CN100397544C - Light emitting device and image display device used said - Google Patents

Abstract

A blue-emitting phosphor is optimized by controlling mole fractions typically of Mg and Si in Sr<SUB>3-e</SUB>Mg<SUB>b</SUB>Si<SUB>2</SUB>cO<SUB>8d</SUB>:Eu<SUB>e </SUB>or by further including an optimal amount of at least one additional component such as Ba or Ca. The resulting phosphor exhibits a higher brightness and a higher color purity upon excitation by ultraviolet light emitted as a result of discharge of xenon gas. The optimized phosphor is incorporated into light emitting devices such as lamps and PDPs, and further into display devices.

Description

Light-emitting device and the image display device that uses this light-emitting device

Technical field

The present invention relates to be subjected to the ultraviolet ray excited and luminous fluorophor in ultraviolet ray, particularly vacuum ultraviolet (VUV) zone, particularly use Eu activated silicates fluorophor and light-emitting device of the fluorescent lamp of the tubulose that constitutes or plane or plasma display panel (PDP) etc. and the image display device (being designated hereinafter simply as display unit) that uses this light-emitting device.

Background technology

In recent years, people increase just day by day for the requirement of the slimming that does not take up space that the display unit that with TV and personal computer display device (パ ソ コ Application モ ニ one) is representative proposes, for as can with the corresponding device of slimming, carrying out energetically such as plasma scope (PDP) device, field emission escope (FED) device, the exploitation that will carry on the back the liquid crystal indicator etc. of irradiation formation display unit with thin LCDs combination.

Plasma display apparatus is a kind of display unit of using plasma display panel (PDP) as light-emitting device, the ultraviolet ray that plasma display panel (PDP) takes place by the cathode glow zone of using in containing the fine discharge space of rare gas is (in the situation of use xenon as rare gas, be the wave band that is in 147nm and 172nm) as excitaton source, excite the fluorophor in the luminescent coating that in this fine discharge space, sets, impelling this light-emitting phosphor, thereby obtain luminous in visibility region.Utilize plasma scope (PDP) device to control this luminous amount and look, and use it in the image demonstration.

In addition, liquid crystal indicator is a kind of by aforesaid back of the body irradiation and the combination of holding liquid crystal constitutes between the pair of electrodes substrate LCDs are constituted, and generally is that amount or the look by the light that taken place by back of the body irradiation in the control of LCDs side carries out desirable image device shown.And, as present situation back of the body irradiation, generally use the tubulose white fluorescent lamp of the straight pipe type that on inwall, is coated with fluorescent material etc.

In addition, as the document relevant, can list patent documentation shown below 1～4 and non-patent literature 1～3 with these technology.

(patent documentation 1) spy opens the 2003-132803 communique

(patent documentation 2) spy opens the 2003-142004 communique

(patent documentation 3) spy opens the 2003-242892 communique

(patent documentation 4) spy opens the 2003-346660 communique

" fluorophor handbook オ one system society III volume in 1987, the 2nd chapter, the 219th page the-the 223rd page are compiled by (non-patent literature 1) fluorophor classmate's association

The 639th page the-the 642nd page of (non-patent literature 2) IDW ' 00 Proceedings of The SeventhInternational Display Workshops

The 45th page the-the 48th page of (non-patent literature 3) TECHNICAL REPORT OF IEICE.EID2003-69 (2004-01)

(non-patent literature 4) " FLAT-PANEL DISPLAY 2003 (practice volume) " Nikkei BP society, PART.7-1, the 210th page the-the 217th page

Summary of the invention

Though people wish to reach high performance at the light-emitting device of plasma display apparatus and FED device and the back of the body irradiation that uses in liquid crystal indicator, the improvement of these characteristics is to a great extent with corresponding various Design of device structures and to constitute the fluorophor that uses in their material, the particularly light-emitting device relevant.

Use red, blue, green versicolor fluorophor in the fluorophor of existing PDP device, but generally use chlorate MClO 3 fluorescent substance (BaMgAl as blue emitting phophor ₁₀O ₁₇: Eu is designated hereinafter simply as BAM).Though this BAM characteristics of luminescence is good, exist the problem of easy deterioration.That is, aspect reliability problem is arranged, the life-span is short, so people's strong request has stability, long lifetime.And, in order to make light-emitting device and then to make display unit high performance further, also require higher colorimetric purity and higher luminosity.

In addition, the back of the body irradiation of using about bulb and liquid crystal indicator, also require the brightness raising of display surface and consider that from the problem of environment aspect requirement reaches mercuryless, the back of the body irradiation of using about liquid crystal indicator, as countermeasure, people are developing the fluorescent lamp etc. of the noble gas discharge formula of plane.As the fluorescent lamp of noble gas discharge, usually use the fluorophor luminous by excited by vacuum ultraviolet, requiring under the excited by vacuum ultraviolet condition can be luminous expeditiously and demonstrate high brightness and high colorimetric purity, and requires long-life fluorophor.

In recent years, developing high brightness, the high color purity of the alternative BAM of a class, the blue emitting phophor of high reliability, and suggestion uses a kind of silicates fluorophor conduct as blue emitting phophor, this fluorophor can be used in the bulb of PDP device and noble gas discharge, and compare with the BAM as blue-light-emitting fluorescent material in the past, have high reliability and long life-span.Specifically, Ca is used in suggestion _1-xMgSi ₂O ₆: Eu _x(being designated hereinafter simply as CMS).

Yet though the ultraviolet ray that CMS is had in the wave band with 147nm has high brightness as the situation of excitaton source, colorimetric purity is also good, has excitation band in the scope of wavelength 160nm～210nm hardly.Therefore, be near the important 172nm vacuum ultraviolet (Xe being subjected to for PDP ₂The luminous intensity that is produced during exciting molecular ray) significantly reduces, and this is the difficult point that exists.

Now, parallel with the high performance research of fluorescent material, in the technical field of PDP device, be the research that purpose is improved display screen structure with the luminous efficiency that improves PDP, as the method for one of them, the Xe gas ratio of components in the discharge gas is increased, utilize Xe energetically ₂The research of molecular ray is carried out widely.Be " high xenonization " technology in the so-called plasma display panel (PDP), the xenon ratio of components in its discharge gas is higher than about 4%, and people are carrying out the research for the high efficiency that makes this PDP display screen.

Yet, with respect to the technology of this PDP high efficiency, Xe ₂The utilization ratio of molecular ray very low CMS originally can not fully meet the requirements.That is, even the ultraviolet ray of 172nm wave band increases, the luminous efficiency under the 172nm shooting condition is also very low, and resulting light characteristic is insufficient.Therefore, even include the high efficiency of PDP in the visual field from now on, also must particularly must improve the luminous efficiency in 172nm wavelength excitation band to utilizing CMS to replace BAM and making its practicability do further improvement.

Therefore, the 1st problem to be solved by this invention is, fluorophor in the past, the particularly blue emitting phophor that under the excited by vacuum ultraviolet condition, uses in the PDP device etc. insufficient aspect the life-span, consequently, use the life-span (be often referred to spendable during) of the light-emitting device of these fluorophor and light characteristic is insufficient, and then use the life-span (be often referred to spendable during) of the image display device of this light-emitting device and light characteristic is insufficient.And performances such as colorimetric purity can not be said very abundant.

In addition, the 2nd problem to be solved by this invention be, in as the silicate phosphor that proposes at the improvement strategy of the problem points of above-mentioned blue emitting phophor in the past, and light characteristic, particularly by Xe ₂The light characteristic that molecular ray (wavelength 172nm) excites is very low, existing light-emitting device and use the display unit of this existing light-emitting device and expectation from now on utilize Xe energetically ₂The light characteristic of the light-emitting device that molecular ray (172nm) excites, particularly PDP device and the light characteristic of PDP image display device insufficient.

In order to finish above-mentioned problem, can list the characteristic point of representational light-emitting device of the present invention, it is to have at least one pair of electrode, possess simultaneously and a kind ofly can discharge and ultraviolet discharge gas takes place by between above-mentioned electrode, applying voltage, and when being subjected to the action of ultraviolet radiation that takes place from this discharge gas, be excited and the light-emitting device of luminous luminescent coating, it is characterized in that, above-mentioned discharge gas contains the Xe ratio of components in the amount more than 6%, preferably at xenon (Xe) gas of the amount more than 10%, the fluorophor that constitutes above-mentioned luminescent coating is a kind of Eu activated silicates fluorophor by following formula (I) expression that is excited as the time spent at the vacuum ultraviolet that contains wavelength 172nm at least that is subjected to taking place based on above-mentioned xenon gaseous discharge that contains.In addition, can list the characteristic point of representational image display device of the present invention, it has above-mentioned light-emitting device and plasma display panel (PDP) structure.

M1 _3a-eMg _bSi _2cO _8d:Eu _e ...(I)

But, in the formula (I), the element a kind or more of M1 for from strontium (Sr), calcium (Ca) and barium (Ba), selecting, 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 be, above-mentioned fluorophor is the Eu activated silicates fluorophor by above-mentioned formula (I) expression, it is characterized in that it is the fluorophor that a kind of value that contains a, b, c and d in the above-mentioned formula (I) is respectively the Eu activated silicates fluorophor of a=1, b=1, c=1, d=1.

And then, it is characterized in that, in employed above-mentioned europium (Eu) activated silicates fluorophor,, be 0.01≤e≤0.05 as the preferred ratio of components of the europium (Eu) of activator according to the record of above-mentioned formula (I).

In addition, it is characterized in that in employed above-mentioned Eu activated silicates fluorophor, according to the record of above-mentioned formula (I), the preferred ratio of components of magnesium (Mg) is 1＜b≤1.2.

In addition, it is characterized in that in employed above-mentioned Eu activated silicates fluorophor, according to the record of above-mentioned formula (I), silicon (Si) ratio of components is 1＜c≤1.2.

In addition, the invention is characterized in that in the light-emitting device that uses fluorophor to constitute, it is that the Eu activated silicates fluorophor that following formula (II) is represented constitutes that employed fluorophor is to use by general formula.

(Sr _1-xM2 _x) _3a-eMg _bSi _2cO _8d:Eu _e ...(II)

Should illustrate, 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), the element of selecting in thallium (T1) and the lutetium (Lu) more than a kind, 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≤0.2,0.1＜x≤0.5, but situation at M2=Ba, x is the scope of 0.1＜x≤0.5, and more preferably x is the scope of 0.1＜x＜0.2 or 0.2＜x≤0.5.

Especially, above-mentioned fluorophor is the Eu activated silicates fluorophor by above-mentioned formula (II) expression, and the value that it is characterized in that wherein containing a, b, c and d in the above-mentioned formula (II) is respectively the fluorophor of the Eu activated silicates fluorophor of a=1, b=1, c=1, d=1.

And especially, feature of the present invention is that in the light-emitting device that uses fluorophor to constitute, it is that the Eu activation fluorophor that following formula (III) is represented constitutes that employed fluorophor is to use by general formula.

(Sr _1-x-yBa _xM3 _y) _3a-eMg _bSi _2cO _8d:Eu _e ...(III)

In the formula (III), M3 is from 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), the element of selecting in thallium (T1) and the lutetium (Lu) more than a kind, 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 ratio of components of barium (Ba) and above-mentioned M3 element, are 0.1＜x+y≤0.5.

Especially, above-mentioned fluorophor is the Eu activated silicates fluorophor by above-mentioned formula (III) expression, it is characterized in that it is the fluorophor that the value that contains a, b, c and d in the above-mentioned formula (III) is respectively the Eu activated silicates fluorophor of a=1, b=1, c=1, d=1.

And then feature of the present invention is that in the light-emitting device that uses fluorophor to constitute, it is that the Eu activation fluorophor that following formula (IV) is represented constitutes that employed fluorophor is to use by general formula.

(Sr _1-x-yCa _xM4 _y) _3a-eMg _bSi _2cO _8d:Eu _e ...(IV)

But, in the formula (VI), M4 is 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), the element of selecting in thallium (Tl) and the lutetium (Lu) more than a kind, 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 ratio of components of calcium (Ca) and above-mentioned M4 element, are 0＜x+y≤0.2.

Especially, above-mentioned fluorophor is the Eu activated silicates fluorophor by above-mentioned formula (IV) expression, and the value that it is characterized in that containing a, b, c and d in the above-mentioned formula (IV) is respectively the fluorophor of the Eu activated silicates fluorophor of a=1, b=1, c=1, d=1.

The effect of invention

The advantage of this light-emitting device among the present invention is, owing to use a kind of except the optical excitation condition of wavelength 147nm, even therefore the Eu activated silicates fluorophor of the also good high brightness of luminous efficiency under the optical excitation condition of wavelength 172nm can obtain high brightness.

In addition, being also advantageous in that of this light-emitting device among the present invention, owing to use a kind of except the optical excitation condition of wavelength 147nm, even therefore the Eu activated silicates fluorophor that luminous efficiency is also good under the optical excitation condition of wavelength 172nm, colorimetric purity is high can obtain the good characteristics of luminescence.

In addition, being also advantageous in that of this display unit among the present invention, because the light-emitting device that is constituted uses the Eu activated silicates fluorophor of high brightness and the Eu activated silicates fluorophor of high color purity, therefore can realize the demonstration of high brightness and the demonstration of high color purity.

Description of drawings

Fig. 1 is for constituting the fluorophor SMS (Sr of first embodiment of the invention _2.98MgSi ₂O ₈: Eu _0.02) with the stimulated luminescence spectrum of the CMS of object as a comparison.

Fig. 2 is the exploded perspective view that illustrates as the structure example of the plasma display panel (PDP) of embodiment of the present invention.

Fig. 3 illustrates the curve chart of first embodiment of the invention as the relation of Eu ratio of components in the fluorophor of PDP component parts and relative brightness.

Fig. 4 is for illustrating the block diagram of the image display device that uses plasma display panel (PDP) of the present invention (PDP).

Fig. 5 illustrates the curve chart of fourth embodiment of the invention as the relation of the Ba ratio of components in the fluorophor of PDP component parts and relative brightness and y value.

Fig. 6 is the cross-sectional view of the structure of rare gas (inclosure xenon) discharge white fluorescent lamp that fifth embodiment of the invention is shown.

Fig. 7 is the exploded perspective view that the structure of liquid crystal indicator of the present invention is shown.

Symbol description

1, the 6... substrate,

2, the 9... electrode,

3... bus rod,

4, the 8... dielectric layer,

5... diaphragm,

7... the next door,

10... luminescent coating,

100... plasma display panel (PDP),

101... drive circuit,

102... the plasma scope display unit,

103... the reflection source,

104... image display device,

110... the noble gas discharge white lamps,

111... glass tube,

112... luminescent coating,

113... electrode,

120... liquid crystal indicator,

121... back light unit,

122... LCDs,

123, the 130... basket,

124... reflecting plate,

126... diffuser plate,

127A, B... prismatic film,

128... reflection polarizing plate,

129... inverter.

Embodiment

Blue emitting phophor BAM in the past has problems aspect reliability, and the life-span is short, therefore uses the light-emitting device of BAM and uses the reliability of the display unit of this device to reduce.

Improve strategy as it, proposed the scheme of high silicate phosphor, particularly CMS of reliability in recent years, but be subjected to the wave band that surpasses 170nm excite resulting light characteristic low, can not constitute the light-emitting device of high brightness, particularly PDP device.

Therefore, it is fluorophor that the inventor etc. are conceived to silicate, explore the synthesizing new material, thereby realized under the optical excitation condition of wavelength 172nm, obtaining the silicate phosphor of high brightness, but and used this silicate phosphor to realize the light-emitting device of high brightness and the display unit that high brightness shows.

The new Eu activated silicates fluorophor of realizing is by the Eu activated silicates fluorophor shown in Eu the activated silicates fluorophor, particularly following formula (V) of following formula (I) expression.Should illustrate, contain following aptly by the Eu activated silicates fluorophor shown in the following formula (V) and by formula (II), (III), (IV), (VII), (IX), (XI), (XII) and the Eu activated silicates fluorophor (XIII) etc. contain strontium (Sr) and magnesium (Mg) as europium (Eu) the activated silicates fluorophor that constitutes element, it is generically and collectively referred to as SMS.

M1 _3a-eMg _bSi _2cO _8d:Eu _e ...(I)

[in the formula (I), the element a kind or more of M1 for from strontium (Sr), calcium (Ca) and barium (Ba), selecting, 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-eMg _bSi _2cO _8d:Eu _e ...(V)

[in the 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].

Should illustrate that according to stoichiometric proportion, the Eu activated silicates fluorophor and the SMS of formula (I) have M1 _3-eMgSi ₂O ₈: Eu _eOr Sr _3-eMgSi ₂O ₈: Eu _eComposition, that is, and the composition of a=1, b=1, c=1 and d=1.The realization of this composition is preferred.

Yet; even if with the stoichiometric proportion shown in above-mentioned formula (I), (V) ratio of components that some deviations, the Sr that is contained, Ca and Ba add up to arranged, also have Mg, further also have silicon (Si) and oxygen (O) the formation element ratio of components separately of etc.ing to compare to reach 1.2 times superfluous or reaches 0.8 times very few with above-mentioned value, even and the ratio of componentss that are accompanied by other formation elements compare with above-mentioned numerical value to some extent that the silicate phosphor of the composition of variation also can use.

And, as described below, can judge in some situation, form the fluorophor that some deviations are arranged with above-mentioned stoichiometric composition by using it, also can obtain higher luminescent properties, therefore might use this class fluorophor energetically.

Secondly, the detailed steps such as synthetic method of the fluorophor that uses among the present invention will describe in the paragraph of the embodiment of back, for the Sr as an example _2.98MgSi ₂O ₈: Eu _0.02, its feature is described.

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

According to conventional method, use deuterium lamp as light source, measure stimulated luminescence spectrum, as shown in Figure 1, as can be known in the stimulated luminescence spectrum of obtained CMS, the luminous intensity that obtains near surpassing 170nm the wave band sharply reduces, and the luminous efficiency that is caused that excites of the light of wavelength 172nm significantly reduces.

On the other hand, as shown in Figure 1, even also demonstrate high luminous intensity as near the zone of SMS 170nm of an example that realizes among the present invention as can be known, and should value more much higher than CMS, under near the exciting of the light the wavelength 172nm, can obtain high luminous efficiency.At this moment, though near the wave band 147nm, above-mentioned SMS also demonstrate with CMS with contour luminosity.

Therefore,, specifically, be used for tubulose or plane fluorescent lamp and plasma display panel (PDP) by this SMS is used for light-emitting device, can obtain high brightness light-emitting device, therefore and can obtain high performance display device.

In addition, about the composition of discharge gas in the plasma display panel (PDP) relation with the uitraviolet intensity that takes place by discharge, distinguish, the ratio of components that contains the Xe composition is big more, the all intensity of sending by discharge of vacuum ultraviolet increases, and the ratio of the constituent in the vacuum ultraviolet that is sent changes.

Specifically, distinguish,, can cause the ultraviolet composition of the wavelength 147nm that in the vacuum ultraviolet that takes place, is contained and the ultraviolet ray (Xe of 172nm by the variation of the Xe ratio of components in the discharge gas ₂Molecular ray) volume efficiency (I of composition ₁₇₂/ I ₁₄₇) change, that is, and along with the increase of Xe ratio of components, volume efficiency (I ₁₇₂/ I ₁₄₇) increase.

The result of study that is obtained shows, with regard to AC type PDP, and when the Xe ratio of components is 4%, I ₁₇₂/ I ₁₄₇(4%)=1.2, with regard to the PDP in the past that the Xe ratio of components is 1～4% normal conditions, owing to the volume efficiency of the ultraviolet composition of the ultraviolet composition of the wavelength 147nm that is contained in the vacuum ultraviolet that takes place of discharge and 172nm, the 172nm composition from intensity slightly greatly some to equal extent or even the intensity of 172nm composition the tendency of reduction is arranged.

And further the result of research shows, when the Xe ratio of components was 6%, the vacuum ultraviolet intensity that takes place owing to discharge increased, simultaneously I ₁₇₂/ I ₁₄₇(6%)=1.9, improve significantly, when the Xe ratio of components was 10%, the vacuum ultraviolet intensity that takes place owing to discharge increased, simultaneously I ₁₇₂/ I ₁₄₇(10%)=3.1, improve by a larger margin, when the Xe ratio of components was 12%, the vacuum ultraviolet intensity that takes place owing to discharge increased, simultaneously I ₁₇₂/ I ₁₄₇(12%)=3.8, improves significantly.

Therefore, a kind of like this fluorophor of preferred use, this fluorophor is compared with the PDP of normal conditions, and the Xe ratio of components in its discharge gas is big, for example with the corresponding PDP of high xenonization with Xe ratio of components of 6% in, the vacuum ultraviolet of 172nm is stimulated luminescence efficiently; For ratio of components surpass 6% and the Xe ratio of components be the higher situation more than 10% etc., people increase just day by day to the demand of this class fluorophor.

Therefore, in the plasma display panel (PDP) of the discharge gas that contains the Xe composition in use, use the situation of Eu activated silicates fluorophor, the particularly SMS of above-mentioned formula (I), in fluorophor, obtain high luminous efficiency owing to the exciting of light of wavelength 172nm, therefore can utilize Xe expeditiously ₂Molecular ray, thus the PDP device of high brightness might be made.

And then, Eu activated silicates fluorophor, the particularly SMS of above-mentioned formula (I) also is applicable to the technology of so-called " PDP corresponding with high xenonization " well, in this technology, for example preferably use the Xe ratio of components at the discharge gas more than 6%, more preferably use by the Xe ratio of components and contain xenon (Xe) gas and the discharge gas that constitutes in the amount more than 10%, the ultraviolet composition that this discharge gas meets 172nm is (to utilize Xe energetically by force with respect to the ratio of the intensity of 147nm composition ₂Molecular ray) therefore condition, even if under the situation of the PDP of the discharge gas that uses high xenonization, also can constitute and have the light-emitting device of high brightness more than CMS.

In addition, make its ratio of components optimization by Eu activated silicates fluorophor, particularly SMS as the basis with above-mentioned formula (I), perhaps by its composition of improvement, the luminosity of the fluorophor that obtains owing to exciting of wavelength 172nm can be improved further, perhaps luminous colorimetric purity can be further improved.

Specifically, likening to the best composition is purpose, the Eu activated silicates fluorophor that meets condition preferably by synthetic Eu ratio of components by following formula (VI) expression, particularly by the Eu activated silicates fluorophor of following formula (VII) expression, can be implemented under the optical excitation condition of wavelength 172nm and obtain the more silicate phosphor of high brightness, by using this fluorophor, can realize the light-emitting device of high brightness, thereby can realize obtaining the display unit that high brightness shows.

M1 _3a-eMg _bSi _2cO _8d:Eu _e ...(VI)

[in the formula (VI), the element a kind or more of M1 for from Sr, Ca and Ba, selecting, 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-eMg _bSi _2cO _8d:Eu _e ...(VII)

[in the 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 synthetic Mg ratio of components meet condition preferably by the Eu activated silicates fluorophor of following formula (VIII) expression, particularly by the Eu activated silicates fluorophor of following formula (IX) expression, can be implemented under the optical excitation condition of wavelength 172nm and obtain the more silicate phosphor of high brightness.By using this fluorophor, can realize the light-emitting device of high brightness, thereby can realize obtaining the display unit that high brightness shows.

M1 _3a-eMg _bSi _2cO _8d:Eu _e ...(VIII)

[in the formula (VIII), the element a kind or more of M1 for from Sr, Ca and Ba, selecting, 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-eMg _bSi _2cO _8d:Eu _e ...(IX)

[in the 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 synthetic Si ratio of components meet condition preferably by the Eu activated silicates fluorophor of following formula (X) expression, particularly by the Eu activated silicates fluorophor of following formula (XI) expression, can be implemented under the optical excitation condition of wavelength 172nm and obtain the more silicate phosphor of high brightness.By using this fluorophor, can realize the light-emitting device of high brightness, thereby can realize obtaining the display unit that high brightness shows.

M1 _3a-eMg _bSi _2cO _8d:Eu _e ...(X)

[in the formula (X), the element a kind or more of M1 for from Sr, Ca and Ba, selecting, 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-eMg _bSi _2cO _8d:Eu _e ...(XI)

[in the 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].

Below, become purpose with improvement group, synthetic is the Eu activation fluorophor of following formula (II) expression by general formula.

For the formation element M 2 in the formula (II), can be from those can with Sr double replacement or mutually solid solution mutually, thereby form the element of selecting in the metallic element of metallic element, particularly divalence of few crystallization of defective or solid solution and rare earth element etc. easily, particularly for example, can be the element of from 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, selecting more than a kind.

And, particularly in the silicate phosphor that obtains by compositionization, can improve the colorimetric purity luminous by exciting, the preferred Ba element of selecting use to obtain high brightness luminescent under the 172nm shooting condition, the preferred following formula (XII), the Eu shown in (III) that contain Ba of using activates fluorophor.

(Sr _1-xM2 _x) _3a-eMg _bSi _2cO _8d:Eu _e ...(II)

[in the formula (II), the element a kind or more of M2 for from 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, selecting, 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≤0.5, but, in the situation of M2=Ba, x is in the scope of 0.1＜x≤0.5].

(Sr _1-xBa _x) _3a-eMg _bSi _2cO _8d:Eu _e ...(XII)

[in the 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, and x is in the scope of 0.1＜x≤0.5].

(Sr _1-x-yBa _xM3 _y) _3a-eMg _bSi _2cO _8d:Eu _e ...(III)

[in the formula (III), the element a kind or more of M3 for from 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, selecting, 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, and x and y are 0.1＜x+y≤0.5].

Should illustrate that according to stoichiometric proportion, the Eu activation fluorophor of being represented by above-mentioned formula (II) has (Sr _1-xM2 _x) _3-eMgSi ₂O ₈: Eu _eComposition; Eu activation fluorophor by above-mentioned formula (XII) expression has (Sr _1-xBa _x) _3-eMgSi ₂O ₈: Eu _eComposition; Eu activation fluorophor by above-mentioned formula (III) expression has (Sr _1-x-yBa _xM3 _y) _3-eMgSi ₂O ₈: Eu _eComposition.

Yet; even if with above-mentioned formula (II), (XII) and the stoichiometric proportion (III) some deviations are arranged; the ratio of components sum of the ratio of components sum of the ratio of components sum of the Sr that is contained and M2, Sr and Ba or Sr and Ba and M3 or the composition of Mg, Si or each element of oxygen (O) are compared the situation such as very few that reaches 1.2 times superfluous or reach 0.8 times with above-mentioned composition; and be accompanied by other ratio of componentss that constitute elements and compare with above-mentioned numerical value when changing to some extent, also can use the silicate phosphor of the composition that changes to some extent.

By above research, realized under the optical excitation condition of wavelength 172nm, obtaining the more luminous silicate phosphor of high brightness and high color purity.And, by using this fluorophor, the light-emitting device of high brightness can be realized, thereby the display unit that high-performance shows can be realized obtaining.

And then, particularly in the silicate phosphor that obtains by compositionization, the preferred Ca element of selecting use can improve the luminous intensity when being subjected to ultraviolet the exciting of wavelength 172nm, the preferred Eu activated silicates fluorophor that contains Ca that uses by following formula (XIII), (IV) expression.

(Sr _1-xCa _x) _3a-eMg _bSi _2cO _8d:Eu _e ...(XIII)

[in the 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-x-yCa _xM4 _y) _3a-eMg _bSi _2cO _8d:Eu _e ...(IV)

[in the formula (IV), the element a kind or more of M4 for from Ba, 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, selecting, 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, and x and y are 0＜x+y≤0.2].

Should illustrate that according to stoichiometric proportion, the Eu activation fluorophor of being represented by above-mentioned formula (XIII), (IV) has (Sr _1-xCa _x) _3-eMgSi ₂O ₈: Eu _e(Sr _1-x-yCa _xM4 _y) _3-eMgSi ₂O ₈: Eu _eComposition.

Yet; even if some deviations are arranged with the stoichiometric proportion shown in above-mentioned formula (XIII), (IV); the ratio of components sum of the ratio of components sum of the Sr that is contained and Ca or Sr and Ca and M4 or the composition of Mg, Si or each element of oxygen (O) are compared with above-mentioned composition and are reached 1.2 times superfluous or reach 0.8 times very few, and are accompanied by and compare the silicate phosphor of forming that changes to some extent with above-mentioned numerical value by other the ratio of components that constitutes element and also can use.

By using above Eu activated silicates fluorophor, thereby the light-emitting device that can realize high brightness can realize obtaining the display unit that high brightness shows.

Based on the above fact, constitute as the plasma display panel (PDP) of embodiment of the present invention of using above-mentioned silicate phosphors such as Eu activated silicates fluorophor, particularly SMS is can be following such.

Fig. 2 is the exploded perspective view of expression as the structure of the plasma display panel (PDP) of embodiment of the present invention.

Plasma display panel (PDP) 100 as embodiment of the present invention has following constitutive characteristic, promptly, it have be used for so-called " face discharge " corresponding structure, and possesses according to the rules a pair of substrate 1 of subtend ground configuration at interval, 6, be arranged on this a pair of substrate 1, between 6 and be used to keep the next door 7 at the interval between this a pair of substrate, be enclosed in the space that forms between this a pair of substrate and also can ultraviolet discharge gas (not shown) take place by discharge, with the show electrode 2 and address (the ア De レ ス) electrode 9 that on the subtend face of this a pair of substrate, dispose respectively, and constitute luminescent coating 10 on side's substrate 6 of the above-mentioned fluorophor that contains Eu activated silicates fluorophor in this a pair of substrate and the surface of next door 7, when being subjected to causing the action of ultraviolet ray of this discharge gas generation owing to discharging, the Eu activated silicates fluorophor that constitutes luminescent coating 10 is excited also luminous.

Should illustrate; the lead of the symbol 3 shown in Fig. 2 is the bus rods 3 that become one with electrode 2 (show electrode); silver or Cu-Cr that it is provided with by being used to reduce electrode resistance constitute; the layer of symbol 4,8 is a dielectric layer 4,8, and the layer of symbol 5 is for being used for the diaphragm 5 that guard electrode is provided with.

In the plasma display panel (PDP) of the surface discharge type color PDP device shown in the present embodiment, for example, by applying negative voltage to show electrode (being commonly referred to as scan electrode), and apply positive voltage (is positive voltage than the voltage that applies to show electrode) to address electrode and show electrode and discharge, can form thus and a kind ofly can assist the wall electric charge (be referred to as and write) that between show electrode and show electrode, begins to discharge.Under this state,, will in two electric discharge between electrodes spaces, discharge by dielectric (and protective layer) if between show electrode and show electrode, apply suitable opposite voltage.

After discharge finishes, if, new discharge will take place then the voltage reversal that is applied on show electrode and the show electrode.By repeating this operation, can discharge constantly (be referred to as and keep discharge or show discharge).

(embodiment)

Below explanation be used to implement the corresponding embodiment of preferred plan of the present invention.

＜embodiment 1 〉

Present embodiment is as an example of image display device, and the manufacturing of the plasma display panel (PDP) of synthesizing, use this fluorophor of fluorophor and a series of technology of using the image display device of this plasma display screen are described with reference to the accompanying drawings successively.

(1) fluorophor is synthetic:

In order to make the plasma display panel (PDP) of first embodiment that the present invention relates to, at first carry out synthetic as the fluorophor of component parts.

At first the chemical formula of He Cheng fluorophor is Sr _2.98MgSi ₂O ₈: Eu _0.02

Synthesize and carry out as described below: take by weighing SrCO respectively as raw material ₃4.399g (29.80mmol), MgCO ₃0.962g (10.00mmol), SiO ₂1.202g (20.00mmol), Eu ₂O ₃0.0352g (0.10mmol) and as the NH of flux ₄Br 0.392g (4.00mmol) after fully mixing in the mortar of agate system, is filled into this mixture in the heatproof container, carries out roasting in 3 hours under reducing atmosphere, under 1250 ℃.

After the calcining matter that obtains pulverized, wash, drying, obtain the silicate phosphor (SMS) of above-mentioned composition.Then, according to conventional method, use deuterium lamp to measure the stimulated luminescence spectrum of the fluorophor that obtains as light source.As a comparative example, also measure the stimulated luminescence spectrum of CMS simultaneously.It the results are shown among Fig. 1.

As shown in Figure 1, in the stimulated luminescence spectrum of the CMS that measures, the luminous intensity that obtains near the wave band surpassing 170nm sharply reduces, therefore as can be known the light by wavelength 172nm excite the luminous efficiency that obtains low.

Therefore on the other hand, even near the zone of the SMS that the present invention obtains 170nm also demonstrates high luminous intensity, and this luminous intensity is more much higher than CMS, and the exciting of light by wavelength 172nm can obtain high luminous efficiency as can be known.At this moment, even near the wave band as can be known 147nm, SMS also demonstrate with CMS with contour luminosity.

Secondly, according to identical method, synthesize 4 kinds of SMS of change Eu ratio of components.

The chemical formula of 4 kinds of fluorophor that synthesized is respectively, Sr _2.995MgSi ₂O ₈: Eu _0.005, Sr _2.99MgSi ₂O ₈: Eu _0.01, Sr _2.95MgSi ₂O ₈: Eu _0.05, Sr _2.90MgSi ₂O ₈: Eu _0.10

When synthetic, for Sr _2.995MgSi ₂O ₈: Eu _0.005, make SrCO as raw material ₃Amount is 4.421g (29.95mmol) and Eu ₂O ₃Amount is 0.0088g (0.025mmol); For Sr _2.99MgSi ₂O ₈: Eu _0.01, make same SrCO as raw material ₃Amount is 4.414g (29.90mmol) and Eu ₂O ₃Amount is 0.0176g (0.050mmol); For Sr _2.95MgSi ₂O ₈: Eu _0.05, make same SrCO as raw material ₃Amount is 4.355g (29.50mmol) and Eu ₂O ₃Amount is 0.0880g (0.25mmol); For Sr _2.90MgSi ₂O ₈: Eu _0.10, make same SrCO as raw material ₃Amount is 4.281g (29.00mmol) and Eu ₂O ₃In addition amount, synthesizes according to method same as described above for 0.1760g (0.50mmol), obtains desirable fluorophor.

The fluorophor that use obtains is estimated luminosity.Evaluation is with CMS control sample as a comparison, according to estimating as the relative luminosity (being expressed as several times) that obtained in 1 o'clock with the luminosity of CMS under the 172nm excited by vacuum ultraviolet.

Fig. 3 is the curve chart that the relation of Eu ratio of components and relative brightness is shown.

Evaluation result is summarized among Fig. 3, and any fluorophor all demonstrates more than 3 times of brightness that are equivalent to CMS, demonstrates the brightness that is significantly higher than CMS under the 172nm shooting condition.

And as can be known, surpass 0.005 and increase to 0.01 by making the Eu ratio of components, and can be so that the brightness under the 172nm shooting condition improves more significantly, in addition,, brightness is reduced significantly if make the Eu ratio of components above 0.05 and increase to 0.1.Therefore, as can be known in order to obtain high significantly brightness, wish that the Eu ratio of components is 0.01～0.05.

Should illustrate, when using Sr _2.98MgSi ₂O ₈: Eu _0.02When estimating the luminosity under the 146nm excited by vacuum ultraviolet, demonstrate 1.22 times the high brightness of brightness of the CMS of the comparative example that is equivalent to estimate under the same conditions.

According to the above fact, as can be known in the situation that SMS is used for using the plasma display panel (PDP) that contains the discharge gas that Xe forms since under the exciting of the light of wavelength 146nm and 172nm, can obtain high luminous, therefore, Xe ₂Molecular ray also can utilize expeditiously, thereby can realize the PDP device of high brightness.

And then as can be known owing to be applicable to the technology of so-called " PDP corresponding with high xenonization " well, in this technology, the ratio of components that uses Xe for example more preferably uses according to utilizing Xe energetically at the discharge gas more than 6% ₂The ratio of components of molecular ray contains xenon (Xe) gas and the discharge gas that constitutes in the amount more than 10%, therefore, even if under the situation of the PDP of the discharge gas that uses high xenonization, also can constitute and a kind ofly compare with the situation of using CMS, have the more light-emitting device of high brightness.

(2) manufacturing of plasma display panel (PDP):

Secondly, use above-mentioned silicate phosphor Sr _2.98MgSi ₂O ₈: Eu _0.02Make the surface discharge type plasma display screen with said structure (PDP) of the light-emitting device that in Fig. 2, has illustrated as the blue emitting phophor that constitutes blue phosphor layers.

PDP as present embodiment, behind the dielectric layer 8 that forms the address electrode 9 that constitutes by silver etc. overleaf on the substrate 6, constitutes by the glass based material, the next door material that thick film screen printing is made of the same glass based material, use sandblast mask (Block ラ ス ト マ ス Network), remove sandblast (Block ラ ス ト), form next door 7 thus.

Secondly, on this next door,, in turn form each luminescent coating of red, green, blue by band (ス ト ラ イ プ) shape according to the form that covers the groove face between the next door.

Herein, each luminescent coating 10 forms as follows, promptly, corresponding with red, green, blue, making red fluorophor particle is that 40 weight portions (carrier 60 weight portions), green luminophore particle are that 35 weight portions (carrier 65 weight portions), blue fluorophor particle are 35 weight portions (carrier 65 weight portions), mix with carrier respectively, make phosphor paste, after adopting silk screen print method to be coated with this phosphor paste, carry out the evaporation and the organic burning of volatile ingredient in the phosphor paste by dry and calcining process and remove, be equipped with luminescent coating thereby form.Should illustrate that the luminescent coating that uses in the present embodiment is that central particle diameter by particle size distribution is that each fluorophor particle of 3 μ m constitutes.

In addition, for each fluorescent material beyond the blueness, red fluorophor is (Y, Gd) BO ₃: Eu fluorophor and Y ₂O ₃: the Eu fluorophor is by 1: 1 mixture of mixing ratio, and green luminophore is Zn ₂SiO ₄: the Mn fluorophor.

Secondly, will form show electrode 2, bus (バ ス) electrode 3, dielectric layer 4, the front substrate 1 of protective layer 5, the not shown frit encapsulation of back substrate 6 usefulness, will inject discharge gas after the vacuum exhaust in the display screen, encapsulation.This discharge gas be a kind of be that 10% amount contains the gas that xenon (Xe) gas constitutes by ratio of components.Said PDP in the present embodiment, it is of a size of 3 types, and the spacing of each pixel is 1000 μ m * 1000 μ m.

Secondly, use a kind of PDP that obtains as blue emitting phophor with the above-mentioned silicate phosphor of first embodiment of the invention to make plasma display apparatus as display unit.

(3) image display device of use plasma display panel (PDP):

Fig. 4 is a block diagram, wherein show an example of the image display system of the plasma scope display unit that has in the first embodiment of the invention, the plasma display panel (PDP) (PDP) that said display unit uses the silicate phosphor of a kind of above-mentioned europium of use (divalent) activation to constitute as blue emitting phophor.

Plasma scope display unit 102 in the present embodiment, by plasma display panel (PDP) 100 and the drive circuit 101 that is used to drive this plasma display screen constitute.In addition, by plasma scope display unit 102, be accompanied by reflection source (image information signal) 103 composing images display unit 104 together, wherein, the signal that drive circuit 101 receives from the display frame in reflection source 103, convert thereof into drive signal, thereby drive plasma display panel (PDP) 100.

This plasma display equipment 102 be high brightness and have the long-life.In addition, among this embodiment, about red and green fluorophor, though not shown detailed result of study, even each fluorophor of forming shown below also can similarly be made PDP.

In the red fluorophor, can contain (Y, Gd) BO ₃: Eu, (Y, Gd) ₂O ₃: Eu and (Y, Gd) (P, V) O ₄: the fluorophor that any among the Eu is above.In addition, green luminophore can contain 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 that select among the Tb.And then, also can be used in combination with unshowned herein fluorophor.

＜embodiment 2 〉

In order to make the plasma display panel (PDP) of second embodiment that relates among the present invention, at first carry out synthetic as the fluorophor of component parts.

Synthetic fluorophor be Mg composition in a kind of the composition than the more slightly silicate phosphor (SMS) of stoichiometric proportion (situation of b=1 in the general formula), chemical formula is Sr _2.97Mg _1.01Si ₂O ₈: Eu _0.03Should illustrate, because the Mg composition is more more than stoichiometric proportion, therefore actual chemical formula and above-mentioned some differences are arranged, in fact the ratio of components of Sr etc. will lack.

Synthesize and carry out as described below: take by weighing SrCO respectively as raw material ₃4.385g (29.70mmol), MgCO ₃0.972g (10.10mmol), SiO ₂1.202g (20.00mmol), Eu ₂O ₃0.0528g (0.15mmol) and as the NH of flux ₄Br 0.392g (4.00mmol) after fully mixing in the mortar of agate system, is filled into this mixture in the heatproof container, under reducing atmosphere, carries out roasting in 3 hours under 1250 ℃.

After the calcining matter that obtains is pulverized, wash, drying, obtain the silicate phosphor (SMS) of above-mentioned composition.In addition, estimate the luminosity of the fluorophor that obtains.Evaluation is the Sr that satisfies stoichiometric proportion with the Mg composition _2.97MgSi ₂O ₈: Eu _0.03(SMS) control sample is as a comparison estimated as the relative luminosity (being expressed as several times) that obtained in 1 o'clock according to the luminosity under the 172nm excited by vacuum ultraviolet.

Evaluation result shows that the fluorophor that obtains demonstrates 1.16 times brightness with respect to the comparison other sample.Therefore, under the 172nm shooting condition, demonstrate high brightness as can be known.At this moment, with the present invention in first embodiment in employed 5 kinds of fluorophor Sr _2.98MgSi ₂O ₈: Eu _0.02, Sr _2.995MgSi ₂O ₈: Eu _0.005, Sr _2.99MgSi ₂O ₈: Eu _0.01, Sr _2.95MgSi ₂O ₈: Eu _0.05And Sr _2.90MgSi ₂O ₈: Eu _0.10Carry out brightness ratio, it is high that any fluorophor of brightness ratio is all wanted.

Therefore, be used for using the situation of the plasma display panel (PDP) of the discharge gas that contains the Xe composition as can be known at the silicate phosphor SMS of the composition that above-mentioned Mg composition is more more slightly than stoichiometric proportion, since under the exciting of the light of wavelength 172nm, can obtain high luminous efficiency, therefore, Xe ₂Molecular ray also can utilize expeditiously, thereby can make the PDP device of high brightness.

And then owing to be applicable to the technology of so-called " PDP corresponding with high xenonization " well, in this technology, for example using, ratio of components more preferably uses according to utilizing Xe energetically at the discharge gas more than 6% as can be known ₂The ratio of components of molecular ray contains xenon (Xe) gas and the discharge gas that constitutes in the amount more than 10%, therefore, even if under the situation of the PDP of the discharge gas that uses high xenonization, also can constitute a kind of comparing and have the more light-emitting device of high brightness with CMS.

Secondly, Mg composition silicate phosphor (SMS) and the chemical formula more more slightly than stoichiometric proportion (being equivalent to b=1 in the general formula) in synthetic a kind of the composition is Sr _2.97Mg _1.1Si ₂O ₈: Eu _0.03SMS.Except using MgCO ₃1.058g similarly synthesize (11.0mmol) in addition, with above-mentioned.

The fluorophor that use obtains is estimated luminosity.Evaluation is that the Mg composition is satisfied the stoichiometric proportion Sr of (being equivalent to b=1 in the general formula) _2.97MgSi ₂O ₈: Eu _0.03(SMS) control sample is as a comparison estimated as the relative luminosity (being expressed as several times) that obtained in 1 o'clock according to the luminosity under the 172nm excited by vacuum ultraviolet.Evaluation result shows that the fluorophor that obtains demonstrates 1.03 times brightness with respect to the comparison other sample.Therefore, under the 172nm shooting condition, demonstrate high brightness as can be known.

Secondly, under the Mg composition is the condition of 1.5 times (being equivalent to b=1.5 in the general formula) of stoichiometric proportion, synthesize, synthesize the Mg composition silicate phosphor (SMS) more much higher in a kind of the composition than stoichiometric proportion.Except using MgCO ₃1.443g similarly synthesize (15.0mmol) in addition, with above-mentioned.Estimate equally, the fluorophor that obtains demonstrates equal brightness with respect to the comparison other sample.

According to the above fact,, wish that the Mg composition is more more slightly than stoichiometric proportion, but be less than 1.5 times as can be known in order to improve the luminosity of the SMS under the 172nm excited by vacuum ultraviolet.Therefore, Mg composition silicate phosphor (SMS) Sr more more slightly in a kind of composition of use than stoichiometric proportion _2.97Mg _1.01Si ₂O ₈: Eu _0.03, similarly make plasma display panel (PDP) (PDP) as light-emitting device with first embodiment among the present invention.This plasma display equipment be high brightness and have the long-life.

＜embodiment 3 〉

In order to make the plasma display panel (PDP) of the 3rd embodiment that relates among the present invention, at first carry out synthetic as the fluorophor of component parts.Synthetic fluorophor is the silicate phosphor (SMS) that the Si composition in a kind of the composition is Duoed than stoichiometric proportion (being equivalent to c=1 in the general formula), and chemical formula is Sr _2.99MgSi _2.1O _8.2: Eu _0.01Should illustrate that because the Si composition is more than stoichiometric proportion, therefore, actual chemical formula has some differently with above-mentioned, the ratio of components of Sr, Mg etc. is smaller actually.

Synthesize and carry out as described below: take by weighing SrCO respectively as raw material ₃4.414g (29.90mmol), MgCO ₃0.962g (10.00mmol), SiO ₂1.262g (21.00mmol), Eu ₂O ₃0.0176g (0.050mmol) and as the NH of flux ₄Br 0.392g (4.00mmol) after fully mixing in the mortar of agate system, is filled into this mixture in the heatproof container, carries out roasting in 3 hours under reducing atmosphere, under 1250 ℃.

After the calcining matter that obtains pulverized, wash, drying, obtain the silicate phosphor (SMS) of above-mentioned composition.And then, the luminosity of the fluorophor that evaluation obtains.Evaluation is that a kind of Si composition is satisfied the stoichiometric proportion Sr of (being equivalent to c=1 in the general formula) _2.99MgSi ₂O ₈: Eu _0.01(SMS) control sample is as a comparison estimated as the relative luminosity (being expressed as several times) that obtained in 1 o'clock according to the luminosity under the 172nm excited by vacuum ultraviolet.

Evaluation result shows that the fluorophor that obtains demonstrates 1.20 times brightness with respect to the comparison other sample.Therefore, under the 172nm shooting condition, demonstrate high brightness as can be known.Therefore, be used for using the situation of the plasma display panel (PDP) of the discharge gas that contains the Xe composition as can be known at the silicate phosphor SMS that above-mentioned Si composition is more more slightly than stoichiometric proportion, since under the exciting of the light of wavelength 172nm, can obtain high luminous efficiency, therefore, Xe ₂Molecular ray also can utilize expeditiously, thereby can realize the PDP device of high brightness.

And then as can be known owing to be applicable to the technology of so-called " PDP corresponding with high xenonization " well, in this technology, the ratio of components that uses xenon (Xe) for example more preferably uses according to utilizing Xe energetically at the discharge gas more than 6% ₂The ratio of components of molecular ray contains xenon (Xe) gas and the discharge gas that constitutes in the amount more than 10%, therefore, even under the situation of the PDP of the discharge gas that uses high xenonization, also can constitute and a kind ofly compare with CMS, has the more light-emitting device of high brightness.

According to the above fact,, wish that the Si composition is more more slightly than stoichiometric proportion as can be known in order to improve the luminosity of the SMS under the 172nm excited by vacuum ultraviolet.Therefore, Si composition silicate phosphor (SMS) Sr more more slightly in a kind of composition of use than stoichiometric proportion _2.99MgSi _2.1O _8.2: Eu _0.01, similarly make plasma display panel (PDP) (PDP) as light-emitting device with first embodiment among the present invention.This plasma display equipment be high brightness and have the long-life.

＜embodiment 4 〉

In order to make the plasma display panel (PDP) of the 4th embodiment that relates among the present invention, at first carry out synthetic as the fluorophor of component parts.At first the chemical formula of He Cheng fluorophor is (Sr _0.9Ba _0.1) _2.97MgSi ₂O ₈: Eu _0.03

Synthesize and carry out as described below:, take by weighing SrCO respectively as raw material ₃3.946g (26.73mmol), BaCO ₃0.586g (2.97mmol), MgCO ₃0.962g (10.00mmol), SiO ₂1.202g (20.00mmol), Eu ₂O ₃0.0528g (0.15mmol) and as the NH of flux ₄Br 0.392g (4.00mmol) after fully mixing in the mortar of agate system, is filled into this mixture in the heatproof container, carries out roasting in 3 hours under reducing atmosphere, under 1250 ℃.

After the calcining matter that obtains pulverized, wash, drying, obtain the silicate phosphor (hereinafter referred to as B-SMS) of above-mentioned composition.

Similarly make the amount x of the Ba of a part of replacing Sr change to 0.2,0.25,0.3,0.4 and 0.5, synthesize (Sr _0.8Ba _0.2) _2.97MgSi ₂O ₈: Eu _0.03, (Sr _0.75Ba _0.25) _2.97MgSi ₂O ₈: Eu _0.03, (Sr _0.7Ba _0.3) _2.97MgSi ₂O ₈: Eu _0.03, (Sr _0.6Ba _0.4) _2.97MgSi ₂O ₈: Eu _0.03And (Sr _0.5Ba _0.5) _2.97MgSi ₂O ₈: Eu _0.03

For (Sr _0.8Ba _0.2) _2.97MgSi ₂O ₈: Eu _0.03, make SrCO ₃Be 3.508g (23.76mmol), BaCO ₃Be 1.172g (5.94mmol); In addition, for (Sr _0.75Ba _0.25) _2.97MgSi ₂O ₈: Eu _0.03, make SrCO ₃Be 3.288g (22.28mmol), BaCO ₃Be 1.465g (7.43mmol); In addition, for (Sr _0.7Ba _0.3) _2.97MgSi ₂O ₈: Eu _0.03, make SrCO ₃Be 3.069g (20.79mmol), BaCO ₃Be 1.758g (8.91mmol); In addition, for (Sr _0.6Ba _0.4) _2.97MgSi ₂O ₈: Eu _0.03, make SrCO ₃Be 2.631g (17.82mmol), BaCO ₃Be 2.344g (11.88mmol); In addition, for (Sr _0.5Ba _0.5) _2.97MgSi ₂O ₈: Eu _0.03, make SrCO ₃Be 2.192g (14.85mmol), BaCO ₃Be 2.930g (14.85mmol), in addition, adopt method same as described above, obtain desirable fluorophor.

The fluorophor group that use obtains in order to estimate the colorimetric purity of the light that sends under the 172nm excited by vacuum ultraviolet, is estimated the X of the light that sends that obtains, the y value in the Y chromatic diagram.Evaluation is with CMS control sample as a comparison, relatively the y value of the light that sends under the 172nm excited by vacuum ultraviolet.

Its result as can be known, with respect to y value=0.108 of CMS, at (Sr _0.9Ba _0.1) _2.97MgSi ₂O ₈: Eu _0.03In, y value=0.0862; At (Sr _0.8Ba _0.2) _2.97MgSi ₂O ₈: Eu _0.03In, y value=0.0702; At (Sr _0.75Ba _0.25) _2.97MgSi ₂O ₈: Eu _0.03In, y value=0.0566; At (Sr _0.7Ba _0.3) _2.97MgSi ₂O ₈: Eu _0.03In, y value=0.0448; At (Sr _0.6Ba _0.4) _2.97MgSi ₂O ₈: Eu _0.03In, y value=0.0311; At (Sr _0.5Ba _0.5) _2.97MgSi ₂O ₈: Eu _0.03In, y value=0.0279.

Secondly, use the fluorophor group that obtains, estimate the luminosity under the 172nm excited by vacuum ultraviolet.Use CMS as the comparison other sample of estimating.Evaluation is with CMS control sample as a comparison, according to estimating as the relative luminosity (being expressed as the value of several times) that obtained in 1 o'clock with the luminosity of CMS under the 172nm excited by vacuum ultraviolet.

Fig. 5 is the curve chart that the relation of Ba ratio of components and relative brightness and y value is shown.The evaluation result of evaluation result and y value is summarized among Fig. 5 jointly, as can be known at (Sr _0.9Ba _0.1) _2.97MgSi ₂O ₈: Eu _0.03In be 4.1 times, at (Sr _0.8Ba _0.2) _2.97MgSi ₂O ₈: Eu _0.03In be 3.7 times, at (Sr _0.75Ba _0.25) _2.97MgSi ₂O ₈: Eu _0.03In be 3.0 times, at (Sr _0.7Ba _0.3) _2.97MgSi ₂O ₈: Eu _0.03In be 2.29 times, at (Sr _0.6Ba _0.4) _2.97MgSi ₂O ₈: Eu _0.03In be 1.12 times, at (Sr _0.5Ba _0.5) _2.97MgSi ₂O ₈: Eu _0.03In be equal brightness.

In sum, the colorimetric purity of the silicate phosphor (B-SMS) in above-mentioned as can be known synthesizing is all good than CMS.And the ratio of components of Ba is below 50% with respect to Sr as can be known, can reach the high luminosity more than the CMS under the excited by vacuum ultraviolet of 172nm.And the ratio of components of Ba is a less than 50% with respect to Sr as can be known, and the luminosity under the excited by vacuum ultraviolet of 172nm is higher than CMS.

Therefore, as can be known preferably the ratio of components of Ba with respect to the fluorophor of Sr at the composition below 50%.And the ratio of components that is more preferably Ba as can be known is with respect to the fluorophor of Sr at the composition of less than 50%.

And, as can be known particularly at the ratio of components of Ba with respect to Sr more than 10% and be less than in the said fluorophor of the embodiment of the invention of 20% ratio of components, under the 172nm excited by vacuum ultraviolet, can obtain very high luminosity, and, in the situation of considering light characteristic, this fluorophor is more preferred as can be known.

In addition, in the main situation of considering the colorimetric purity characteristic, surpass with respect to Sr in the fluorophor of composition of 20% amount at the ratio of components of Ba, the y value can realize high colorimetric purity less than 0.07, thereby can seek to take into account high-caliber two aspects of brightness and colorimetric purity, as shown in Figure 5 the ratio of components of Ba with respect to Sr in the fluorophor of the composition more than 23%, the y value can realize higher levels of colorimetric purity, thereby can obtain the fluorophor of the higher levels of characteristics of luminescence less than about 0.06.

Therefore, as can be known in the main situation of considering light characteristic, preferably the ratio of components of Ba with respect to Sr more than 10% and be less than the fluorophor of 20% ratio of components, particularly in the situation of considering the colorimetric purity characteristic, preferably the Ba ratio of components below 50% (in/Sr) the scope, and surpass 20% Ba ratio of components (/Sr), be more preferably the Ba ratio of components more than 23% (/Sr).

And, as can be known in the situation of considering luminous efficiency, can adopt easy method, just will calculate resulting value, by estimating this value as the light-emitting phosphor brightness of evaluation result y value divided by fluorophor, the ratio of components of Ba has high luminous efficiency with respect to Sr at the fluorophor of the composition below 40% as can be known, therefore be preferred, and have higher luminous efficiency at the fluorophor of the composition below 30%, therefore more preferred.

Therefore, preferred as can be known Ba ratio of components can realize having the fluorophor of the characteristics of luminescence like this 10% or more and be less than 20% compositing area or Ba ratio of components above 20% amount and in the zone below 40%.And, as can be known more preferably, at the Ba ratio of components more than 10% and be less than 20% compositing area or Ba ratio of components and surpass 20% amount and in the compositing area below 30%, can realize the fluorophor of the higher characteristics of luminescence.

In addition, as can be known when using (Sr _0.8Ba _0.2) _2.97MgSi ₂O ₈: Eu _0.03, when estimating the luminosity under the 146nm excited by vacuum ultraviolet, demonstrate the equal brightness of brightness with the CMS that estimates under the same conditions.

According to the above fact, as can be known in the situation that above-mentioned synthetic this silicate phosphor (B-SMS) is used to use the plasma display panel (PDP) that contains the discharge gas that Xe forms, since under the exciting of the light of wavelength 172nm, can obtain high luminous efficiency, therefore, Xe ₂Molecular ray also can utilize expeditiously, thereby can realize the PDP device of high brightness.

And then owing to be applicable to the technology of so-called " PDP corresponding with high xenonization " well, in this technology, for example using, ratio of components more preferably uses according to utilizing Xe energetically at the discharge gas more than 6% as can be known ₂The ratio of components of molecular ray contains xenon (Xe) gas and the discharge gas that constitutes in the amount more than 10%, therefore, even under the situation of the PDP of the discharge gas that uses high xenonization, also can constitute and a kind ofly compare with CMS, has the more light-emitting device of high brightness.

Secondly, use (Sr _0.75Ba _0.25) _2.97MgSi ₂O ₈: Eu _0.03(B-SMS), with the present invention in first embodiment similarly make plasma display panel (PDP) (PDP) as light-emitting device.This plasma display equipment be high brightness and show that look clear, and have the long-life.

＜embodiment 5 〉

As blue emitting phophor, use employed (Sr in the light-emitting device of fourth embodiment of the invention _0.75Ba _0.25) _2.97MgSi ₂O ₈: Eu _0.03(being called B-SMS),, make rare gas { inclosure xenon (Xe) gas } discharge white fluorescent lamp as other light-emitting devices as the 5th embodiment.

Fig. 6 illustrates the structure of this rare gas { inclosure xenon } discharge white fluorescent lamp,, uses employed (Sr in the light-emitting device of fourth embodiment of the invention that is _0.75Ba _0.25) _2.97MgSi ₂O ₈: Eu _0.03(B-SMS) cross-sectional view of the structure of the light-emitting device of the 5th embodiment that the present invention relates to that constitutes.

As the rare gas (xenon) of the light-emitting device that relates among the present invention discharge white fluorescent lamp 110, be by being constituted by the glass tube 111 of airtight protection, the xenon (not shown) that is enclosed in glass tube 111 inside, the fluorophor 112 that is coated on glass tube 111 inner faces, the electrode 113 that is arranged on glass tube 111 two ends.And, utilize two electric discharge between electrodes, can make electric energy change the ultraviolet radiation into by using the xenon as discharge gas, this ultraviolet radiation excites luminescent coating 112 on the glass tube walls, promptly constitutes the fluorophor of luminescent coating, thereby makes luminescent coating 112 send visible light.

Should illustrate, above-mentioned luminescent coating 112 is in the present invention the said silicate phosphor (blue emitting phophor), can also use divalent manganese activated zinc silicate fluorophor as green-emitting phosphor, perhaps in red-emitting phosphors, use 3 valency europiums activation acidifying yttrium gadolinium fluorophor, make rare gas (xenon) the discharge white fluorescent lamp 110 that is commonly called 3 wavelength fluorescent lamps.This lamp 110 be high-luminous-efficiency and have the long-life.

In addition, by with the lamp of present embodiment as back of the body irradiation, combine with the LCDs of other preparation, made liquid crystal indicator 120 as display unit.

Fig. 7 uses the exploded perspective view of the structure of the liquid crystal indicator that rare gas (inclosure xenon) the discharge white fluorescent lamp of the 5th embodiment constitutes for expression, and employed (Sr in the light-emitting device of said white fluorescent lamp the 4th embodiment that to be the application of the invention relate to _0.75Ba _0.25) _2.97MgSi ₂O ₈: Eu _0.03(B-SMS) make.

Use rare gas (inclosure xenon) the discharge white fluorescent lamp 110 of several present embodiments, be configured in the basket 123.Require in the liquid crystal indicator of high brightness in LCD TV etc., adopt the mode of several fluorescent lamp plane earth alignment arrangements more, be the mode of (down straight) under the what is called.

Between basket 123 and fluorescent lamp 110, set and be used for utilizing expeditiously the reflection of light plate 124 that injects to basket 123 sides by fluorescent lamp 110.In addition, in order to distribute configuration diffuser plate 126 directly over fluorescent lamp 110 in the face that reduces the brightness in the liquid crystal indicator.And then, in order to improve the brightness of liquid crystal indicator 120, set prismatic film (プ リ ズ system シ one ト) 127A, 127B, reflection polarizing plate 128.

Inverter (イ Application バ one ) 129 is connected on the fluorescent lamp 110, so as need to fluorescent lamp 110 light a lamp control situation, can control by the driving of inverter and light a lamp.Should illustrate, below rare gas (xenon) discharge white fluorescent lamp 110, basket 123, reflecting plate 124, diffuser plate 126, prismatic film 127A, 127B, reflection polarizing plate 128, inverter 129 are generically and collectively referred to as back light unit 121.

Directly over back light unit 121, adjust the transit dose of the light that sends by back light unit 121, each pixel arrangement is a kind of to possess the LCDs 122 that light is divided into the colour filter of redness, green, blue light.In LCDs 122,, just can carry out the color demonstration by the TFT that controls on each pixel for each pixel is provided with electrode and thin-film transistor (TFT).Promptly, its constituted mode is, to each pixel service voltage, by applying the liquid crystal generation change in orientation that this voltage makes each pixel, the refractive index of each pixel is changed, adjust transit dose whereby, the light of this amount of having adjusted is carried out beam split with colour filter, show thereby carry out colour from the light of back light unit 121.

In the present embodiment,, use the transverse electric field mode, be the LCDs of so-called IPS pattern as LCDs.But, also can use the LCDs of the LCDs, for example TN pattern, VA pattern, ocb mode etc. of other patterns.

At last, back light unit 121 and LCDs 122 is overlapping, cover with basket 130, obtain liquid crystal indicator thus.In the present embodiment said liquid crystal indicator be high brightness, be can clear demonstration display unit.

＜embodiment 6 〉

Use is employed (Sr in the light-emitting device of fourth embodiment of the invention _0.75Ba _0.25) _2.97MgSi ₂O ₈: Eu _0.03As blue emitting phophor, make the white fluorescent lamp of plane rare gas (inclosure xenon) discharge.

For the fluorophor beyond the blue emitting phophor, use divalent manganese activated zinc silicate fluorophor as green-emitting phosphor, perhaps use 3 valency europiums activation acidifying yttrium gadolinium fluorophor as red-emitting phosphors.

This lamp be high brightness and have the long-life.In addition, make up as back of the body irradiation and the LCDs of preparing in addition, can be made as the clear liquid crystal indicator of display unit by lamp with present embodiment.

＜embodiment 7 〉

In order to make the plasma display panel (PDP) of the 7th embodiment that the present invention relates to, at first carry out synthetic as the fluorophor of component parts.At first the chemical formula of He Cheng fluorophor is (Sr _0.9Ca _0.1) _2.97MgSi ₂O ₈: Eu _0.03

The synthetic of this fluorophor carries out as described below: as raw material, take by weighing SrCO respectively ₃3.946g (26.73mmol), CaCO ₃0.297g (2.97mmol), MgCO ₃0.962g (10.00mmol), SiO ₂1.202g (20.00mmol), Eu ₂O ₃0.0528g (0.15mmol) and as the NH of flux ₄Br 0.392g (4.00mmol) after fully mixing in the mortar of agate system, is filled into this mixture in the heatproof container, carries out roasting in 3 hours under reducing atmosphere, under 1250 ℃.

After the calcining matter that obtained pulverized, wash, drying, obtain the silicate phosphor (hereinafter referred to as C-SMS) of above-mentioned composition.Use the fluorophor C-SMS that is obtained, estimate luminosity.Evaluation is with CMS control sample as a comparison, obtains relative luminosity (being expressed as the value of several times) according to the luminosity under the 172nm excited by vacuum ultraviolet as 1 o'clock and estimates.

Evaluation result shows that the fluorophor that obtains demonstrates 5.30 times brightness with respect to the comparison other sample.Therefore, under the 172nm shooting condition, demonstrate high brightness as can be known.At this moment, with the fluorophor Sr that in first embodiment of the invention, uses _2.98MgSi ₂O ₈: Eu _0.02, Sr _2.995MgSi ₂O ₈: Eu _0.005, Sr _2.99MgSi ₂O ₈: Eu _0.01, Sr _2.95MgSi ₂O ₈: Eu _0.05, Sr _2.90MgSi ₂O ₈: Eu _0.10Carry out brightness ratio, any fluorophor wherein all is a high brightness.

Therefore, as can be known with above-mentioned basic SMS (Sr _2.97MgSi ₂O ₈: Eu _0.03) the part of Sr composition replace with Ca and the C-SMS that obtains is used to use the situation of the plasma display panel (PDP) that contains the discharge gas that Xe forms, can obtain high luminous efficiency down the exciting of the light of wavelength 172nm, so can utilize Xe expeditiously ₂Molecular ray, thus can realize the PDP device of high brightness.

And then, as can be known owing to be applicable to the technology of so-called " PDP corresponding " well, in this technology, for example use the xenon ratio of components more than 6%, more preferably use according to utilizing Xe energetically with high xenonization ₂The ratio of components of molecular ray contains xenon (Xe) gas and the discharge gas that constitutes in the amount more than 10%, therefore, even under the situation of the PDP of the discharge gas that uses high xenonization, also can constitute a kind of light-emitting device of comparing with CMS with high brightness.

Secondly, adopt method same as described above, synthesize (Sr _0.8Ca _0.2) _2.97MgSi ₂O ₈: Eu _0.03(Sr _0.7Ca _0.3) _2.97MgSi ₂O ₈: Eu _0.03

For (Sr _0.8Ca _0.2) _2.97MgSi ₂O ₈: Eu _0.03, make SrCO ₃Be 3.508g (23.76mmol), CaCO ₃For 0.595g (5.94mmol) and for (Sr _0.7Ca _0.3) _2.97MgSi ₂O ₈: Eu _0.03, make SrCO ₃Be 3.069g (20.79mmol), CaCO ₃Be 0.892g (8.91mmol), in addition, adopt method same as described above, obtain desirable fluorophor.

The fluorophor group that use obtains in order to estimate the colorimetric purity of the light that sends under the 172nm excited by vacuum ultraviolet, estimates the X of the light that sends that obtains, the y value in the Y chromatic diagram.Evaluation result shows, for (Sr _0.8Ca _0.2) _2.97MgSi ₂O ₈: Eu _0.03, the y value is below the CMS, for (Sr _0.7Ca _0.3) _2.97MgSi ₂O ₈: Eu _0.03, the y value is greater than CMS, though be high brightness, colorimetric purity is poorer than CMS.

According to the above fact, with above-mentioned basic SMS (Sr _2.97MgSi ₂O ₈: Eu _0.03) the C-SMS of a part with Ca displacement of Sr composition in, the replacement amount of Ca is preferably below 0.2 of Sr (below 20%).

Secondly, as blue emitting phophor, use (Sr _0.90Ca _0.10) _2.97MgSi ₂O ₈: Eu _0.03(C-SMS), except using this C-SMS, make with the present invention in the plasma display panel (PDP) (PDP) of light-emitting device of the first embodiment same structure that relates to.This plasma display equipment has high brightness and shows that look bright-coloured, has the long-life.

＜embodiment 8 〉

As blue emitting phophor, use employed (Sr in the light-emitting device of seventh embodiment of the invention _0.90Ca _0.10) _2.97MgSi ₂O ₈: Eu _0.03(C-SMS), except using this C-SMS, making and fifth embodiment of the invention are with the rare gas in the light-emitting device of spline structure (xenon) discharge white fluorescent lamp.

As the fluorophor beyond the blue emitting phophor, use divalent manganese activated zinc silicate fluorophor as green-emitting phosphor, use 3 valency europiums activation acidifying yttrium gadolinium fluorophor as red-emitting phosphors, make rare gas (xenon) discharge white fluorescent lamp.This lamp is high-luminous-efficiency and has the long-life.

In addition, with the lamp of present embodiment as back of the body irradiation, according to the same formation of above-mentioned the 5th embodiment, by combining, can make bright liquid crystal indicator as display unit with the LCDs of other preparation.

＜embodiment 9 〉

As blue emitting phophor, employed (Sr in the light-emitting device of use seventh embodiment of the invention _0.90Ca _0.10) _2.97MgSi ₂O ₈: Eu _0.03(C-SMS), make plane rare gas (xenon) discharge white fluorescent lamp.

For the fluorophor beyond this blue emitting phophor, use divalent manganese activated zinc silicate fluorophor as green-emitting phosphor, use 3 valency europiums activation acidifying yttrium gadolinium fluorophor as red-emitting phosphors.This lamp is high brightness and has the long-life.

In addition, the lamp of present embodiment as back of the body irradiation, by combining with the LCDs of other preparation, as display unit, can be made bright liquid crystal indicator.

According to the present invention, be based upon the fluorescent material of long-life and high brightness, can stably carry out high performance demonstration, by constituting more large-scale light-emitting device, go for requiring long-term lighting, need the purposes of high brightness and long-life indispensable large-scale home-use flat display apparatus.

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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