CN100397544C - Light emitting device and image display device using the same - Google Patents

Abstract

The object of the present invention is to improve the reliability, luminance characteristics and color purity characteristics of a light-emitting device and a display device using a phosphor such as a lamp or a PDP. The solution is to use Sr as a blue phosphor_3a-eMg_bSi_2cO_8d:Eu_cPhosphors produced by optimizing the composition ratio of Mg, Si, etc. or by optimizing the composition of new components such as Ba, Ca, etc. as the base material are excited by ultraviolet rays generated by xenon discharge to emit light to achieve high luminance and high color purity of the phosphors, and light emitting devices such as lamps, PDPs, etc. and display devices are constructed using the optimized phosphors.

Description

Light emitting device and image display device using the light emitting device

technical field

The present invention relates to phosphors that emit light when excited by ultraviolet rays, especially ultraviolet rays in the vacuum ultraviolet region, especially tubular or planar fluorescent lamps or plasma display screens that are formed using Eu-activated silicate phosphors, and their use An image display device (hereinafter simply referred to as a display device) of the light emitting device.

Background technique

In recent years, people have increasingly high demands on display devices such as TVs and personal computer monitors (Pasoconmonita) that do not take up space and are thinner. Developments such as plasma display (PDP) devices, field emission display (FED) devices, and liquid crystal display devices that combine a backlight with a thin liquid crystal panel to form a display device are being actively carried out.

A plasma display device is a display device that uses a plasma display as a light emitting device. 147nm and 172nm band) as an excitation source to excite the phosphor in the phosphor layer arranged in the tiny discharge space to promote the phosphor to emit light, thereby obtaining light in the visible region. The amount and color of this light emission is controlled by a plasma display (PDP) device and used for image display.

In addition, the liquid crystal display device is composed of a combination of the above-mentioned backlight and a liquid crystal display panel formed by sandwiching liquid crystal between a pair of electrode substrates. A device that displays the desired image using the amount or color of light. In addition, as the current backlight, a tubular white fluorescent lamp such as a straight tube type in which a phosphor material is coated on an inner wall is generally used.

In addition, as documents related to these technologies, Patent Documents 1 to 4 and Non-Patent Documents 1 to 3 shown below are cited.

(Patent Document 1) JP-A-2003-132803

(Patent Document 2) JP-A-2003-142004

(Patent Document 3) JP-A-2003-242892

(Patent Document 4) JP-A-2003-346660

(Non-Patent Document 1) "Phosphor Handbook" edited by Phosphor Alumni Society, 1987, III, Chapter 2, pp. 219-223

(Non-Patent Document 2) IDW'00 Proceedings of The Seventh International Display Workshops, page 639-page 642

(Non-Patent Document 3) TECHNICAL REPORT OF IEICE.EID2003-69 (2004-01) Page 45-48

(Non-Patent Document 4) "FLAT-PANEL DISPLAY 2003 (Practice Edition)", Nikkei BP, PART.7-1, pp. 210-217

Contents of the invention

Although it is hoped that the light-emitting devices of plasma display devices and FED devices, as well as the backlight used in liquid crystal display devices, will achieve high performance, but the improvement of these characteristics is largely related to the design structure and configuration of various devices. They are related to their materials, especially phosphors used in light-emitting devices.

Red, blue, and green phosphors are used as phosphors in conventional PDP devices, and aluminate phosphors (BaMgAl ₁₀ O ₁₇ :Eu, hereinafter abbreviated as BAM) are generally used as blue phosphors. Although this BAM has excellent light emitting characteristics, it has a problem of being easily deteriorated. That is, there is a problem in terms of reliability and the life is short, so stability and long life are strongly demanded. Furthermore, in order to further improve the performance of light-emitting devices, and furthermore, display devices, higher color purity and higher light emission luminance are required.

In addition, with regard to the backlight for light bulbs and liquid crystal display devices, it is also required to improve the brightness of the display surface and to achieve mercury-free in consideration of environmental problems. As a countermeasure, people are developing flat type LED backlights for liquid crystal display devices. rare gas discharge fluorescent lamps, etc. As a rare gas discharge fluorescent lamp, phosphors that are excited by vacuum ultraviolet rays are usually used to emit light with high efficiency, high brightness and high color purity under vacuum ultraviolet excitation conditions, and long-life phosphors are required. .

In recent years, a class of high-brightness, high-color-purity, and high-reliability blue phosphors that can replace BAM is being developed, and a silicate-based phosphor is proposed as a blue phosphor, which can be used It is used in PDP devices and rare gas discharge bulbs, and has high reliability and long life compared with BAM, which is a conventional blue light-emitting phosphor. Specifically, Ca _1-x MgSi ₂ O ₆ : _Eux (hereinafter abbreviated as CMS) is proposed.

However, although CMS has high luminance and good color purity when using ultraviolet light in the wavelength band of 147 nm as an excitation source, there is almost no excitation band in the wavelength range of 160 nm to 210 nm. Therefore, there is a problem that the intensity of light emitted when excited by vacuum ultraviolet rays (Xe ₂ molecular rays) near 172 nm, which is important for PDPs, is significantly reduced.

Currently, in parallel with the research on improving the performance of phosphor materials, in the technical field of PDP devices, research is being carried out to improve the structure of the display screen for the purpose of improving the luminous efficiency of the PDP. As one of the methods, making the discharge gas The composition ratio of Xe gas is increased, and researches on actively utilizing Xe ₂ molecular rays are being carried out extensively. This is the so-called "high xenonization" technology in the plasma display panel. The composition ratio of xenon gas in the discharge gas is higher than about 4%, and people are conducting research to increase the efficiency of this PDP display panel.

However, CMS, which has a very low utilization efficiency of Xe ₂ molecular rays, cannot fully meet the requirements of this technology for increasing the efficiency of PDPs. That is, even if the ultraviolet light in the 172 nm band is increased, the luminous efficiency under the excitation condition of 172 nm is low, and the obtained luminance characteristics are not sufficient. Therefore, even if the high efficiency of PDP is taken into consideration in the future, it is necessary to further improve the practical use of CMS instead of BAM, especially the luminous efficiency in the 172nm wavelength excitation band must be improved.

Therefore, the first problem to be solved by the present invention is that conventional phosphors used under vacuum ultraviolet excitation conditions in PDP devices and the like, especially blue phosphors, have insufficient lifetime. As a result, using these fluorescent Insufficient life (generally, usable period) and luminance characteristics of a body light-emitting device, and insufficiency in life (generally, usable period) and luminance characteristics of an image display device using the light-emitting device. Moreover, performance such as color purity cannot be said to be sufficient.

In addition, the second problem to be solved by the present invention is that, in the silicate phosphor proposed as an improvement strategy for the problem of the above-mentioned conventional blue phosphor, the luminance characteristics, particularly the Xe ₂ molecular rays ( The luminance characteristic excited by the wavelength 172nm) is very low, and the luminance characteristics of the current light-emitting device and the display device using the current light-emitting device, and the light-emitting device excitedly using _Xe2 molecular rays (172nm) to be excited in the future, especially the PDP device , and insufficient luminance characteristics of the PDP image display device.

In order to accomplish the above-mentioned problems, the characteristic points of the representative light-emitting device of the present invention can be enumerated. It has at least one pair of electrodes, and at the same time, it has a discharge gas that can discharge and generate ultraviolet rays by applying a voltage between the electrodes, And a light-emitting device of a phosphor layer that is excited and emits light when it is subjected to the action of ultraviolet rays generated from the discharge gas, wherein the discharge gas contains Xe in an amount of 6% or more, preferably 10% or more Xenon (Xe) gas, the phosphor constituting the above-mentioned phosphor layer is a kind of Eu activated by the following formula (I) that is excited when it is subjected to the action of vacuum ultraviolet rays with a wavelength of at least 172 nm generated based on the above-mentioned xenon discharge. silicate phosphor. In addition, the characteristic points of a representative image display device of the present invention, which has the above-mentioned light emitting device and plasma display panel structure, can be cited.

M1 _3a-e Mg _b Si _2c O _8d :Eu _e ...(I)

However, in formula (I), M1 is one or more elements selected from strontium (Sr), calcium (Ca) and barium (Ba), and a, b, c, d and e are respectively 0.8≤a≤ 1.2, 0.8≤b≤1.2, 0.8≤c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2.

Particularly preferably, the above-mentioned phosphor is an Eu-activated silicate phosphor represented by the above-mentioned formula (I), characterized in that it is a phosphor containing a, b, c, and d in the above-mentioned formula (I). Phosphors of Eu-activated silicate phosphors whose values are a=1, b=1, c=1, and d=1, respectively.

Furthermore, it is characterized in that, in the above-mentioned europium (Eu)-activated silicate phosphor used, according to the description of the above-mentioned formula (I), the more preferable composition ratio of europium (Eu) as an activator is 0.01≤e ≤0.05.

In addition, it is characterized in that, in the Eu-activated silicate phosphor used, a more preferable composition ratio of magnesium (Mg) is 1<b≦1.2 as described in the above formula (I).

In addition, it is characterized in that, in the Eu-activated silicate phosphor used, the composition ratio of silicon (Si) is 1<c≦1.2 as described in the above formula (I).

In addition, the present invention is characterized in that, in the light-emitting device composed of phosphors, the phosphors used are composed of Eu-activated silicate phosphors represented by the general formula (II) below.

(Sr _1-x M2 _x ) _3a-e Mg _b Si _2c O _8d :Eu _e ...(II)

It should be noted that in the formula (II), M2 is from barium (Ba), calcium (Ca), zinc (Zn), manganese (Mn), titanium (Ti), vanadium (V), cobalt (Co), palladium ( Pd), platinum (Pt), nickel (Ni), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium ( Sm), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), antimony (Sb), thallium (T1), and lutetium ( One or more elements selected from Lu), a, b, c, d, e and x are 0.8≤a≤1.2, 0.8≤b≤1.2, 0.8≤c≤1.2, 0.8≤d≤1.2, 0.001, respectively ≤e≤0.2, 0.1<x≤0.5, but in the case of M2=Ba, x is in the range of 0.1<x≤0.5, more preferably x is in the range of 0.1<x<0.2 or 0.2<x≤0.5.

In particular, the above-mentioned phosphor is an Eu-activated silicate phosphor represented by the above-mentioned formula (II), which is characterized in that the values of a, b, c, and d in the above-mentioned formula (II) are respectively a=1 , b=1, c=1, d=1 Eu-activated silicate phosphor phosphor.

In particular, the present invention is characterized in that, in the light-emitting device composed of phosphors, the phosphors used are composed of Eu-activated phosphors represented by the general formula (III) below.

(Sr _1-xy Ba _x M3 _y ) _3a-e Mg _b Si _2c O _8d :Eu _e ...(III)

In formula (III), M3 is calcium (Ca), zinc (Zn), manganese (Mn), titanium (Ti), vanadium (V), cobalt (Co), palladium (Pd), platinum (Pt), nickel (Ni), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), antimony (Sb), thallium (T1), and lutetium (Lu) The elements of a, b, c, d and e are respectively 0.8≤a≤1.2, 0.8≤b≤1.2, 0.8≤c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2, x and y are barium ( The composition ratio of Ba) to the above-mentioned M3 element is 0.1<x+y≦0.5.

In particular, the above-mentioned phosphor is an Eu-activated silicate phosphor represented by the above-mentioned formula (III), and it is characterized in that it contains the values of a, b, c, and d in the above-mentioned formula (III) respectively being a =1, b=1, c=1, d=1 Eu-activated silicate phosphor phosphor.

Furthermore, the present invention is characterized in that, in the light-emitting device composed of phosphors, the phosphors used are composed of Eu-activated phosphors represented by the general formula (IV) below.

(Sr _1-xy Ca _x M4 _y ) _3a-e Mg _b Si _2c O _8d :Eu _e ...(IV)

However, in formula (VI), M4 is derived from barium (Ba), zinc (Zn), manganese (Mn), titanium (Ti), vanadium (V), cobalt (Co), palladium (Pd), platinum (Pt) , nickel (Ni), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), gadolinium (Gd) , terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), antimony (Sb), thallium (Tl) and lutetium (Lu) More than one element, a, b, c, d and e are respectively 0.8≤a≤1.2, 0.8≤b≤1.2, 0.8≤c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2, x and y are The composition ratio of calcium (Ca) to the above M4 element is 0<x+y≦0.2.

In particular, the above-mentioned phosphor is an Eu-activated silicate phosphor represented by the above-mentioned formula (IV), which is characterized in that the values of a, b, c, and d in the above-mentioned formula (IV) are respectively a=1, Eu-activated silicate phosphors with b=1, c=1, and d=1.

The effect of the invention

The light-emitting device of the present invention is advantageous in that, since a high-brightness Eu-activated silicate phosphor with good luminous efficiency is used even under the light-excitation condition of a wavelength of 172 nm in addition to the light-excitation condition of a wavelength of 147 nm, Therefore, high luminance can be obtained.

In addition, the light-emitting device in the present invention is also advantageous in that Eu-activated silicic acid with good luminous efficiency and high color purity is used even under the light-excitation condition of wavelength 172 nm in addition to the light-excitation condition of wavelength 147 nm. Salt phosphor, so excellent luminescent properties can be obtained.

In addition, the advantage of this display device in the present invention is that since the light-emitting device constituted uses high-brightness Eu-activated silicate phosphor and Eu-activated silicate phosphor with high color purity, high brightness can be achieved. display and display with high color purity.

Description of drawings

FIG. 1 shows the excitation and luminescence spectra of the phosphor SMS (Sr _2.98 MgSi ₂ O ₈ :Eu _0.02 ) constituting the first embodiment of the present invention and CMS as a comparison object.

Fig. 2 is an exploded perspective view showing a structural example of a plasma display panel as an embodiment of the present invention.

FIG. 3 is a graph showing the relationship between the Eu composition ratio and the relative luminance in phosphors serving as PDP components in the first embodiment of the present invention.

FIG. 4 is a block diagram showing an image display device using a plasma display panel (PDP) of the present invention.

5 is a graph showing the relationship between the Ba composition ratio, the relative luminance, and the y value in a phosphor serving as a PDP component according to a fourth embodiment of the present invention.

6 is a cross-sectional view showing the structure of a rare gas (xenon-enclosed gas) discharge white fluorescent lamp according to a fifth embodiment of the present invention.

Fig. 7 is an exploded perspective view showing the structure of the liquid crystal display device of the present invention.

Symbol Description

1, 6...substrate,

2, 9... electrodes,

3... busbar,

4, 8...dielectric layer,

5...protective film,

7...next door,

10... Phosphor layer,

100...plasma display,

101...drive circuit,

102...plasma display display device,

103...image source,

104...image display device,

110...rare gas discharge white lamp,

111... glass tube,

112... Phosphor layer,

113 ... electrodes,

120... liquid crystal display device,

121...Backlight unit,

122...LCD display,

123, 130...casing,

124...reflector,

126...diffuser plate,

127A, B... Prism film,

128...Polarizing reflector,

129...inverter.

Detailed ways

The conventional blue phosphor BAM has reliability problems and has a short life, so the reliability of a light emitting device using BAM and a display device using this device is lowered.

As its improvement strategy, highly reliable silicate phosphors, especially CMS, have been proposed in recent years, but the luminance characteristics obtained by excitation in a wavelength band exceeding 170 nm are low, and high-brightness light-emitting devices cannot be constructed, especially is a PDP device.

Therefore, the inventors of the present invention focused on silicate-based phosphors and searched for the synthesis of new materials, thereby achieving high-brightness silicate phosphors under the condition of light excitation with a wavelength of 172 nm, and using the silicate phosphors to achieve A high-brightness light-emitting device and a display device capable of high-brightness display are provided.

The newly realized Eu-activated silicate phosphor is an Eu-activated silicate phosphor represented by the following formula (I), particularly an Eu-activated silicate phosphor represented by the following formula (V). It should be noted that the following Eu-activated silicate phosphors represented by the following formula (V) and the formulas (II), (III), (IV), (VII), (IX), (XI) Europium (Eu)-activated silicate phosphors containing strontium (Sr) and magnesium (Mg) as constituent elements, such as Eu-activated silicate phosphors shown in (XII) and (XIII), are collectively referred to as SMS.

M1 _3a-e Mg _b Si _2c O _8d :Eu _e ...(I)

[In the formula (I), M1 is one or more elements selected from strontium (Sr), calcium (Ca) and barium (Ba), and a, b, c, d and e are respectively 0.8≤a≤1.2 , 0.8≤b≤1.2, 0.8≤c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2].

Sr _3a-e Mg _b Si _2c O _8d :Eu _e ...(V)

[In formula (V), a, b, c, d and e are respectively 0.8≤a≤1.2, 0.8≤b≤1.2, 0.8≤c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2].

It should be noted that according to the stoichiometric ratio, the Eu-activated silicate phosphor of formula (I) and SMS have a composition of M1 _3-e MgSi ₂ O ₈ :Eu _e or Sr _3-e MgSi ₂ O ₈ :Eu _e , That is, the composition of a=1, b=1, c=1, and d=1. Realization of this composition is preferred.

However, even if there is some deviation from the stoichiometric ratio shown in the above formulas (I) and (V), the composition ratio of the total of Sr, Ca, and Ba contained, Mg, and silicon (Si) and oxygen Composition ratios of constituent elements such as (O) are 1.2 times excess or 0.8 times too low compared to the above values, and the composition ratios of other constituent elements are changed from the above values. Silicate phosphors can also be used.

Also, as described below, it can be judged that higher luminous performance can also be obtained by using a phosphor whose composition deviates somewhat from the above-mentioned stoichiometric composition in some cases, so it is possible to actively use such a phosphor.

Next, detailed procedures such as the synthesis method of the phosphor used in the present invention will be described later in the paragraphs of Examples, and the characteristics of Sr _2.98 MgSi ₂ O ₈ :Eu _0.02 as an example will be described.

Fig. 1 is the excitation luminescence spectra of SMS (Sr _2.98 MgSi ₂ O ₈ :Eu _0.02 ) and CMS constituting the present invention.

According to a conventional method, using a deuterium lamp as a light source, the excitation luminescence spectrum is measured, as shown in Figure 1, it can be seen that in the excitation luminescence spectrum of the obtained CMS, the luminescence intensity obtained in the band near 170nm decreases sharply, and the wavelength 172nm The luminous efficiency due to the excitation of light is significantly lowered.

On the other hand, as shown in FIG. 1, it can be seen that SMS, which is an example realized in the present invention, exhibits high luminous intensity even in the region near 170 nm, and this value is much higher than that of CMS. High luminous efficiency can be obtained under excitation. In this case, even in the wavelength band around 147nm, the above-mentioned SMS exhibits the same high emission luminance as that of CMS.

Therefore, by using the SMS in light emitting devices, in particular, tubular or flat type fluorescent lamps and plasma display screens, high luminance light emitting devices and thus high performance display devices can be obtained.

In addition, regarding the relationship between the composition of the discharge gas in the plasma display panel and the intensity of ultraviolet rays generated by the discharge, it has been found that the greater the composition ratio of the Xe component, the greater the overall intensity of the vacuum ultraviolet rays emitted by the discharge, and the emitted The ratio of the constituent components in the vacuum ultraviolet rays changes.

Specifically, it has been found that the _intensity ratio (I ₁₇₂ /I ₁₄₇ ) changes, that is, as the Xe composition ratio increases, the intensity ratio (I ₁₇₂ /I ₁₄₇ ) increases.

The obtained research results show that, in the AC type PDP, when the Xe composition ratio is 4%, I ₁₇₂ /I ₁₄₇ (4%)=1.2. In terms of PDP, the intensity ratio of the ultraviolet component with a wavelength of 147nm and the ultraviolet component with a wavelength of 172nm contained in the vacuum ultraviolet rays generated by discharge tends to decrease from a slightly higher intensity to the same level at the 172nm component or even decrease the intensity of the 172nm component. .

Moreover, the results of further research show that when the Xe composition ratio is 6%, the intensity of the vacuum ultraviolet rays generated due to discharge increases, and at the same time I ₁₇₂ /I ₁₄₇ (6%) = 1.9, which is greatly improved. When the Xe composition When the ratio is 10%, the intensity of vacuum ultraviolet rays generated due to discharge increases, and at the same time I ₁₇₂ /I ₁₄₇ (10%) = 3.1, which is more greatly improved. When the Xe composition ratio is 12%, the intensity of vacuum ultraviolet rays generated due to discharge increases. The intensity of the vacuum ultraviolet rays increases, and at the same time I ₁₇₂ /I ₁₄₇ (12%) = 3.8, which is significantly improved.

Therefore, it is preferable to use a phosphor whose Xe composition ratio in the discharge gas is larger than that of a PDP in the usual case, for example, in a PDP corresponding to high xenonization having a Xe composition ratio of 6%. , Vacuum ultraviolet light at 172nm can efficiently excite luminescence; for the case where the composition ratio exceeds 6% and the Xe composition ratio is higher than 10%, the demand for this type of phosphor is increasing day by day.

Therefore, when using the Eu-activated silicate phosphor of the above-mentioned formula (I) in a plasma display screen using a discharge gas composed of Xe, especially SMS, due to the excitation of light with a wavelength of 172nm, in the phosphor High luminous efficiency is obtained, so Xe ₂ molecular rays can be efficiently utilized, and thus it is possible to manufacture a high-brightness PDP device.

Furthermore, the Eu-activated silicate phosphor of the above formula (I), especially SMS, is also well suited for the so-called "PDP corresponding to high xenonization" technology. In this technology, it is preferable to use, for example, the Xe composition ratio In the discharge gas of 6% or more, it is more preferable to use a discharge gas composed of Xe composition ratio of 10% or more containing xenon (Xe) gas, and this discharge gas conforms to the ratio of the intensity of the ultraviolet component of 172nm to the component of 147nm This is a strong condition (active use of Xe ₂ molecular rays), so even in the case of a PDP using a highly xenonized discharge gas, it is possible to configure a light-emitting device with higher luminance than CMS.

In addition, by optimizing the composition ratio based on the Eu-activated silicate phosphor of the above formula (I), especially SMS, or by improving its composition, the fluorescence obtained by excitation at a wavelength of 172 nm can be further improved. The luminous brightness of the body can be improved, or the color purity of the luminescent can be further improved.

Specifically, for the purpose of optimizing the composition ratio, by synthesizing the Eu-activated silicate phosphor represented by the following formula (VI) in which the Eu composition ratio meets more suitable conditions, especially the Eu-activated silicate phosphor represented by the following formula (VII) By activating the silicate phosphor, a silicate phosphor with higher brightness can be obtained under the condition of light excitation with a wavelength of 172nm. By using this phosphor, a high-brightness light-emitting device can be realized, so that a high-brightness display can be achieved display device.

M1 _3a-e Mg _b Si _2c O _8d :Eu _e ...(VI)

[In the formula (VI), M1 is one or more elements selected from Sr, Ca and Ba, and a, b, c, d and e are respectively 0.8≤a≤1.2, 0.8≤b≤1.2, 0.8≤ c≤1.2, 0.8≤d≤1.2, 0.01≤e≤0.05].

Sr _3a-e Mg _b Si _2c O _8d :Eu _e ...(VII)

[In formula (VII), a, b, c, d and e are respectively 0.8≤a≤1.2, 0.8≤b≤1.2, 0.8≤c≤1.2, 0.8≤d≤1.2, 0.01≤e≤0.05].

In addition, by synthesizing the Eu-activated silicate phosphor represented by the following formula (VIII), especially the Eu-activated silicate phosphor represented by the following formula (IX), in which the Mg composition ratio meets more suitable conditions, it is possible to achieve The silicate phosphor with higher brightness can be obtained under the condition of 172nm light excitation. By using such a phosphor, a high-brightness light-emitting device can be realized, and a display device capable of displaying a high-brightness display can be realized.

M1 _3a-e Mg _b Si _2c O _8d :Eu _e ...(VIII)

[In the formula (VIII), M1 is one or more elements selected from Sr, Ca and Ba, and a, b, c, d and e are respectively 0.8≤a≤1.2, 1<b≤1.2, 0.8≤ c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2].

Sr _3a-e Mg _b Si _2c O _8d :Eu _e ...(IX)

[In formula (IX), a, b, c, d and e are respectively 0.8≤a≤1.2, 1<b≤1.2, 0.8≤c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2].

In addition, by synthesizing the Eu-activated silicate phosphor represented by the following formula (X), especially the Eu-activated silicate phosphor represented by the following formula (XI), in which the Si composition ratio satisfies more favorable conditions, it is possible to achieve The silicate phosphor with higher brightness can be obtained under the condition of 172nm light excitation. By using such a phosphor, a high-brightness light-emitting device can be realized, and a display device capable of displaying a high-brightness display can be realized.

M1 _3a-e Mg _b Si _2c O _8d :Eu _e ...(X)

[In the formula (X), M1 is one or more elements selected from Sr, Ca and Ba, and a, b, c, d and e are respectively 0.8≤a≤1.2, 0.8≤b≤1.2, 1< c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2].

Sr _3a-e Mg _b Si _2c O _8d :Eu _e ...(XI)

[In formula (XI), a, b, c, d and e are respectively 0.8≤a≤1.2, 0.8≤b≤1.2, 1<c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2].

Next, for the purpose of improving the composition, a Eu-activated phosphor represented by the following formula (II) was synthesized.

For the constituent element M2 in the formula (II), it can be from those metal elements that can replace each other with Sr or solid solution with each other, thereby easily forming crystals or solid solutions with few defects, especially divalent metal elements and rare earth elements, etc. Elements selected from, specifically, for example, may be Ba, Ca, Zn, Mn, Ti, V, Co, Pd, Pt, Ni, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Gd , Tb, Dy, Ho, Er, Tm, Yb, Sb, Tl and Lu at least one element selected.

Moreover, especially in the silicate phosphor obtained by composition, the color purity of light emitted by excitation can be improved, and it is preferable to select and use Ba element that can obtain high-brightness light emission under the excitation condition of 172nm, and it is preferable to use the following formula containing Ba: Eu-activated phosphors shown in (XII) and (III).

(Sr _1-x M2 _x ) _3a-e Mg _b Si _2c O _8d :Eu _e ...(II)

[In formula (II), M2 is from Ba, Ca, Zn, Mn, Ti, V, Co, Pd, Pt, Ni, SC, Y, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, One or more elements selected from Dy, Ho, Er, Tm, Yb, Sb, Tl and Lu, a, b, c, d, e and x are 0.8≤a≤1.2, 0.8≤b≤1.2, 0.8≤c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2, 0<x≤0.5, however, in the case of M2=Ba, x is in the range of 0.1<x≤0.5].

(Sr _1-x Ba _x ) _3a-e Mg _b Si _2c O _8d :Eu _e ... (XII)

[In formula (XII), a, b, c, d and e are respectively 0.8≤a≤1.2, 0.8≤b≤1.2, 0.8≤c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2, x is in 0.1 < the range of x ≤ 0.5].

(Sr _1-xy Ba _x M3 _y ) _3a-e Mg _b Si _2c O _8d :Eu _e ...(III)

[In the formula (III), M3 is from Ca, Zn, Mn, Ti, V, Co, Pd, Pt, Ni, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, One or more elements selected from Ho, Er, Tm, Yb, Sb, Tl and Lu, a, b, c, d and e are respectively 0.8≤a≤1.2, 0.8≤b≤1.2, 0.8≤c≤ 1.2, 0.8≤d≤1.2, 0.001≤e≤0.2, x and y are 0.1<x+y≤0.5].

It should be noted that according to the stoichiometric ratio, the Eu-activated phosphor represented by the above formula (II) has a composition of (Sr _1-x M2 _x ) _3-e MgSi ₂ O ₈ :Eu _e ; represented by the above formula (XII) The Eu-activated phosphor has a composition of (Sr _1-x Ba _x ) _3-e MgSi ₂ O ₈ :Eu _e ; the Eu-activated phosphor represented by the above formula (III) has (Sr _1-xy Ba _x M3 _y ) _3-e Composition of MgSi ₂ O ₈ :Eu _e .

However, even if there are some deviations from the stoichiometric ratios shown in the above formulas (II), (XII) and (III), the sum of the composition ratios of Sr and M2, the sum of the composition ratios of Sr and Ba, or the Sr The sum of the composition ratios of Ba and M3, or the composition of each element of Mg, Si, or oxygen (O) is 1.2 times excess or 0.8 times too small compared to the above composition, and there are other compositions When the composition ratio of the elements is changed from the above numerical values, a silicate phosphor having a changed composition can also be used.

Through the above studies, a silicate phosphor that emits light with higher brightness and high color purity under the condition of light excitation with a wavelength of 172 nm has been realized. Furthermore, by using such a phosphor, a high-brightness light-emitting device can be realized, and a display device capable of achieving high-performance display can be realized.

Furthermore, especially in the silicate phosphor obtained by composition, it is preferable to select and use Ca element that can improve the luminous intensity when excited by ultraviolet rays with a wavelength of 172nm, and it is preferable to use the element containing Ca expressed by the following formula (XIII): , Eu-activated silicate phosphor represented by (IV).

(Sr _1-x Ca _x ) _3a-e Mg _b Si _2c O _8d :Eu _e ... (XIII)

[In formula (XIII), a, b, c, d, e and x are respectively 0.8≤a≤1.2, 0.8≤b≤1.2, 0.8≤c≤1.2, 0.8≤d≤1.2, 0.001≤e≤0.2, 0<x≤0.2].

(Sr _1-xy Ca _x M4 _y ) _3a-e Mg _b Si _2c O _8d :Eu _e ...(IV)

[In formula (IV), M4 is from Ba, Zn, Mn, Ti, V, Co, Pd, Pt, Ni, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, One or more elements selected from Ho, Er, Tm, Yb, Sb, Tl and Lu, a, b, c, d and e are respectively 0.8≤a≤1.2, 0.8≤b≤1.2, 0.8≤c≤ 1.2, 0.8≤d≤1.2, 0.001≤e≤0.2, x and y are 0<x+y≤0.2].

It should be noted that according to the stoichiometric ratio, the Eu-activated phosphor represented by the above formulas (XIII) and (IV) has (Sr _1-x Ca _x ) _3-e MgSi ₂ O ₈ :Eu _e and (Sr _1-xy Ca _x M4 _y ) _3-e MgSi ₂ O ₈ :Eu _e composition.

However, even if there are some deviations from the stoichiometric ratios shown in the above formulas (XIII) and (IV), the sum of the composition ratios of Sr and Ca or the sum of the composition ratios of Sr, Ca and M4, or Mg, The composition of each element of Si or oxygen (O) is 1.2 times excess or 0.8 times too small compared with the above composition, and the composition ratio of other constituent elements is changed from the above value. A silicate phosphor can also be used.

By using the above-mentioned Eu-activated silicate phosphor, a high-brightness light-emitting device can be realized, and thus a display device capable of high-brightness display can be realized.

Based on the above facts, a plasma display panel which is an embodiment of the present invention using the above-mentioned Eu-activated silicate phosphor, especially a silicate phosphor such as SMS, can be configured as follows.

Fig. 2 is an exploded perspective view showing the structure of a plasma display panel as an embodiment of the present invention.

The plasma display panel 100 as an embodiment of the present invention has the following structural features, that is, it has a structure for responding to a so-called "surface discharge" and includes a pair of substrates 1 arranged opposite to each other at a predetermined interval. , 6. The partition wall 7 arranged between the pair of substrates 1, 6 and used to maintain the gap between the pair of substrates is sealed in the space formed between the pair of substrates and can generate ultraviolet rays by discharge Discharge gas (not shown in the figure), and display electrodes 2 and address electrodes 9 respectively arranged on the opposing surfaces of the pair of substrates, and the above-mentioned phosphors containing Eu-activated silicate phosphors The phosphor layer 10 is formed on one substrate 6 of the pair of substrates and on the surface of the partition wall 7. When receiving the action of ultraviolet rays generated by the discharge gas due to discharge, the Eu-activated silicic acid constituting the phosphor layer 10 is activated. The salt phosphor is excited and emits light.

It should be noted that the wire shown in Figure 2 with the symbol 3 is the busbar 3 integrated with the electrode 2 (display electrode), which is made of silver or Cu-Cr for reducing the electrode resistance, and the symbols 4, 8 The layers in are the dielectric layers 4 and 8, and the layer in symbol 5 is the protective film 5 provided for protecting the electrodes.

In the plasma display panel of the surface discharge type color PDP device shown in this embodiment, for example, by applying a negative voltage to the display electrodes (generally referred to as scan electrodes), and applying a positive voltage to the address electrodes and display electrodes (compared to The voltage applied to the display electrodes is a positive voltage) to generate a discharge, thereby forming a wall charge that assists the start of discharge between the display electrodes (this is called writing). In this state, if an appropriate reverse voltage is applied between the display electrodes and the display electrodes, a discharge will occur in the discharge space between the two electrodes via the dielectric (and protective layer).

After the discharge is over, if the voltage applied to the display electrode and the display electrode is reversed, a new discharge will occur. By repeating this operation, discharge can be continuously generated (this is called sustain discharge or display discharge).

(Example)

Examples corresponding to the best modes for carrying out the present invention are described below.

<Example 1>

In this embodiment, as an example of an image display device, synthesis of a phosphor, manufacture of a plasma panel using the phosphor, and a series of techniques for an image display device using the plasma panel will be sequentially described with reference to the drawings.

(1) Synthesis of Phosphor:

In order to manufacture the plasma display panel according to the first embodiment of the present invention, first, synthesis of phosphors as components is carried out.

The chemical formula of the first synthesized phosphor is Sr _2.98 MgSi ₂ O ₈ :Eu _0.02 .

The synthesis was carried out as follows: SrCO ₃ 4.399g (29.80mmol), MgCO ₃ 0.962g (10.00mmol), SiO ₂ 1.202g (20.00mmol), Eu ₂ O ₃ 0.0352g (0.10 mmol), and NH ₄ Br 0.392g (4.00mmol) as a flux, after fully mixing in an agate mortar, the mixture was filled in a heat-resistant container, and 3 hour roasting.

The obtained baked product was pulverized, washed with water, and dried to obtain a silicate phosphor (SMS) having the above composition. Next, the excitation emission spectrum of the obtained phosphor was measured according to a conventional method using a deuterium lamp as a light source. As a comparative example, the excitation emission spectrum of CMS was also measured at the same time. The results are shown in Fig. 1 .

As shown in FIG. 1 , in the measured excitation luminescence spectrum of CMS, the luminescence intensity obtained in the wavelength band exceeding 170 nm sharply decreases, so it can be seen that the luminescence efficiency obtained by excitation with light having a wavelength of 172 nm is low.

On the other hand, the SMS obtained by the present invention shows high luminous intensity even in the region around 170nm, and the luminous intensity is much higher than that of CMS, so it can be seen that excitation by light with a wavelength of 172nm can obtain high luminous efficiency. In this case, it can be seen that SMS exhibits emission luminance as high as that of CMS even in a wavelength band around 147 nm.

Next, according to the same method, four kinds of SMSs with different Eu composition ratios were synthesized.

The chemical formulas of the four synthesized phosphors are: Sr _2.995 MgSi ₂ O ₈ :Eu _0.005 , Sr _2.99 MgSi ₂ O ₈ :Eu _0.01 , Sr _2.95 MgSi ₂ O ₈ :Eu 0.05 , Sr 2.90 MgSi 2 O 8 :Eu _0.05 , Sr _2.90 MgSi ₂ O ₈ :Eu _0.10 .

During synthesis, for Sr _2.995 MgSi ₂ O ₈ :Eu _0.005 , the amount of SrCO ₃ as raw material is 4.421 g (29.95 mmol) and the amount of Eu ₂ O ₃ is 0.0088 g (0.025 mmol); for Sr _2.99 MgSi ₂ O ₈ : Eu _0.01 , make the same amount of SrCO ₃ as raw material 4.414g (29.90mmol) and Eu ₂ O ₃ amount as 0.0176g (0.050mmol); for Sr _2.95 MgSi ₂ O ₈ :Eu _0.05 , make SrCO ₃ The amount is 4.355g (29.50mmol) and the amount of Eu ₂ O ₃ is 0.0880g (0.25mmol); for Sr _2.90 MgSi ₂ O ₈ :Eu _0.10 , the amount of SrCO ₃ that is also used as a raw material is 4.281g (29.00mmol) and Eu Except that the amount of ₂ O ₃ was 0.1760 g (0.50 mmol), it was synthesized in the same manner as above to obtain the desired phosphor.

Using the obtained phosphor, the emission luminance was evaluated. The evaluation is based on the relative luminance (expressed as several times) obtained when the luminance of CMS under 172nm vacuum ultraviolet ray excitation is taken as 1, using CMS as a comparative control sample.

FIG. 3 is a graph showing the relationship between the Eu composition ratio and the relative luminance.

The evaluation results are summarized in FIG. 3 , and all phosphors exhibited luminances equivalent to CMS three times or more, and showed significantly higher luminances than CMS under excitation conditions of 172 nm.

Furthermore, it can be seen that by increasing the Eu composition ratio beyond 0.005 to 0.01, the luminance under the excitation condition of 172nm can be significantly improved, and that the luminance is significantly reduced by increasing the Eu composition ratio beyond 0.05 to 0.1. . Therefore, it can be seen that in order to obtain remarkably high luminance, it is desirable that the Eu composition ratio is 0.01 to 0.05.

It should be noted that when Sr _2.98 MgSi ₂ O ₈ :Eu _0.02 was used to evaluate the emission luminance under 146 nm vacuum ultraviolet ray excitation, it showed a high luminance equivalent to 1.22 times the luminance of the CMS of the comparative example evaluated under the same conditions. .

Based on the above facts, it can be seen that when SMS is used in a plasma display panel using a discharge gas composed of Xe, since high luminescence can be obtained under the excitation of light with wavelengths of 146nm and 172nm, _Xe2 molecular rays It can also be used efficiently, and a high-brightness PDP device can be realized.

Furthermore, it can be seen that it is well applicable to the technology of the so-called "PDP corresponding to high xenonization", in which, for example, a discharge gas having a composition ratio of Xe of 6% or more is used, and it is more preferable to use the gas according to the active use The Xe ₂ molecular ray is a discharge gas composed of xenon (Xe) gas in a composition ratio of 10% or more. Therefore, even in the case of a PDP using a highly xenonized discharge gas, it is possible to constitute a discharge gas that is comparable to that using a CMS. A light-emitting device with higher brightness than the case.

(2) Manufacture of plasma display screen:

Next, using the above-mentioned silicate phosphor Sr _2.98 MgSi ₂ O ₈ :Eu _0.02 as the blue phosphor constituting the blue phosphor layer, the surface discharge device having the above-mentioned structure of the light-emitting device described in FIG. 2 was fabricated. type plasma display (PDP).

In the PDP of this embodiment, after forming address electrodes 9 made of silver or the like and a dielectric layer 8 made of a glass-based material on the rear substrate 6, a barrier rib material made of the same glass-based material is thick-film printed, The partition wall 7 is formed by removing a mold (blast mask) and blasting (blast).

Next, red, green, and blue phosphor layers are sequentially formed in strips on the barrier ribs so as to cover the groove surfaces between the barrier ribs.

Here, each phosphor layer 10 is formed by making 40 parts by weight of red phosphor particles (60 parts by weight of carrier) and 35 parts by weight of green phosphor particles corresponding to red, green, and blue colors. 65 parts by weight of the carrier), 35 parts by weight of the blue phosphor particles (65 parts by weight of the carrier), are mixed with the carrier respectively to make a phosphor paste, and after the phosphor paste is coated by the screen printing method, it is dried and baked. To carry out the evaporation of volatile components in the phosphor paste and the combustion and removal of organic matter, thereby forming a phosphor layer. It should be noted that the phosphor layer used in this example is composed of phosphor particles having a particle size distribution with a central particle diameter of 3 μm.

In addition, for each phosphor material other than blue, the red phosphor is a mixture of (Y, Gd)BO ₃ :Eu phosphor and Y ₂ O ₃ :Eu phosphor at a mixing ratio of 1:1, and the green phosphor is Zn ₂ SiO ₄ :Mn phosphor.

Next, the front substrate 1 and the back substrate 6 on which the display electrodes 2, the bus electrodes 3, the dielectric layer 4, and the protective layer 5 have been formed are encapsulated with glass frit not shown in the figure, and the display screen is vacuum-exhausted. Inject discharge gas and seal. The discharge gas is a gas containing xenon (Xe) gas in a composition ratio of 10%. The PDP mentioned in this embodiment has a size of type 3, and the pitch of each pixel is 1000 μm×1000 μm.

Next, a plasma display device as a display device was produced using a PDP obtained by using the above-mentioned silicate phosphor of the first embodiment of the present invention as a blue phosphor.

(3) Image display devices using plasma display screens:

FIG. 4 is a block diagram showing an example of an image display system having a plasma display device using a silicate activated using the above-mentioned europium (divalent) in the first embodiment of the present invention. Phosphor is a plasma display panel (PDP) composed of blue phosphor.

The plasma display device 102 in this embodiment is composed of a plasma display screen 100 and a driving circuit 101 for driving the plasma display screen. In addition, the image display device 104 is constituted by the plasma display device 102 together with the image source (image information signal) 103, wherein the drive circuit 101 receives the signal of the display screen from the image source 103, converts it into a drive signal, Thus, the plasma display screen 100 is driven.

The plasma display device 102 is high brightness and has a long life. In addition, in this example, although detailed investigation results are not shown for red and green phosphors, PDPs can be produced in the same way even with phosphors of the respective compositions shown below.

In the red phosphor, any one or more fluorescent substances of (Y, Gd)BO ₃ :Eu, (Y,Gd) ₂ O ₃ :Eu, and (Y,Gd)(P,V)O ₄ :Eu may be contained. body. In addition, the green phosphor can contain Zn ₂ SiO ₄ :Mn, (Y, Gd, Sc) ₂ SiO ₅ :Tb, (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ :Tb, (Y, Gd) ₃ One or more phosphors selected from (Al,Ga) ₅ O ₁₂ :Ce, (Y,Gd)B ₃ O ₆ :Tb, and (Y,Gd)PO ₄ :Tb. Furthermore, it can also be used in combination with phosphors not shown here.

<Example 2>

In order to manufacture the plasma display panel according to the second embodiment of the present invention, first, synthesis of phosphors as constituent components is carried out.

The synthesized phosphor is a silicate phosphor (SMS) with slightly more Mg composition than the stoichiometric ratio (in the case of b=1 in the general formula), and the chemical formula is Sr _2.97 Mg _1.01 Si ₂ O ₈ : Eu _0.03 . It should be noted that since the Mg component is more than the stoichiometric ratio, the actual chemical formula is slightly different from the above, and the composition ratio of Sr and the like is actually slightly less.

The synthesis was carried out as follows: SrCO ₃ 4.385g (29.70mmol), MgCO ₃ 0.972g (10.10mmol), SiO ₂ 1.202g (20.00mmol), Eu ₂ O ₃ 0.0528g (0.15 mmol), and NH ₄ Br 0.392g (4.00mmol) as a flux, after fully mixing in an agate mortar, the mixture was filled in a heat-resistant container, and in a reducing atmosphere, 3 hour roasting.

The obtained fired product was pulverized, washed with water, and dried to obtain a silicate phosphor (SMS) having the above composition. In addition, the emission luminance of the obtained phosphor was evaluated. The evaluation takes Sr _2.97 MgSi ₂ O ₈ :Eu _0.03 (SMS) whose Mg composition satisfies the stoichiometric ratio as a comparative control sample, according to the relative luminous luminance obtained when the luminous luminance under 172nm vacuum ultraviolet excitation is set as 1 (expressed as several times ) for evaluation.

As a result of the evaluation, the obtained phosphor showed luminance 1.16 times higher than that of the comparative sample. Therefore, it can be seen that high luminance is exhibited under the excitation condition of 172 nm. At this time, with the five phosphors used in the first embodiment of the present invention, Sr _2.98 MgSi ₂ O ₈ :Eu _0.02 , Sr _2.995 MgSi ₂ O ₈ :Eu _0.005 , Sr _2.99 MgSi ₂ O ₈ :Eu _0.01 , Compared with Sr _2.95 MgSi ₂ O ₈ :Eu _0.05 and Sr _2.90 MgSi ₂ O ₈ :Eu _0.10 , the brightness is higher than that of any phosphor.

Therefore, it can be seen that when the above-mentioned silicate phosphor SMS having a slightly more Mg composition than the stoichiometric ratio is used in a plasma display panel using a discharge gas containing Xe composition, due to the High luminous efficiency can be obtained under excitation, therefore, Xe ₂ molecular rays can also be used efficiently, so that a high-brightness PDP device can be manufactured.

Furthermore, it was found that it is suitable for the technology of so-called "PDP corresponding to high xenonization", in which, for example, a discharge gas having a composition ratio of 6% or more is used, and it is more preferable to use a gas according to the principle that _Xe2 can be actively used. The composition ratio of molecular rays is more than 10% of the discharge gas containing xenon (Xe) gas. Therefore, even in the case of a PDP using a highly xenonized discharge gas, it is possible to constitute a discharge gas that has an Higher brightness light emitting device.

Secondly, synthesize a silicate phosphor (SMS) with slightly more Mg than the stoichiometric ratio (equivalent to b=1 in the general formula) and the chemical formula is Sr _2.97 Mg _1.1 Si ₂ O ₈ :Eu _0.03 SMS. Synthesis was carried out in the same manner as above except that 1.058 g (11.0 mmol) of MgCO ₃ was used.

Using the obtained phosphor, the emission luminance was evaluated. The evaluation is to take Sr _2.97 MgSi ₂ O ₈ :Eu _0.03 (SMS) whose Mg composition satisfies the stoichiometric ratio (equivalent to b=1 in the general formula) as a comparative control sample, and take the luminance under 172nm vacuum ultraviolet excitation as 1 The obtained relative luminance (expressed as several times) was evaluated. As a result of the evaluation, the obtained phosphor showed luminance 1.03 times higher than that of the comparative sample. Therefore, it can be seen that high luminance is exhibited under the excitation condition of 172 nm.

Secondly, the synthesis is carried out under the condition that the Mg composition is 1.5 times the stoichiometric ratio (equivalent to b=1.5 in the general formula), and a silicate phosphor with a much higher Mg composition than the stoichiometric ratio is synthesized. (SMS). It synthesized similarly to the above except having used 1.443 g (15.0 mmol) of _MgCO3 . When evaluated in the same manner, the obtained phosphor exhibited brightness equivalent to that of the comparative sample.

From the above facts, it can be seen that in order to increase the luminance of SMS under 172nm vacuum ultraviolet excitation, it is desirable that the Mg component is slightly more than the stoichiometric ratio, but less than 1.5 times. Therefore, using a silicate phosphor (SMS) Sr _2.97 Mg _1.01 Si ₂ O ₈ :Eu _0.03 in which the Mg component is slightly more than the stoichiometric ratio in one composition, it was produced in the same manner as in the first embodiment of the present invention. A plasma display panel (PDP) as a light emitting device. The plasma display device is high brightness and has a long life.

<Example 3>

In order to manufacture the plasma display panel according to the third embodiment of the present invention, first, synthesis of phosphors as constituent components is carried out. The synthesized phosphor is a silicate phosphor (SMS) with more Si in the composition than the stoichiometric ratio (equivalent to c=1 in the general formula), and the chemical formula is Sr _2.99 MgSi _2.1 O _8.2 :Eu _0.01 . It should be noted that since the Si component is more than the stoichiometric ratio, the actual chemical formula is slightly different from the above, and the composition ratio of Sr, Mg, etc. is actually smaller.

Synthesis was carried out as follows: SrCO ₃ 4.414g (29.90mmol), MgCO ₃ 0.962g (10.00mmol), SiO ₂ 1.262g (21.00mmol), Eu ₂ O ₃ 0.0176g (0.050 mmol), and NH ₄ Br 0.392g (4.00mmol) as a flux, after fully mixing in an agate mortar, the mixture was filled in a heat-resistant container, and 3 hour roasting.

The obtained baked product was pulverized, washed with water, and dried to obtain a silicate phosphor (SMS) having the above composition. Furthermore, the emission luminance of the obtained phosphor was evaluated. The evaluation is to take a Sr _2.99 MgSi ₂ O ₈ :Eu _0.01 (SMS) whose Si composition satisfies the stoichiometric ratio (equivalent to c=1 in the general formula) as a comparative control sample, according to the luminous brightness under 172nm vacuum ultraviolet excitation as The relative luminance (expressed as several times) obtained at 1 time was evaluated.

As a result of the evaluation, the obtained phosphor showed luminance 1.20 times higher than that of the comparative sample. Therefore, it can be seen that high luminance is exhibited under the excitation condition of 172 nm. Therefore, it can be seen that when the above-mentioned silicate phosphor SMS having a slightly higher Si composition than the stoichiometric ratio is used in a plasma display panel using a discharge gas containing Xe composition, due to excitation by light with a wavelength of 172nm Since high luminous efficiency can be obtained, Xe ₂ molecular rays can also be efficiently used, and a high-brightness PDP device can be realized.

Furthermore, it can be seen that it is suitable for the technology of so-called "PDP corresponding to high xenonization" in which, for example, a discharge gas having a composition ratio of xenon (Xe) of 6% or more is used, and it is more preferable to use a gas according to the Actively utilize the Xe ₂ molecular radiation composition ratio in the amount of 10% or more containing xenon (Xe) gas constituted discharge gas, therefore, even in the case of PDP using highly xenonized discharge gas, also can constitute a A light emitting device with higher brightness compared to CMS.

From the above facts, it can be seen that in order to increase the luminance of SMS under 172nm vacuum ultraviolet excitation, it is desirable to have a slightly larger Si component than the stoichiometric ratio. Therefore, using a silicate phosphor (SMS) Sr _2.99 MgSi _2.1 O _8.2 :Eu _0.01 in which the Si component in the composition is slightly more than the stoichiometric ratio, a luminescent phosphor is produced in the same manner as in the first embodiment of the present invention. The device's plasma display (PDP). The plasma display device is high brightness and has a long life.

<Example 4>

In order to manufacture the plasma display panel according to the fourth embodiment of the present invention, first, synthesis of phosphors as components is carried out. The chemical formula of the phosphor synthesized first is (Sr _0.9 Ba _0.1 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 .

Synthesis was carried out as follows: as raw materials, respectively weigh SrCO ₃ 3.946g (26.73mmol), BaCO ₃ 0.586g (2.97mmol), MgCO ₃ 0.962g (10.00mmol), SiO ₂ 1.202g (20.00mmol) , Eu ₂ O ₃ 0.0528g (0.15mmol), and NH ₄ Br 0.392g (4.00mmol) as a flux were thoroughly mixed in an agate mortar, the mixture was filled in a heat-resistant container, and the Baking was performed at 1250° C. for 3 hours under an atmosphere.

The obtained calcined product was pulverized, washed with water, and dried to obtain a silicate phosphor (hereinafter referred to as B-SMS) having the above composition.

Similarly, by changing the amount x of Ba substituting part of Sr to 0.2, 0.25, 0.3, 0.4, and 0.5, (Sr _0.8 Ba _0.2 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , (Sr _0.75 Ba _0.25 ) _2.97 MgSi ₂ were synthesized. O ₈ :Eu _0.03 , (Sr _0.7 Ba _0.3 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , (Sr _0.6 Ba _0.4 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 and (Sr _0.5 Ba _0.5 ) _2.97 MgSi ₂ O ₈ : _{3Eu 0} . .

For (Sr _0.8 Ba _0.2 ) _2.97 MgSi ₂ O _{8 :} Eu _0.03 , make _{SrCO 3 3.508g} (23.76mmol) and BaCO _{3 1.172g} (5.94mmol); ₈ :Eu _0.03 , set SrCO ₃ to 3.288g (22.28mmol), BaCO ₃ to 1.465g (7.43mmol); for (Sr _0.7 Ba _0.3 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , set SrCO ₃ to 3.069g (20.79mmol), BaCO ₃ is 1.758g (8.91mmol); In addition, for (Sr _0.6 Ba _0.4 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , SrCO ₃ is 2.631g (17.82mmol), BaCO ₃ is 2.344g ( 11.88mmol); In addition, for (Sr _0.5 Ba _0.5 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , SrCO ₃ is 2.192g (14.85mmol), BaCO ₃ is 2.930g (14.85mmol), in addition, using The desired phosphor was obtained by the same method as above.

Using the obtained phosphor group, in order to evaluate the color purity of emitted light under 172 nm vacuum ultraviolet ray excitation, the y value in the X, Y chromaticity diagram of the obtained emitted light was evaluated. The evaluation is to compare the y value of the light emitted under the excitation of 172nm vacuum ultraviolet rays by using CMS as a comparative control sample.

As a result, it can be seen that _the value _of y=0.0862 _in (Sr _0.9 Ba _0.1 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 relative to the y value _of CMS= _{0.108 ;} In (Sr _0.75 Ba _0.25 ) _2.97 MgSi ₂ O ₈ :Eu 0.03, y value=0.0702; in (Sr 0.75 Ba 0.25 ) _2.97 MgSi 2 O 8 :Eu 0.03, y value=0.0566; in (Sr _0.7 Ba _0.3 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , y value=0.0448 ; in (Sr _0.6 Ba _0.4 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , the value of y=0.0311; in (Sr _0.5 Ba _0.5 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , the value of y=0.0279.

Next, using the obtained phosphor group, the emission luminance under 172 nm vacuum ultraviolet ray excitation was evaluated. CMS was used as a comparison object sample for evaluation. The evaluation is based on the relative luminance obtained when the luminance of CMS under the excitation of 172nm vacuum ultraviolet rays is set as 1 (expressed as a value of several times) by using CMS as a comparative control sample.

FIG. 5 is a graph showing the relationship between the Ba composition ratio and the relative luminance and y value. The evaluation results and the evaluation results of the y value are summarized in Fig. 5, and it can be seen that in (Sr _0.9 Ba _0.1 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , it is 4.1 times, and in (Sr _0.8 Ba _0.2 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , 3.7 times, (Sr _0.75 Ba _0.25 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , 3.0 times, (Sr _0.7 Ba _0.3 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , 2.29 times, (Sr _0.6 Ba _0.4 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 is 1.12 times brighter, and (Sr _0.5 Ba _0.5 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 is equivalent in brightness.

In summary, it can be seen that the color purity of the silicate phosphor (B-SMS) synthesized above is better than that of CMS. Furthermore, it can be seen that the composition ratio of Ba to Sr is 50% or less, and high emission luminance of CMS or higher can be achieved under the excitation of vacuum ultraviolet rays at 172 nm. Furthermore, it can be seen that the composition ratio of Ba to Sr is less than 50%, and the emission luminance under excitation of vacuum ultraviolet rays at 172 nm is higher than that of CMS.

Therefore, it can be seen that a phosphor having a composition ratio of Ba to Sr of 50% or less is preferable. Furthermore, it was found that a phosphor having a composition ratio of Ba to Sr of less than 50% is more preferable.

In addition, it was found that particularly in the phosphors of the examples of the present invention in which the composition ratio of Ba to Sr is 10% or more and less than 20%, very high luminescence can be obtained under 172nm vacuum ultraviolet ray excitation. Moreover, it can be seen that this phosphor is more preferable in consideration of brightness characteristics.

In addition, when the color purity characteristics are mainly considered, in a phosphor having a Ba composition ratio exceeding 20% relative to Sr, the y value is less than 0.07, and high color purity can be achieved, thereby achieving both brightness and color. The two aspects of the high level of purity, as can be seen from Figure 5, in the phosphor with the composition ratio of Ba relative to Sr of 23% or more, the y value is less than about 0.06, and a higher level of color purity can be achieved, so that a higher level of color purity can be obtained. Phosphor with high level of luminescent properties.

Therefore, it can be seen that when the luminance characteristics are mainly considered, a phosphor having a composition ratio of Ba to Sr of 10% or more and less than 20% is preferable, and in particular, when the color purity characteristics are considered, it is preferably 50%. The Ba composition ratio (/Sr) is within the following range, and the Ba composition ratio (/Sr) exceeds 20%, and more preferably the Ba composition ratio (/Sr) is 23% or more.

Moreover, it can be seen that in the case of considering the luminous efficiency, a simple method can be adopted, that is, dividing the luminance of the phosphor as the evaluation result by the y value of the phosphor to calculate the obtained value, and by evaluating the value, the composition of Ba can be known. Phosphors with a composition of 40% or less relative to Sr have high luminous efficiency and are therefore preferable, and phosphors with a composition of 30% or less have higher luminous efficiency and are more preferable.

Therefore, it can be seen that a composition region where the Ba composition ratio is 10% to less than 20%, or a region where the Ba composition ratio exceeds 20% to 40% is preferable, so that a phosphor having light-emitting characteristics can be realized. Furthermore, it can be seen that it is more preferable to achieve higher luminous characteristics in the composition region in which the Ba composition ratio is 10% to less than 20%, or in the composition region in which the Ba composition ratio exceeds 20% and is 30% or less. of phosphors.

In addition, it was found that when (Sr _0.8 Ba _0.2 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 was used to evaluate the emission luminance under 146 nm vacuum ultraviolet ray excitation, the luminance was equivalent to the luminance of CMS evaluated under the same conditions.

Based on the above facts, it can be known that when the above-mentioned synthesized silicate phosphor (B-SMS) is used in a plasma display screen using a discharge gas containing Xe, it can be excited by light with a wavelength of 172nm Since high luminous efficiency is obtained, Xe ₂ molecular rays can also be efficiently used, and a high-brightness PDP device can be realized.

Furthermore, it was found that it is suitable for the technology of so-called "PDP corresponding to high xenonization", in which, for example, a discharge gas having a composition ratio of 6% or more is used, and it is more preferable to use a gas according to the principle that _Xe2 can be actively used. The discharge gas composed of xenon (Xe) gas is included in the molecular beam composition ratio of 10% or more. Therefore, even in the case of a PDP using a highly xenonized discharge gas, it can constitute a Light emitting device with higher brightness.

Next, using (Sr _0.75 Ba _0.25 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 (B-SMS), a plasma display panel (PDP) as a light emitting device was produced in the same manner as in the first embodiment of the present invention. The plasma display device has high brightness and clear display colors, and has a long lifespan.

<Example 5>

As the blue phosphor, (Sr _0.75 Ba _0.25 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 (called B-SMS) used in the light-emitting device of the fourth embodiment of the present invention was used, and as the fifth embodiment, a Rare gas {enclosed xenon (Xe) gas} discharge white fluorescent lamp used as other light-emitting devices.

Fig. 6 shows the structure of the rare gas {enclosed xenon gas} discharge white fluorescent lamp, that is, using (Sr _0.75 Ba _0.25 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 (B -SMS) is a cross-sectional view of the structure of the light-emitting device according to the fifth embodiment of the present invention.

As the rare gas (xenon) discharge white fluorescent lamp 110 of the luminous device involved in the present invention, by the glass tube 111 that is airtightly protected, the xenon gas (not shown) that is sealed in the glass tube 111 inside, is coated on glass. The phosphor 112 on the inner surface of the tube 111 and the electrodes 113 provided at both ends of the glass tube 111 are constituted. Moreover, by using the discharge between the two electrodes, electric energy can be converted into ultraviolet radiation by using xenon gas as the discharge gas, and the ultraviolet radiation excites the phosphor layer 112 on the glass tube wall, that is, the phosphor constituting the phosphor layer, thereby Phosphor layer 112 is made to emit visible light.

It should be noted that, in addition to the silicate phosphor (blue phosphor) mentioned in the present invention, the above-mentioned phosphor layer 112 may also use divalent manganese-activated zinc silicate phosphor as a green phosphor, or Trivalent europium is used in the red phosphor to activate the yttrium-gadolinium acid phosphor to produce a rare gas (xenon) discharge white fluorescent lamp 110 generally called a 3-wavelength fluorescent lamp. The lamp 110 is highly luminous efficient and has a long life.

In addition, a liquid crystal display device 120 as a display device was manufactured by combining the lamp of this embodiment as a backlight with a separately prepared liquid crystal display panel.

7 is an exploded perspective view showing the structure of a liquid crystal display device constructed using a rare gas (xenon-enclosed) discharge white fluorescent lamp of a fifth embodiment, wherein the white fluorescent lamp emits light by using a fourth embodiment of the present invention. (Sr _0.75 Ba _0.25 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 (B-SMS) used in the device.

The rare gas (xenon gas enclosed) discharge white fluorescent lamp 110 of several embodiments is disposed in the casing 123 . In liquid crystal display devices requiring high luminance, such as liquid crystal televisions, a system in which several fluorescent lamps are arranged in a planar manner, that is, a so-called directly below (directly below) system is often used.

Between the housing 123 and the fluorescent lamp 110, a reflector 124 for efficiently utilizing light emitted from the fluorescent lamp 110 to the housing 123 side is disposed. In addition, in order to reduce the in-plane distribution of luminance in the liquid crystal display device, the diffuser plate 126 is arranged directly above the fluorescent lamp 110 . Furthermore, in order to increase the luminance of the liquid crystal display device 120 , prism films 127A and 127B and a polarizing reflection plate 128 are disposed.

An inverter (inverter) 129 is connected to the fluorescent lamp 110 so that when it is necessary to control the lighting of the fluorescent lamp 110, the lighting can be controlled by driving the inverter. It should be noted that the rare gas (xenon) discharge white fluorescent lamp 110 , housing 123 , reflector 124 , diffuser 126 , prism films 127A, 127B, polarizing reflector 128 , and inverter 129 are collectively referred to as backlight unit 121 hereinafter.

Directly above the backlight unit 121 , the amount of light transmitted by the backlight unit 121 is adjusted, and each pixel is provided with a liquid crystal display 122 equipped with a color filter for separating light into red, green, and blue light. Electrodes and thin film transistors (TFTs) are provided for each pixel in the liquid crystal display 122 , and color display can be performed by controlling the TFTs on each pixel. That is, it is configured in such a way that a voltage is supplied to each pixel, and by applying the voltage, the orientation of the liquid crystal of each pixel is changed, and the refractive index of each pixel is changed, thereby adjusting the intensity of light from the backlight unit 121. As for the amount of transmission, the adjusted amount of light is split by a color filter to perform color display.

In this embodiment, as the liquid crystal display, a transverse electric field method, that is, a so-called IPS mode liquid crystal display is used. However, liquid crystal displays of other modes, such as liquid crystal displays of TN mode, VA mode, OCB mode, etc., may also be used.

Finally, the backlight unit 121 is overlapped with the liquid crystal display 122 and covered with the casing 130, thereby obtaining a liquid crystal display device. The liquid crystal display device mentioned in this embodiment is a high-brightness display device capable of displaying clearly.

<Example 6>

Using (Sr _0.75 Ba _0.25 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 used in the light-emitting device of the fourth embodiment of the present invention as the blue phosphor, a flat rare gas (enclosed xenon gas) discharge white fluorescent lamp was produced.

For phosphors other than the blue phosphor, a divalent manganese-activated zinc silicate phosphor is used as a green phosphor, or a trivalent europium-activated acidified yttrium-gadolinium phosphor is used as a red phosphor.

The lamp is high brightness and has a long life. In addition, by combining the lamp of this embodiment as a backlight with a separately prepared liquid crystal display device, a clear liquid crystal display device can be produced as a display device.

<Example 7>

In order to manufacture the plasma display panel according to the seventh embodiment of the present invention, first, a phosphor as a component is synthesized. The chemical formula of the first synthesized phosphor is (Sr _0.9 Ca _0.1 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 .

The synthesis of the phosphor is carried out as follows: as raw materials, respectively weigh SrCO ₃ 3.946g (26.73mmol), CaCO ₃ 0.297g (2.97mmol), MgCO ₃ 0.962g (10.00mmol), SiO ₂ 1.202g (20.00mmol), Eu ₂ O ₃ 0.0528g (0.15mmol), and NH ₄ Br 0.392g (4.00mmol) as a flux, after mixing well in an agate mortar, the mixture was filled into a heat-resistant container , under a reducing atmosphere, at 1250 ° C for 3 hours of firing.

The obtained calcined product was pulverized, washed with water, and dried to obtain a silicate phosphor (hereinafter referred to as C-SMS) having the above composition. Using the obtained phosphor C-SMS, the emission brightness was evaluated. The evaluation takes CMS as a comparative control sample, and evaluates according to the relative luminance obtained when the luminance under 172nm vacuum ultraviolet excitation is set as 1 (expressed as a value of several times).

As a result of the evaluation, the obtained phosphor exhibited luminance 5.30 times higher than that of the comparative sample. Therefore, it can be seen that high luminance is exhibited under the excitation condition of 172 nm. At this time, the phosphors Sr _2.98 MgSi ₂ O ₈ :Eu _0.02 , Sr _2.995 MgSi ₂ O ₈ :Eu _0.005 , Sr _2.99 MgSi ₂ O ₈ :Eu _0.01 , Sr _2.95 MgSi ₂ O ₈ :Eu _0.05 , Sr _2.90 MgSi ₂ O ₈ :Eu _0.10 are compared in brightness, and any one of them has high brightness.

Therefore, it can be seen that when the C-SMS obtained by substituting part of the Sr component of the above-mentioned basic SMS (Sr _2.97 MgSi ₂ O ₈ :Eu _0.03 ) with Ca is used for a plasma display panel using a discharge gas containing Xe composition, High luminous efficiency can be obtained under the excitation of light with a wavelength of 172nm, so Xe ₂ molecular rays can be used efficiently, and a high-brightness PDP device can be realized.

Furthermore, it can be seen that it is well applicable to the so-called "PDP corresponding to high xenonization" technology, in which, for example, a xenon gas composition ratio of 6% or more is used, and it is more preferable to use _Xe2 molecular rays according to the active use The discharge gas is formed by containing xenon (Xe) gas at a composition ratio of 10% or more. Therefore, even in the case of a PDP using a highly xenonized discharge gas, it is possible to constitute a discharge gas having a high luminance compared with a CMS. light emitting device.

Next, (Sr _0.8 Ca _0.2 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 and (Sr _0.7 Ca _0.3 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 were synthesized by the same method as above.

For (Sr _0.8 Ca _0.2 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , make SrCO ₃ 3.508 g (23.76 mmol), CaCO ₃ 0.595 g (5.94 mmol), and for (Sr _0.7 Ca _0.3 ) _2.97 MgSi ₂ O ₈ : Eu _0.03 , except that SrCO ₃ was 3.069 g (20.79 mmol) and CaCO ₃ was 0.892 g (8.91 mmol), the desired phosphor was obtained in the same manner as above.

Using the obtained phosphor group, in order to evaluate the color purity of light emitted under 172 nm vacuum ultraviolet ray excitation, the y value in the X, Y chromaticity diagram of the obtained emitted light was evaluated. The evaluation results show that for (Sr _0.8 Ca _0.2 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , the y value is below CMS, and for (Sr _0.7 Ca _0.3 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 , the y value is larger than CMS, although it is high Brightness, but the color purity is worse than CMS.

Based on the above facts, in the C-SMS in which part of the Sr component of the above-mentioned basic SMS (Sr _2.97 MgSi ₂ O ₈ :Eu _0.03 ) is substituted with Ca, the substitution amount of Ca is preferably 0.2 or less (20% or less) of Sr. ).

Next, (Sr _0.90 Ca _0.10 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 (C-SMS) was used as the blue phosphor, and the same as the first embodiment related to the present invention was made except that this C-SMS was used. Plasma display screen (PDP) of the light-emitting device of the structure. The plasma display device has high luminance and vivid display colors, and has a long lifespan.

<Embodiment 8>

As the blue phosphor, (Sr _0.90 Ca _0.10 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 (C-SMS) used in the light-emitting device of the seventh embodiment of the present invention was used. In addition to using this C-SMS, a A rare gas (xenon) discharge white fluorescent lamp in a light emitting device having the same structure as the fifth embodiment of the present invention.

As phosphors other than the blue phosphor, a divalent manganese-activated zinc silicate phosphor was used as the green phosphor, and a trivalent europium-activated yttrium-gadolinium acid phosphor was used as the red phosphor to produce a rare gas (xenon) discharge white fluorescent lamp. The lamp is highly luminously efficient and has a long life.

In addition, by using the lamp of this embodiment as a backlight and combining it with a separately prepared liquid crystal display panel in the same configuration as the fifth embodiment, a bright liquid crystal display device can be produced as a display device.

<Example 9>

As the blue phosphor, (Sr _0.90 Ca _0.10 ) _2.97 MgSi ₂ O ₈ :Eu _0.03 (C-SMS) used in the light-emitting device of the seventh embodiment of the present invention was used to produce a planar rare gas (xenon) discharge white fluorescent light.

For phosphors other than the blue phosphor, a divalent manganese-activated zinc silicate phosphor was used as a green phosphor, and a trivalent europium-activated acidified yttrium-gadolinium phosphor was used as a red phosphor. The lamp is bright and has a long life.

In addition, by using the lamp of this embodiment as a backlight and combining it with a separately prepared liquid crystal display as a display device, a bright liquid crystal display device can be produced.

According to the present invention, stable high-performance display can be performed based on the long-life and high-brightness phosphor material, and by configuring a larger light-emitting device, it can be applied to indispensable devices that require long-time lighting, high brightness, and long life. The use of large-scale household flat-panel display devices.

Claims (9)

1. plasm display device has following formation:

The a pair of substrate of subtend ground configuration at interval according to the rules, be arranged between the above-mentioned a pair of substrate, between above-mentioned a pair of substrate, form the next door in space, the electrode pair that at least one side of the subtend face of above-mentioned a pair of substrate, sets, be enclosed in the above-mentioned space that forms between the above-mentioned a pair of substrate and can discharge and ultraviolet discharge gas takes place by between above-mentioned electrode pair, applying voltage, with containing of forming at least one side of the wall in the subtend face of above-mentioned a pair of substrate in above-mentioned space and above-mentioned next door by the luminescent coating of ultraviolet ray excited and luminous fluorophor

It is characterized in that above-mentioned discharge gas is to contain the gas that ratio of components constitutes at the Xe of the amount more than 6%,

Above-mentioned fluorophor contains the Eu activated silicates fluorophor by following general formula (1) expression;

(Sr _1-xBa _x) _3-eMgSi ₂O ₈:Eu _e ...(1)

In the formula, the x of the ratio of components of expression composition Ba and the e of the ratio of components of expression composition Eu are respectively 0.1＜x≤0.5,0.001≤e≤0.2.

2. the plasm display device described in the claim 1 is characterized in that, represents that the x of ratio of components of the composition Ba of the Eu activated silicates fluorophor shown in the above-mentioned general formula (1) is 0.2＜x≤0.5.

3. the plasm display device described in the claim 1 is characterized in that, represents that the x of ratio of components of the composition Ba of the Eu activated silicates fluorophor shown in the above-mentioned general formula (1) is 0.2＜x≤0.4.

4. the plasm display device described in the claim 1 is characterized in that, represents that the x of ratio of components of the composition Ba of the Eu activated silicates fluorophor shown in the above-mentioned general formula (1) is 0.2＜x≤0.3.

5. the plasm display device described in the claim 1 is characterized in that, represents that the e of ratio of components of the composition Eu of the Eu activated silicates fluorophor shown in the above-mentioned general formula (1) is 0.01≤e≤0.05.

6. the plasm display device described in the claim 1 is characterized in that, above-mentioned discharge gas is to contain the gas that ratio of components constitutes at the Xe of the amount more than 10%.

7. the plasm display device described in the claim 1 is characterized in that, above-mentioned discharge gas is to contain the gas that ratio of components constitutes at the Xe of the amount more than 12%.

8. the plasm display device described in the claim 1, it is characterized in that, form the luminescent coating of any formation of red light-emitting phosphor, green emitting fluorophor and blue-light-emitting fluorescent material in each above-mentioned space, wherein blue-light-emitting fluorescent material contains the Bu activated silicates fluorophor shown in the above-mentioned general formula (1).

9. the plasm display device described in the claim 8 is characterized in that, above-mentioned red light-emitting phosphor contains and is selected from (Y, Gd) BO ₃: Eu, Y ₂O ₃: Eu, (Y, Gd) ₂O ₃: Eu and (Y, Gd) (P, V) O ₄: the fluorophor of more than one among the Eu, above-mentioned green-emitting phosphor contain and are selected from Zn ₂SiO ₄: Mn, (Y, Gd, Sc) ₂SiO ₅: Tb, (Y, Gd) ₃(Al, Ga) ₅O ₁₂: Tb, (Y, Gd) ₃(Al, Ga) ₅O ₁₂: Ce, (Y, Gd) B ₃O ₆: Tb and (Y, Gd) PO ₄: the fluorophor of more than one among the Tb.

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