittance spectrum of a filter layer formed by using red iron oxide. The light transmittance of the colloidal gold dispersed oxide matrix thin film in the ultraviolet wavelength range is about five times that of the filter layer composed of red iron oxide in the ultraviolet wavelength range.
It was confirmed that the absorption in the ultraviolet wavelength region was significantly reduced as compared with the filter layer made of Bengala.

In order to clarify such an effect, when a thin film containing red iron oxide and a colloidal gold-dispersed silica matrix thin film are used as a phosphor coating film or a color filter of a color display device, respectively, a phosphor layer forming step is performed. Table 1 shows the amount of UV irradiation (exposure) required for the photoresist in the above.

[0054]

[Table 1] From Table 1, it can be seen that, by using the colloidal gold dispersed oxide matrix thin film, in both the phosphor coating film and the color filter, the necessary exposure amount to the photoresist at the time of forming the phosphor layer is reduced. It was confirmed that the productivity of the product improved.

Next, the conductivity of the phosphor coating film and the color filter using the gold colloid-dispersed oxide matrix thin film and the luminance characteristics of the color cathode ray tube provided with the same were measured. Table 2 shows the measurement results. The production of the color cathode ray tube was performed as follows.

That is, the black matrix (B
M) is prepared, and a gold colloid-dispersed oxide matrix thin film is formed as a color filter on the inner surface of the face panel, or a filter layer is formed using red iron oxide, and a phosphor layer is formed thereon by a slurry method. Was formed and assembled by a known method to obtain a color cathode ray tube. Also, a phosphor layer is formed on a face panel on which a BM is formed in advance, using phosphor particles having a surface coated with a colloidal gold-dispersed oxide matrix thin film or phosphor particles having a surface coated with red iron oxide. After that, it was assembled by a known method to obtain a color cathode ray tube.

[0057]

[Table 2] From Table 2, it was found that by using a phosphor coated with a thin film in which a gold colloid was dispersed in an appropriate metal oxide matrix or a color filter, a conventional phosphor coated with a red iron oxide or a color filter was used. It was confirmed that the surface resistance value was significantly reduced as compared with that of the above, and as a result, the brightness of the color cathode ray tube was improved.

The present invention is mainly applied to a red phosphor coating or a red filter, but the bottom wavelength of the light transmission spectrum is changed by controlling the particle size of the gold colloid. It is possible to obtain phosphor coating thin films and color filters having various optical characteristics from blue to green.

Next, specific examples of the present invention will be described.

Example 1 A colloidal gold-dispersed silica matrix thin film was prepared in the following procedure.
A coating solution A for forming a film was prepared. That is,
Trachloroaurate (III) tetrahydrate (HAuCl ₄・ 4H
₂O) Dissolve 2.000 g in 7.990 g of ethanol and add 35%
Aqueous solution of acid obtained by adding 0.601 g of water to 3.613 g of hydrochloric acid (HCl)
Was added dropwise to obtain a solution of chloroauric acid. Then, the obtained solution
The solution was treated with 18.066 g of tetraethoxysilane (TEOS)
The mixture was added dropwise after refluxing at 40 ° C for about 2 hours.
By hydrolyzing, the coating liquid A (gold colloid)
Dispersion).

Next, a red phosphor (Y ₂ O ₂ S: Eu) is mixed into the coating liquid A, and the mixture is stirred. Then, the precipitated phosphor is taken out, dried and baked at 500 ° C. for 3 minutes. As a result, a red phosphor having a particle surface coated with a colloidal gold-dispersed silica matrix thin film (hereinafter referred to as a colloidal gold-dispersed silica-coated red phosphor) was obtained.

Using this phosphor, a color cathode ray tube was manufactured by a conventional method. That is, BM
Are prepared, and a blue phosphor (ZnS: Δg, Al) and a green phosphor (ZnS: C) are prepared.
u, Αl), and the above-described colloidal gold-dispersed silica-coated red phosphor were mixed with water together with PVA, ADC and a surfactant, and stirred to prepare phosphor slurries of each color. Then, the phosphor slurry of each color
Was sequentially applied on the BM of the panel, dried, exposed to a predetermined position via a shadow mask, and developed to form a phosphor layer of each color. Next, after forming a metal back layer on the phosphor layer thus formed, a funnel was sealed, an electron gun was installed, and the inside of the tube was evacuated to complete a color cathode ray tube. Further, as Comparative Example 1, a color cathode ray tube was manufactured in the same manner using a red phosphor having a surface coated with red iron oxide.

With respect to the color cathode ray tubes obtained in Example 1 and Comparative Example 1, chromaticity characteristics of red light emission and display characteristics of luminance and contrast were measured. Table 3 shows the measurement results.

Example 2 A field emission display (FED) was manufactured using the colloidal gold-dispersed silica-coated red phosphor prepared in Example 1 as follows. That is, a blue phosphor layer, a green phosphor layer, and a colloidal gold-dispersed silica-coated red phosphor layer were respectively placed at predetermined positions on a face plate (glass panel) on which a BM was previously formed in the same manner as in Example 1. After patterning and forming a metal back layer thereon, this face plate is sealed with a back substrate (rear plate) on which electron-emitting devices have been formed in advance, and the face plate is evacuated.
ED was completed. Further, as Comparative Example 2, an FED was manufactured in the same manner using a red phosphor having a surface coated with red iron oxide.

For the FEDs obtained in Example 2 and Comparative Example 2, the chromaticity characteristics of red light emission and the display characteristics of luminance and contrast were measured. Table 3 shows the measurement results.

Example 3 Using the colloidal gold-dispersed silica-coated red phosphor prepared in Example 1, a plasma display was produced as follows. That is, a blue phosphor, a green phosphor, and a colloidal gold-dispersed silica-coated red phosphor were mixed with terpineol and ethylcellulose, respectively, and stirred to prepare pastes. These phosphor pastes were mixed with a glass substrate on which a barrier was previously formed. By forming by screen printing in the predetermined position of
A back substrate having a phosphor pattern was obtained. Then, this back substrate was combined with a front substrate on which a BM, a composite electrode, a dielectric layer and a protective layer had been formed in advance to complete a plasma display. Further, as Comparative Example 3, a plasma display was manufactured in the same manner using a red phosphor whose surface was coated with red iron oxide.

With respect to the plasma displays obtained in Example 3 and Comparative Example 3, the chromaticity characteristics of red emission and the display characteristics of luminance and contrast were measured. Table 3 shows the measurement results.

[0068]

[Table 3] From Table 3, it can be seen that in each of Examples 1, 2, and 3, the contrast is improved as compared with the corresponding Comparative Examples 1, 2, and 3, and the chromaticity of red emission is significantly improved. .

Example 4 A coating solution for a red filter was prepared by adding an appropriately selected photosensitive agent to the coating solution A (colloidal gold dispersion) used in Example 1. Then, this red filter coating solution and a blue pigment prepared by a known method (for example, cobalt aluminate (Al ₂ O ₃ —Co
O)) and a green pigment (for example, TiO ₂ —NiO—CoO—Zn)
A color filter was formed on the face panel on which the BM was formed by performing patterning by a known photolithography method using each of the green filter coating solutions containing O).

Thereafter, a phosphor layer and a metal back layer are sequentially formed in the same manner as in Example 1, sealed with a funnel, an electron gun is installed, and the inside of the tube is evacuated to thereby provide a color filter having a color filter. The cathode ray tube was completed. In addition,
The coating layer of the above-described gold colloid dispersion liquid becomes a gold colloid-dispersion silica matrix thin film useful as a red filter layer by heat treatment in the sealing and evacuation steps.

Further, as Comparative Example 4, a red filter layer was formed using a red pigment, which is a conventional red pigment, and a color cathode ray tube having a color filter was manufactured in the same manner.

With respect to the color cathode ray tubes obtained in Example 4 and Comparative Example 4, the chromaticity characteristics of red emission and the display characteristics of luminance and contrast were measured. Table 4 shows the measurement results.

Example 5 The same procedure as in Example 4 was carried out, except that a coating solution for a red filter prepared by adding an appropriately selected photosensitive agent to the coating solution A (colloidal gold dispersion) used in Example 1 was used. Then, a filter pattern was formed on a face plate (glass panel), and using this panel, a field emission display (FED) provided with a color filter was manufactured in the same manner as in Example 2. In addition, as Comparative Example 5, a red filter layer was formed using a red pigment, which is a conventional red pigment, and an FED having a color filter was manufactured in the same manner.

With respect to the FEDs obtained in Example 5 and Comparative Example 5, the chromaticity characteristics of red emission and the display characteristics of luminance and contrast were measured. Table 4 shows the measurement results.

Example 6 In the same manner as in Example 4 except that a coating solution for a red filter prepared by adding a photosensitizer appropriately selected to the coating solution A (colloidal gold dispersion) used in Example 1 was used. Then, a filter pattern was formed on the inner surface of the glass substrate on the front side in the same manner as in Example 4, and this substrate was used as a front substrate, and a plasma display having a color filter was manufactured in the same manner as in Example 3. Also,
As Comparative Example 6, a red filter layer was formed using a red pigment, a conventional red pigment, and a plasma display having a color filter was manufactured in the same manner.

With respect to the plasma displays obtained in Example 6 and Comparative Example 6, the chromaticity characteristics of red emission and the display characteristics of luminance and contrast were measured. Table 4 shows the measurement results.

[0077]

[Table 4] From Table 4, it can be seen that in each of Examples 4, 5, and 6, the contrast is improved as compared with the corresponding Comparative Examples 4, 5, and 6, and the chromaticity of red emission is significantly improved. .

Example 7 A coating solution B for forming a colloidal gold-dispersed ITO (indium-tin oxide) matrix thin film was prepared by the following procedure. That is, tetrachloroaurate (III) tetrahydrate _{(HAuCl 4 · 4H 2 O)} 2.000g ethanol
Indium nitrate In (N
A solution obtained by dissolving 23.66 g of O ₃ ) _{3 in} 37.00 g of ethanol was added dropwise, and the resulting solution was further added to tetra-t (tertiary).
-Coating solution B (colloidal gold dispersion) by dropping 3.31 g of butoxytin in a solution of 10.00 g of ethanol and then refluxing at 40 ° C. for about 2 hours to effect hydrolysis.
I got

Next, a red phosphor (Y ₂ O ₂ S: Eu) was mixed into the coating liquid B and stirred. The phosphor was taken out, dried and baked at 500 ° C. for 3 minutes. Red phosphor whose particle surface is coated with a colloidal gold-dispersed ITO matrix thin film (hereinafter referred to as colloidal gold-dispersed I
Shown as TO coated red phosphor. ) Got. Further, using this phosphor, a color cathode ray tube was manufactured in the same manner as in Example 1.

With respect to the color cathode ray tube obtained in Example 7, the chromaticity characteristics of red light emission and the display characteristics of luminance and contrast were measured. Table 5 shows the measurement results along with the characteristics of the color cathode ray tube of Comparative Example 1 described above.

Example 8 A field emission display (FED) was manufactured in the same manner as in Example 2 except that the red phosphor coated with the colloidal gold dispersed in ITO prepared in Example 7 was used.

With respect to the FED obtained in Example 8, the chromaticity characteristics of red light emission and the display characteristics of luminance and contrast were measured. Table 5 shows the measurement results along with the characteristics of the FED of Comparative Example 2 described above.

[0083]

[Table 5] From Table 5, in Examples 7 and 8, the corresponding Comparative Example 1,
It can be seen that the luminance is significantly improved as compared to 2.

Example 9 A color cathode ray tube equipped with a color filter was manufactured in the same manner as in Example 4, except that the coating liquid B for forming a colloidal gold-dispersed ITO matrix thin film prepared in Example 7 was used. At this time, the coating layer of the coating liquid B becomes a useful gold colloid-dispersed ITO matrix thin film as a red filter layer by heat treatment in the sealing and evacuation steps.

With respect to the color cathode ray tube provided with the color filter obtained in Example 9, the chromaticity characteristics of red light emission and the display characteristics of luminance and contrast were measured. Table 6 shows the measurement results along with the characteristics of the color cathode ray tube of Comparative Example 4 described above.

Example 10 A field emission display (FED) provided with a color filter was manufactured in the same manner as in Example 5, except that the coating liquid B for forming a colloidal gold-dispersed ITO matrix thin film prepared in Example 7 was used.

With respect to the FED provided with the color filter obtained in Example 10, the chromaticity characteristics of red light emission and the display characteristics of luminance and contrast were measured. By aligning the measurement results with the characteristics of the FED of Comparative Example 5 described above,
It is shown in Table 6.

[0088]

[Table 6] From Table 6, it can be seen that in Examples 9 and 10, the luminance was significantly improved as compared with the corresponding Comparative Examples 4 and 5.

[0089]

As described above, according to the present invention, it is possible to obtain a phosphor or a color filter excellent in optical characteristics, heat resistance and non-toxicity, and to provide such a phosphor or a color filter to provide a luminescent color. It is possible to obtain a color display device having excellent degree characteristics and luminance / contrast display characteristics. Therefore, the industrial value is extremely large.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a schematic configuration of a phosphor according to a first embodiment of the present invention, the entire surface of which is coated with a coating film.

FIG. 2 is a cross-sectional view illustrating a schematic configuration of a phosphor according to a second embodiment, the surface of which is partially covered with a coating film.

FIG. 3 is a sectional view showing a schematic configuration of a color filter for a cathode ray tube according to a third embodiment of the present invention.

4A and 4B show a color cathode ray tube as a first example of a color display device of the present invention, wherein FIG. 4A is a cross-sectional view showing the overall schematic configuration, and FIG. 4B is an enlarged cross-sectional view of a phosphor screen.

FIG. 5 is a second example of the color display device of the present invention, FE.
Sectional drawing which shows schematic structure of D.

FIG. 6 shows a PD as a third example of the color display device of the present invention.
Sectional drawing which shows schematic structure of P.

FIG. 7 is a graph showing the relationship between the particle size of colloidal gold and the optical characteristics (maximum absorption wavelength) of a colloidal gold-dispersed silica matrix thin film in the present invention.

FIG. 8 is a graph showing the relationship between the particle size of gold colloid and chromaticity characteristics of red light emission in the color display device of the present invention.

FIG. 9 is a graph showing the relationship between the molar ratio of tetrachloroaurate (III) tetrahydrate and tetraethoxysilane (TEOS) and the particle size of the obtained gold colloid.

FIG. 10 is a view showing a spectral transmittance spectrum of a filter layer formed by using a colloidal gold-dispersed silica matrix thin film and red iron oxide.

[Explanation of symbols]

1 phosphor particles 2 gold colloid dispersed oxide matrix coating film 3, 7, 28 glass panel 4, 16 light absorbing layer 5, 19 color filter 6, 17 ... Phosphor layer 8 Funnel 10 Phosphor screen 13 Electron gun 15 Deflector 18 Filter layer 20 Emitting substrate 21 Emitting substrate 27 Electron-emitting device 30 Back substrate 31 Front substrate 31a Glass substrate 32 Cell barrier 35 Composite electrode 36 Address electrode

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G02B 5/20 101 G02B 5/20 101 H01J 1/63 H01J 1/63 1/74 1/74 11/02 11/02 Z 29/20 29/20 29/32 29/32 31/12 31/12 C (72) Inventor Tsuyoshi Koyanatsu 1-9-2 Hara-cho, Fukaya-shi, Saitama Pref. ) Inventor Hiroshi Makihara 19-23 Leopalace 21-6-209, Saganakayamacho, Ukyo-ku, Kyoto-shi, Kyoto (72) Inventor Tosumi Fukui 4-15-39 Karasaki, Otsu-shi, Shiga F-term (reference) 2H048 BA47 BA48 BB01 BB02 BB14 BB41 4H001 CA01 CA05 CA06 CC01 CC04 CC05 CC06 CC11 CF02 XA08 XA16 XA30 XA39 YA63 5C036 CC11 CC18 EE05 EF01 EF06 EF09 EG28 EG36 EH07 EH08 EH09 EH12 EH18 EH22 EH04 KB03040 KB03040 MA04 MA 05

Claims (23)

[Claims] 1. A phosphor which is disposed in a layer inside a panel of a color display device so as to form a layer, and has a thin film containing fine gold particles on the surface of phosphor main body particles. 2. The gold fine particles having a particle size of 2.5 to 35.
2. The phosphor according to claim 1, wherein the thickness is 0 nm. 3. The phosphor according to claim 1, wherein the thin film is a thin film in which the fine gold particles are dispersed in an oxide matrix. 4. The method according to claim 1, wherein the oxide is silica (SiO 2).₂),acid
Aluminum chloride (Al₂O₃), Cerium oxide (Ce)₂
O₃), Indium oxide (In)₂O₃), Lanthanum oxide
(La₂O₃), Tin oxide (SnO)₂), Tantalum oxide
(TaO_x), Zinc oxide (ZnO)₂), Titanium oxide (T
iO₂), Yttrium oxide (Y₂O ₃), Zirconium oxide
(ZrO₂), Tin (Sn) doped oxidation
Indium and antimony (Sb) doped oxide
From tin oxide doped with aluminum (Al)
At least one selected from the group consisting of:
3. The phosphor according to 3. 5. The phosphor according to claim 4, wherein said oxide is silica (SiO ₂ ). 6. The phosphor according to claim 5, wherein a ratio of the gold fine particles to the silica in the thin film is 1.0 to 8.0% in a molar ratio. 7. The phosphor according to claim 3, wherein the oxide is an oxide semiconductor having an electric resistivity of 1 × 10 ⁻⁵ Ω · m or less. 8. The phosphor according to claim 7, wherein a ratio of the gold fine particles to the oxide semiconductor in the thin film is 0.1 to 8.0% in a molar ratio. 9. The oxide semiconductor according to claim 1, wherein the oxide semiconductor is indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), ruthenium oxide (RuO _x ), rhenium oxide (ReO _x ), zinc oxide (ZnO), germanium oxide ( GeO ₂ ), copper oxide (Cu ₂ O), silver oxide (Ag ₂ O), vanadium oxide (V ₂ O ₅ ), titanium oxide (TiO ₂ ), and tungsten oxide (WO _x ). The phosphor according to claim 7 or 8, wherein: 10. A method of forming a thin film containing the fine gold particles on the surface of the main phosphor particles by adding and mixing the phosphor main particles to a coating liquid containing the fine gold particles, followed by drying and baking. A method for producing a phosphor which is characterized by the following. 11. The step of preparing a coating liquid containing gold fine particles comprises the step of preparing tetrachlorogold (II) dissolved in an organic solvent.
I) a step of adding an acidic aqueous solution to a solution of an acid tetrahydrate, and a step of hydrolyzing the solution obtained in the step by adding the solution to an alkoxysilane or a metal alkoxide. Item 11. The method for producing a phosphor according to Item 10. 12. A color filter in which filter layers of a plurality of colors are arranged in a predetermined pattern on the inner surface of a light-transmitting panel, wherein at least one of the filter layers contains fine gold particles dispersed in an oxide matrix. A color filter characterized by being a thin film. 13. The gold fine particles having a particle size of 2.5 to 3
13. The color filter according to claim 12, wherein the thickness is 5.0 nm. 14. The method according to claim 1, wherein the oxide is silica (SiO ₂ ),
Aluminum oxide (Al ₂ O ₃ ), cerium oxide (Ce)
₂ O ₃ ), indium oxide (In ₂ O ₃ ), lanthanum oxide (La ₂ O ₃ ), tin oxide (SnO ₂ ), tantalum oxide (TaO _x ), zinc oxide (ZnO ₂ ), titanium oxide (TiO ₂ ) , Yttrium oxide (Y ₂ O ₃ ), zirconium oxide (ZrO ₂ ), indium oxide doped with tin (Sn), tin oxide doped with antimony (Sb), and tin oxide doped with aluminum (Al) 14. The color filter according to claim 12, wherein the color filter is at least one selected from the group consisting of: 15. The color filter according to claim 14, wherein the oxide is silica (SiO ₂ ). 16. The color filter according to claim 15, wherein a ratio of the gold fine particles to the silica in the thin film is 1.0 to 8.0% in a molar ratio. 17. The color filter according to claim 12, wherein the oxide is an oxide semiconductor having an electric resistivity of 1 × 10 ⁻⁵ Ω · m or less. 18. The color filter according to claim 17, wherein a ratio of the gold fine particles to the oxide semiconductor in the thin film is 0.1 to 8.0% in a molar ratio. 19. The oxide semiconductor may be formed of indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), ruthenium oxide (RuO _x ), rhenium oxide (ReO _x ), zinc oxide (ZnO), germanium oxide ( GeO ₂ ), copper oxide (Cu ₂ O), silver oxide (Ag ₂ O), vanadium oxide (V ₂ O ₅ ), titanium oxide (TiO ₂ ), and tungsten oxide (WO _x ). 19. The color filter according to claim 17, wherein: 20. A coating liquid containing gold fine particles and an alkoxysilane or a metal alkoxide, respectively, is applied on a light-transmitting panel, and then dried and fired, whereby the gold fine particles are dispersed and contained in an oxide matrix. A method for producing a color filter, characterized by forming a thin film formed. 21. The step of preparing the coating liquid, the step of adding an acidic aqueous solution to a solution of tetrachloroaurate (III) tetrahydrate dissolved in an organic solvent, and the step of preparing the solution obtained in the step. 21. A method for producing a color filter according to claim 20, comprising a step of hydrolyzing in addition to an alkoxysilane or a metal alkoxide. 22. A light-transmitting panel, a light-absorbing layer disposed on an inner surface of the panel, and a phosphor layer disposed on a back side opposite to the panel with respect to the light-absorbing layer. Prepared,
A color display device, wherein the phosphor layer includes the phosphor according to claim 1. 23. A light-transmitting panel, a light-absorbing layer and a color filter respectively disposed on an inner surface of the panel, and a phosphor disposed on a back side opposite to the panel with respect to the color filter. 20. A color display device comprising: a color filter, wherein the color filter is the color filter according to claim 12.