JP2003027054A - Aluminosilicate phosphor excitable with vacuum ultraviolet ray, method for producing the same, and vacuum-ultraviolet-ray-excitable luminescent element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkaline earth metal aluminosilicate phosphor which highly efficiently emits blue to bluish green light when excited with a vacuum ultraviolet ray of a wavelength of 200 nm or shorter, to provide a method for producing the same, and to provide a luminescent element excitable with a vacuum ultraviolet ray. SOLUTION: There are provided the vacuum-ultraviolet-ray-excitable alkaline earth metal aluminosilicate phosphor which contains at least one alkaline earth metal element selected from the group consisting of Ba, Sr, and Ca, an Al element, an Si element, and an Eu element and emits a blue to bluish green light when excited with the vacuum ultraviolet ray of the wavelength of 200 nm or shorter, the method for producing the same, and the vacuum-ultraviolet- ray-excitable luminescent element.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an alkaline earth metal aluminosilicate phosphor which is excited by vacuum ultraviolet rays having a wavelength of 200 nm or less and emits mainly blue to blue green light, a method for producing the same, and the above phosphor. The present invention relates to a VUV-excited light-emitting device equipped with a fluorescent film using.

[0002]

2. Description of the Related Art In recent years, rare gases such as Ar, Xe, He and Ne or a mixed gas thereof are enclosed in an envelope such as glass and the envelope is exposed by vacuum ultraviolet rays emitted by the discharge of the rare gas. The development of a VUV-excited light-emitting device that excites the fluorescent film formed inside the device to emit light is actively being carried out.

One example is a thin tube lamp used as a light source for reading in a scanner. X for thin tubes for lamps
A rare gas such as e, Xe-He, Xe-Ne, or Xe-He-Ne is enclosed, and a fluorescent film made of a fluorescent substance for exciting vacuum ultraviolet rays is formed on the inner surface of the tube. For example, when electric energy is applied from electrodes provided at both ends of the tube, a rare gas discharge occurs in the cell, and vacuum ultraviolet rays are emitted. The vacuum ultraviolet rays excite the phosphor to emit visible light. As the phosphor, a mixture of three colors of monochromatic materials of red, blue and green is used. The phosphors are (Y, Gd) BO ₃ : Eu as a red phosphor and LaPO as a green phosphor.
₄ : Ce, Tb, BaMgAl as blue phosphor
₁₀ O ₁₇ : Eu, (Ba, Sr) Mg as blue-green phosphor
Al ₁₀ O ₁₇ : Eu, Mn, etc. are used.

Another example of the VUV-excited light emitting device is a plasma display panel (hereinafter referred to as "PDP"). In principle, the PDP can be considered to be a matrix tube or a stripe array of lamps of different three colors in which a capillary tube excited by vacuum ultraviolet rays is made small. In other words, the narrow discharge spaces (hereinafter referred to as "cells") are arranged in a matrix or stripes. An electrode is provided in each cell, a phosphor film coated with a phosphor is formed inside each cell, and a rare gas such as Xe or Xe—Ne is sealed in each cell. When electric energy is applied from the electrodes, a rare gas discharge is generated in the cell and vacuum ultraviolet rays are emitted. This vacuum ultraviolet ray excites the phosphor to emit visible light, and an image is displayed by this emission.

In the case of full color PDP, vacuum ultraviolet ray excitation
The red, blue, and green phosphors in a matrix or
By applying it in stripes, the full color
The display can be done. In this case, for example, red phosphor
As (Y, Gd) BO₃: Eu, Z as green phosphor
n₂SiO_Four: Mn, BaMgAl as blue phosphor _Ten
O₁₇: Eu and others are used ("Electronic Material Magazine" 1997
December issue, published by Industrial Research Council).

Among these phosphors, BaMgAl ₁₀ O ₁₇ : Eu which is mainly used as a blue light emitting phosphor for PDP.
And (Ba, Sr) MgAl ₁₀ O ₁₇ used as a blue-green light emitting phosphor for improving the color rendering of fluorescent lamps:
Aluminate phosphors such as Eu and Mn emit light with high brightness when excited by vacuum ultraviolet rays, and have been practically used as blue to blue-green phosphors of typical vacuum ultraviolet ray excited light emitting devices.

However, these aluminate phosphors are not able to maintain the brightness of the phosphor powder as powder due to thermal deterioration in the baking process during the formation of the phosphor film when manufacturing a VUV-excited light emitting device. In addition, when it is irradiated with vacuum ultraviolet rays for a long time, the emission luminance is reduced (luminance deterioration), so it has the drawback that the emission luminance decreases over time during operation as an ultraviolet excitation light emitting element. Was there. Therefore, it is desired to develop a new phosphor for exciting VUV light, which replaces the aluminate phosphor that emits blue to blue-green light with high brightness when excited with VUV light.

[0008]

DISCLOSURE OF THE INVENTION The present invention has solved the above-mentioned problems, and an aluminosilicate phosphor of an alkaline earth metal which efficiently emits blue or blue-green light by excitation with vacuum ultraviolet rays having a wavelength of 200 nm or less and a phosphor thereof. It is intended to provide a manufacturing method and a VUV-excited light-emitting device provided with a fluorescent film using this phosphor.

[0009]

The inventors of the present invention have synthesized various phosphors of oxyacid salt system and irradiate them with vacuum ultraviolet rays having a wavelength of 200 nm or less to determine whether blue or blue-green light is emitted and its emission intensity. As a result of investigating the degree and conducting extensive studies, an aluminosilicate of an alkaline earth metal was used as a host crystal, and Eu was added to this.
By activating the element, the peak wavelength is 400 to 50.
The inventors have found that a phosphor showing 0 nm emission can be obtained, and that a vacuum ultraviolet ray excited light emitting device that emits blue to blue green light with high efficiency can be obtained by using this phosphor as a phosphor film, and completed the present invention. . The configuration of the present invention is as follows.

(1) It contains at least one alkaline earth metal element, Al element, Si element and Eu element selected from the group consisting of Ba, Sr and Ca, and has a wavelength of 200 n.
An aluminosilicate phosphor of alkaline earth metal for vacuum ultraviolet ray excitation, which emits blue or blue-green light when excited by vacuum ultraviolet ray of m or less.

(2) Vacuum-ultraviolet ray excitation, characterized in that the alkaline earth metal aluminosilicate phosphor is represented by the following general formula and emits blue or blue-green light when excited by vacuum ultraviolet ray having a wavelength of 200 nm or less. Alkaline earth metal aluminosilicate phosphor for use. (M _1-x Eu _x ) O · aAl ₂ O ₃ · bSiO ₂ (wherein, M represents at least one alkaline earth metal element selected from the group consisting of Ba, Sr and Ca, and x = 0.02-1.0, a = 0.9-1.1, b
= A number satisfying the conditions of 1.8 to 2.2)

(3) The alkaline earth metal aluminosilicate phosphor has a main phase of a crystal whose crystal system is a monoclinic system or a triclinic system.
The alkaline earth metal aluminosilicate phosphor for exciting VUV light according to (2).

(4) A wavelength of 200 containing at least one alkaline earth metal element selected from the group consisting of Ba, Sr and Ca, an Al element, a Si element and a Eu element, respectively.
In the method for producing an alkaline earth metal aluminosilicate phosphor that emits blue or blue-green light when excited by vacuum ultraviolet light having a wavelength of nm or less, the vacuum ultraviolet light is characterized in that the phosphor material is fired in the presence of a fluorine compound. Method for producing aluminosilicate phosphor of alkaline earth metal for excitation. (5) The alkaline earth metal aluminosilicic acid for VUV excitation according to (4), wherein the fluorine compound is at least one selected from the group consisting of ammonium fluoride, aluminum fluoride and lithium fluoride. Method for producing salt.

(6) The envelope has a fluorescent film inside, and the fluorescent film emits light by being excited by vacuum ultraviolet rays having a wavelength of 200 nm or less generated by the discharge of the rare gas enclosed in the envelope. In the VUV-excited light-emitting device, the fluorescent film contains the VUV-excited luminescence characterized by containing the alkaline earth metal aluminosilicate phosphor according to any one of (1) to (3). element.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The phosphor of the present invention comprises at least one alkaline earth metal selected from the group consisting of Ba, Sr and Ca and an alkaline earth metal having Al and Si as constituent elements. Aluminosilicate as a host crystal,
It is an alkali metal aluminosilicate phosphor containing Eu as an activator, absorbs vacuum ultraviolet rays having a wavelength of 200 nm or less, and emits blue to blue-green light having a peak wavelength of 400 to 500 nm with high efficiency. It is a thing.

In order to produce the alkaline earth metal aluminosilicate phosphor of the present invention, at least one alkaline earth metal element selected from the group of Ba, Sr and Ca,
The oxides, carbonates, nitrates, oxalates, etc. of Al element, Si element, and Eu element are used so that the composition ratio of each element in the compound becomes a desired chemical composition. Weigh and mix well to prepare a phosphor raw material. Fill this into a heat-resistant container such as an alumina crucible,
It is fired at a temperature in the range of 1100 to 1600 ° C. once or more for 2 to 40 hours including the temperature raising / lowering time, and the obtained fired product is dispersed, washed with water, dried, sieved, and the like. It can be manufactured through a usual post-treatment method adopted as a post-treatment step during production. However, it is desirable that at least one of the firing is performed in a reducing atmosphere. The preferable firing conditions are 115 in a reducing atmosphere.
That is, firing is performed at 0 to 1500 ° C. for 2 to 40 hours including the temperature raising and lowering time.

One of the features of the present invention is that the phosphor raw material contains
That is, a fluorine compound is mixed and baked as a flux which is a reaction accelerator, and at least one selected from the group of ammonium fluoride, aluminum fluoride, and lithium fluoride among the fluorine compounds is the vacuum of the present invention. It is more preferable as a flux for producing an aluminosilicate phosphor of an alkaline earth metal for ultraviolet ray excitation. As a result, monoclinic or triclinic crystals are formed as the main phase, and highly efficient blue to blue-green light is emitted.

Alkaline Earth Metal Aluminosilicates of the Invention
The salt phosphor has a monoclinic or triclinic crystal as the main phase.
To do. Its composition formula is (M_1-xEu_x) Oa
Al ₂O₃・ BSiO₂(Where M is Ba, Sr and C
at least one alkaline earth gold selected from the group a)
Represents a genus element, x = 0.02-1, a = 0.9-1.
1, b is a number in the range of 1.8 to 2.2, and so on.
is there. ), The main phase of the crystal is monoclinic or
When it is a triclinic system, it changes from blue to blue due to vacuum ultraviolet excitation.
Since it is possible to obtain a phosphor with a high green emission intensity,
Good

In the phosphor of this composition, for example, when the alkaline earth metal element M is Ba and a = 1 and b = 2, the matrix of the phosphor has a composition formula of BaAl ₂ Si ₂ O ₈ (= BaO.Al ₂
O ₃ · 2SiO ₂ ), and it emits light by substituting a part of the Ba position of this host crystal with divalent Eu as an activator. The emission color of this phosphor changes from blue to blue-green as the substitution amount of Eu as an activator increases. Usually, when the concentration of the activator in the phosphor is too high, a phenomenon called concentration quenching in which the luminous efficiency is reduced is observed, but in the phosphor of the present invention, this concentration quenching is not observed, and the Eu substitution amount It is possible to obtain a highly efficient phosphor that emits blue to blue-green light by changing. However, if the amount of substitution of Eu is too small, the amount of emission centers will be insufficient, and the emission intensity will decrease. When the above phosphors were manufactured by changing the Eu substitution amount and the emission intensity under the vacuum ultraviolet ray excitation was examined, the Eu substitution amount (x value) was 0.02 ≦.
It has been found that blue to blue-green light emission is exhibited particularly efficiently when adjusted to a range of x ≦ 1. A more preferable range of the Eu substitution amount (x value) is 0.1 ≦ x ≦ 1.

The crystal system of the phosphor of the present invention can be confirmed by comparing the X-ray diffraction data of JCPDS with that of the phosphor. In FIG. 1, the composition formula is (Ba _0.9 Eu _0.1 ) Al ₂ Si
₂ shows a powder diffraction X-ray spectrum of a phosphor of the present invention which is ₂ O ₈ . This spectrum has the same pattern as the data of monoclinic BaAl ₂ Si ₂ O ₈ announced by JCPDS.

FIG. 2 shows that the composition formula is (Ba _0.9 Eu _0.1 ) A.
l is a phosphor diagram illustrating an excitation spectrum over the UV range from vacuum ultraviolet ray region of the present invention which is a ₂ Si ₂ O _8. The horizontal axis of FIG. 2 represents the vacuum ultraviolet rays and the wavelengths of the ultraviolet rays with which this phosphor is irradiated, and the relative quantum efficiency of the vertical axis is the emission intensity of the phosphor when irradiated with the vacuum ultraviolet rays and ultraviolet rays of each wavelength, and 120. The emission intensity of sodium salicylate having a constant quantum efficiency in the wavelength range of up to 300 nm is measured, and the emission quantum efficiency of sodium salicylate is 100%.
Is shown as a relative value.

As is clear from FIG. 2, the phosphor of the present invention maintains a high quantum efficiency in the wavelength range of 120 to 200 nm in the vacuum ultraviolet wavelength range as well as in the ultraviolet wavelength range of 200 to 300 nm. I understand.

FIG. 3 is a barium aluminosilicate phosphor [(Ba _1-x Eu _x ), which is one of the alkaline earth metal aluminosilicate phosphors of the present invention having different Eu concentrations (x values).
[Al ₂ Si ₂ O ₈ ] is each emission spectrum when excited by vacuum ultraviolet light having a wavelength of 146 nm,
In the figure, curves a, b, c, d and e are spectra when the Eu concentration (x value) is 0.02, 0.10, 0.30, 0.50 and 0.90, respectively. Thus, the barium aluminosilicate phosphor (Ba _1-x Eu _x ) Al ₂
With Si ₂ O ₈ , the peak wavelength of the emission spectrum shifts to the long wavelength side as the activator Eu concentration (x value) increases, and changes from deep blue to blue green.

Although not illustrated, the emission spectrum of the Eu-activated alkaline earth metal aluminosilicate phosphor of the present invention when excited by vacuum ultraviolet rays is as follows even if the alkaline earth metal element is other than Ba. The emission spectrum has almost the same emission spectrum as that illustrated in FIG. 3, and it was found that the peak wavelength of the emission spectrum shifts to the long wavelength side as the Eu concentration (x value) increases, and the emission color changes. .

The VUV-excited light-emitting device of the present invention has a phosphor film containing the above-described alkaline earth metal aluminosilicate phosphor formed inside an envelope. The fluorescent film is manufactured as follows. First, the alkaline earth metal aluminosilicate phosphor and ethyl cellulose,
Binder resin such as nitrocellulose, polyethylene oxide, acrylic resin, and further for viscosity adjustment,
A phosphor paste composition is prepared by mixing water, a solvent such as butyl acetate, butyl carbitol, and terpineol, and thoroughly kneading. The phosphor paste is applied to the inside of the envelope, dried, and then baked to form a phosphor coating film inside the envelope.

The phosphor sample for measuring the brightness and chromaticity of the phosphor is prepared by pressing the phosphor powder into a cell having a recess having a diameter of 15 mm and a depth of 1 mm and flattening the surface with a glass plate. To form a smooth surface, and
A 6 nm vacuum ultraviolet ray was irradiated to emit light, and the chromaticity and emission luminance at that time were measured. The brightness of the blue phosphor greatly changes in proportion to the emission color (y value of the chromaticity point). As a simple method for comparing the luminous efficiencies between phosphors having different emission color y values, it is common practice to compare the luminance by dividing the luminance by the y value (luminance / y) value (hereinafter referred to as stimulus sum). . Therefore, also in the present invention, the luminous efficiency between the phosphors is compared using the stimulus sum.

[0027]

The present invention will be described below with reference to examples. (Example 1) BaCO ₃ 0.98 moles Eu ₂ O ₃ were mixed thoroughly 0.01 mole Al ₂ O ₃ 0.926 mol SiO ₂ 2 mol AlF ₃ 0.148 moles above phosphor materials, an alumina crucible And was fired in a reducing atmosphere at a maximum temperature of 1300 ° C. for 24 hours including a temperature raising / lowering time. The fired product was dispersed, washed with water, dried, and sieved to give a composition of (Ba _0.98 Eu).
_{A 0.02} ) Al ₂ Si ₂ O ₈ Eu-activated aluminosilicate phosphor was obtained. The powder diffraction X-ray spectrum of the characteristic X-ray of CuKα1 of this phosphor was measured, and it was confirmed that the phosphor showed almost the same pattern as the phosphor shown in FIG. 1 and that the phosphor had a monoclinic system as the main phase. Was done.

This phosphor was irradiated with vacuum ultraviolet rays having a wavelength of 146 nm to examine the emission chromaticity. The chromaticity coordinate value is x = 0.1
51 and y = 0.080. In addition, the brightness of this phosphor was measured. Sum of stimuli based on the brightness (brightness /
y) was set to 100, and the stimulus sum of the luminescence of the phosphors in the following examples was expressed as a relative stimulus sum value based on this.

(Examples 2 to 8) The starting material compounds used,
Eu of Examples 2 to 8 was performed in the same manner as in Example 1 except that the compounding ratio was changed as shown in Table 1 to change the Eu activation amount.
An activated aluminosilicate phosphor was obtained. The compositions of the phosphors of Examples 2 to 8 are shown in Table 2. Further, the powder diffraction X-ray spectra of the phosphors of Examples 2 to 8 by characteristic X-ray of CuKα1 were measured, and it was confirmed that all of the phosphors of Examples 2 to 8 had a monoclinic system as the main phase. Was done.

The Eu-activated aluminosilicate phosphors of Examples 2 to 8 were irradiated with vacuum ultraviolet rays of 146 nm under the same conditions as in Example 1, and the chromaticity coordinate values of the emission and the chromaticity coordinate values of Example 1 were measured. Table 2 shows the relative sum of stimuli when the sum of the stimuli of luminescence of the phosphors was 100, together with the luminescence chromaticity values (x value and y value) of each phosphor.

[0031]

[Table 1]

[0032]

[Table 2]

Examples 9 to 16 Eu-activated aluminosilicate fluorescent materials of Examples 9 to 16 were prepared in the same manner as in Example 1 except that the starting compounds used and the compounding ratios thereof were changed as shown in Table 3. Got the body The composition of each phosphor of Examples 9 to 16 is shown in Table 4 together with the emission chromaticity values (x value and y value) of each phosphor. The powder diffraction X-ray spectra of the phosphors of Examples 9 to 16 by characteristic X-ray of CuKα1 were measured, and the phosphors of Examples 9 to 15 were composed of barium aluminosilicate and strontium aluminosilicate having a monoclinic system. It was confirmed that the solid solution was the main phase and the phosphor of Example 16 was a monoclinic strontium aluminosilicate crystal.
FIG. 4A is a powder diffraction X-ray spectrum of the strontium aluminosilicate phosphor {(Sr _0.9 Eu _0.1 ) Al ₂ Si ₂ O ₈ } of Example 16.

The Eu-activated aluminosilicate phosphors of Examples 9 to 16 were irradiated with vacuum ultraviolet rays of 146 nm under the same conditions as in Example 1, and the chromaticity coordinate values of light emission and that of Example 1. Table 4 shows the relative sum of stimuli with the stimulus sum of luminescence of the phosphor being 100, together with the luminescence chromaticity values (x value and y value) of each phosphor.

[0035]

[Table 3]

[0036]

[Table 4]

(Examples 17 to 24) Eu-activated aluminosilicate fluorescent materials of Examples 17 to 24 were prepared in the same manner as in Example 1 except that the starting compounds used and the compounding ratios thereof were changed as shown in Table 5. Got the body The composition of each phosphor of Examples 17 to 24 is shown in Table 6 together with the emission chromaticity values (x value and y value) of each phosphor. When the powder diffraction X-ray spectra by the characteristic X-rays of CuKα1 of the phosphors of Examples 17 to 24 were measured,
It was confirmed that the phosphors of Examples 17 to 24 were a mixed crystal of monoclinic barium aluminosilicate and triclinic calcium aluminosilicate. FIG. 4B illustrates the powder diffraction X-ray spectrum of (Ca _0.9 Eu _0.1 ) Al ₂ Si ₂ O ₈ of Example 24.

The Eu-activated aluminosilicate phosphors of Examples 17 to 24 were irradiated with vacuum ultraviolet rays of 146 nm under the same conditions as in Example 1, and the chromaticity coordinate values of the emitted light and the value of Example 1. Table 6 shows the relative sum of stimuli when the sum of stimuli of luminescence of the phosphors was 100, together with the luminescence chromaticity values (x value and y value) of each phosphor.

[0039]

[Table 5]

[0040]

[Table 6]

Example 25 BaCO ₃ 0.9 mol Eu ₂ O ₃ 0.05 mol Al ₂ O ₃ 1 mol SiO ₂ 2 mol LiF 0.480 mol Other than changing the compounding ratio of the raw material compounds as described above In the same manner as in Example 1 except that the composition of Example 25 (Ba _0.9 Eu
_0.1 ) An Eu-activated aluminosilicate phosphor of Al ₂ Si ₂ O ₈ was obtained. When the powder diffraction X-ray spectrum of CuKα1 of this phosphor was measured by a characteristic X-ray, it was confirmed to be almost monoclinic.

When this phosphor was irradiated with vacuum ultraviolet rays having a wavelength of 146 nm under the same conditions as in Example 1, the emission chromaticity coordinate values were x = 0.157 and y = 0.109. Further, the stimulus sum of the luminescence of the phosphor of Example 1 is set to 100.
The sum of relative stimuli of luminescence was 146.

Example 26 BaCO ₃ 0.9 mol Eu ₂ O ₃ 0.05 mol Al ₂ O ₃ 1 mol SiO ₂ 2 mol NH ₄ F 0.336 mol The compounding ratio of the raw material compounds was changed as described above. Except that, the composition of Example 26 (Ba _0.9 Eu) is obtained in the same manner as in Example 1.
_0.1 ) An Eu-activated aluminosilicate phosphor of Al ₂ Si ₂ O ₈ was obtained. When the powder diffraction X-ray spectrum of CuKα1 of this phosphor was measured by a characteristic X-ray, it was confirmed to be almost monoclinic.

When this phosphor was irradiated with vacuum ultraviolet rays having a wavelength of 146 nm under the same conditions as in Example 1, the chromaticity coordinate values of the emitted light were x = 0.150 and y = 0.087. Further, the stimulus sum of the luminescence of the phosphor of Example 1 is set to 100.
Was 148, and the relative stimulation sum of luminescence was 148.

Comparative Example 1 BaCO ₃ 0.9 mol Eu ₂ O ₃ 0.05 mol Al ₂ O ₃ 1 mol SiO ₂ 2 mol Example 1 except that the compounding ratio of the raw material compounds was changed as described above. The composition of Comparative Example 1 (Ba _0.9 E
An Eu-activated aluminosilicate phosphor of u _0.1 ) Al ₂ Si ₂ O ₈ was obtained. The powder diffraction X-ray spectrum of this phosphor with CuKα1 characteristic X-ray was measured, and as a result, it was confirmed to be almost hexagonal.

When this phosphor was irradiated with vacuum ultraviolet rays having a wavelength of 146 nm under the same conditions as in Example 1, the main emission was ultraviolet emission having a peak wavelength of 370 nm,
The chromaticity coordinate values of the emitted light were x = 0.199 and y = 0.166.

[0047]

EFFECTS OF THE INVENTION The present invention, by adopting the above-mentioned constitution, exhibits an alkaline earth metal aluminosilicate phosphor that emits blue or blue-green light with high brightness when excited by vacuum ultraviolet rays having a wavelength of 200 nm or less. It is possible to provide a VUV-excited light-emitting device that emits excellent blue to blue-green light by applying it to the fluorescent film of the VUV-excited light-emitting device.

[Brief description of drawings]

FIG. 1 has a composition formula of (Ba _0.9 Eu _0.1 ) Al ₂ Si ₂ O.
₉ is a powder diffraction X-ray spectrum of the phosphor of the present invention which is No. ₈ ;

FIG. 2 is a composition formula of (Ba _0.9 Eu _0.1 ) Al ₂ Si ₂ O.
_{FIG. 8} is an excitation spectrum in the wavelength range from vacuum ultraviolet rays to ultraviolet rays of the phosphor of the present invention which is No.

FIG. 3 is an emission spectrum when each aluminosilicate phosphor of the present invention having a different Eu concentration is excited by vacuum ultraviolet light.

FIG. 4 is a composition formula of (Sr _0.9 Eu _0.1 ) Al ₂ Si ₂ O
₈ of the present invention (curve a) and the composition formula is (Ca
₃ is a powder diffraction X-ray spectrum of the phosphor of the present invention (curve b) which is _0.9 Eu _0.1 ) Al ₂ Si ₂ O ₈ .

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01J 61/44 H01J 61/44 NF term (reference) 4H001 CF02 XA08 XA13 XA14 XA20 XA38 XA56 YA63 5C040 GG08 KA20 KB08 KB28 MA10 5C043 AA07 CC09 DD28 EB04 EC16 EC20

Claims (5)

[Claims] 1. At least one alkaline earth metal element, Al element and S selected from the group of Ba, Sr and Ca.
Each contains i element and Eu element, and has a wavelength of 200 nm.
An alkaline earth metal aluminosilicate phosphor for exciting vacuum ultraviolet rays, which emits blue or blue-green light when excited by the following vacuum ultraviolet rays. 2. A vacuum ultraviolet ray excitation, wherein the alkaline earth metal aluminosilicate phosphor is represented by the following general formula and emits blue or blue green when excited by vacuum ultraviolet ray having a wavelength of 200 nm or less. Alkaline earth metal aluminosilicate phosphor. (M _1-x Eu _x ) O · aAl ₂ O ₃ · bSiO ₂ (wherein, M represents at least one alkaline earth metal element selected from the group consisting of Ba, Sr and Ca, and x = 0.02-1.0, a = 0.9-1.1, b
= A number satisfying the conditions of 1.8 to 2.2) 3. The alkaline earth metal aluminosilicate phosphor has as a main phase a crystal whose crystal system is a monoclinic system or a triclinic system. An alkaline earth metal aluminosilicate phosphor for excitation by vacuum ultraviolet ray as described above. 4. At least one alkaline earth metal element, Al element and S selected from the group consisting of Ba, Sr and Ca.
Wavelength 200n containing i element and Eu element, respectively
In the method for producing an alkaline earth metal aluminosilicate phosphor that emits blue or blue-green light when excited with vacuum ultraviolet light of m or less, the vacuum ultraviolet light is characterized in that the phosphor material is fired in the presence of a fluorine compound. Method for producing aluminosilicate phosphor of alkaline earth metal for excitation. 5. The fluorescent film is provided inside the envelope, and the fluorescent film is caused to emit light by being excited by vacuum ultraviolet rays having a wavelength of 200 nm or less generated by discharge of a rare gas enclosed in the envelope. A VUV-excited light-emitting device, wherein the phosphor film contains the alkaline earth metal aluminosilicate phosphor according to any one of claims 1 to 3.