JP2008169326A - Vacuum ultraviolet excitation phosphor and plasma display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plasma display device having a green color emitting phosphor having superior color purity. <P>SOLUTION: By constituting a green color phosphor membrane with the use of a green color phosphor of superior color purity and having a composition represented by the formula: Li<SB>5</SB>Zn<SB>8-x</SB>Al<SB>5</SB>(MO<SB>4</SB>)<SB>9</SB>:Mn<SB>x</SB>(wherein M is at least one element of Ge and Si and x is a value in the range of 0.001≤x≤0.5), the plasma display device having superior color purity can be obtained. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a phosphor that emits light by being excited by ultraviolet rays in the vacuum ultraviolet region, and a plasma display (PDP) apparatus using the phosphor.

  As described in Patent Document 1, the phosphor emits light by excitation energy such as an electron beam, X-rays, and ultraviolet rays. The light emission phenomenon of the phosphor is widely used as various display devices and light emitting devices. For example, it is used in fluorescent lamps and recently in plasma display devices (PDP (Plasma Display Panel) devices). In a plasma display (PDP) device, a phosphor emits light when excited by a vacuum ultraviolet ray having a wavelength of 200 nm or less generated by discharge of a rare gas such as xenon, helium, or neon. The plasma display (PDP) device is a display device using a plasma display panel (PDP) as a light emitting device, and is widely used as a thin large-screen television (TV).

  The plasma display panel (PDP) uses ultraviolet light generated in a negative glow region in a minute discharge space containing a rare gas (when using xenon as a rare gas, vacuum ultraviolet rays in the wavelength regions of 146 nm and 172 nm) as an excitation source. Luminescence in the visible region is obtained by exciting the phosphor in the phosphor layer disposed in the minute discharge space to emit light. In the plasma display (PDP) apparatus, the light emission amount and red, green, and blue colors corresponding to the three primary colors are controlled and used for display. Therefore, the phosphor in the phosphor layer is a very important main constituent member for constituting a plasma display (PDP) device.

  References relating to this type of material and technology include, for example, Japanese Patent Application Laid-Open No. 2004-176010 (Patent Document 2) and “Phosphor Handbook” edited by Phosphors Society of Japan. Non-patent document 1) ”.

The phosphors that form a phosphor layer that emits visible light when excited by vacuum ultraviolet rays as provided in the plasma display panel (PDP) device include red (R), green (G), and blue (B). Phosphors that emit light for each color are used, and white light is obtained by combining the light emission from these three color phosphors. In a conventional plasma display panel (PDP), (Y, Gd) BO ₃ : Eu phosphor as a red light-emitting phosphor, Zn ₂ SiO ₄ : Mn phosphor as a green light-emitting phosphor, and BaMgAl ₁₀ O ₁₇ as a blue light-emitting phosphor. : Eu (BAM) or the like is generally used.

JP-A-52-8993 JP 2004-176010 A “Phosphor Handbook” edited by Phosphors Society of Japan Ohmsha 1987 Chapter III Chapter 7 330-335

  In particular, since a green light-emitting phosphor having high visibility is a phosphor that plays an important role in determining white luminance, it is desired to provide a green light-emitting phosphor that emits light with high luminance and high color purity. Yes.

Currently, as a green light-emitting phosphor for a plasma display panel (PDP), a phosphor that is excited by vacuum ultraviolet rays having a wavelength of 200 nm or less and can obtain light emission with high efficiency is used. Specifically, Zn ₂ SiO ₄ : Mn and YBO ₃ : Tb are well known, and Zn ₂ SiO ₄ : Mn is mainly used among them. However, among the above phosphors, YBO ₃ : Tb has a problem of low brightness and poor color purity. Zn ₂ SiO ₄ : Mn has an excellent feature that the emission luminance is higher than that of the green light-emitting phosphor. However, the color purity of the Zn ₂ SiO ₄ : Mn green light-emitting phosphor is not sufficient, and further improvement in chromaticity characteristics is desired.

  In the above-mentioned Patent Document 1, a manganese (Mn) -activated germanate phosphor was developed as a phosphor applied to a high color rendering fluorescent lamp, a photocopy light source, a cathode ray tube light emitting screen, and the like. Therefore, there is no suggestion of application to a PDP device because the evaluation in the vacuum ultraviolet region has not been studied. New phosphors are desired for use in PDP devices or vacuum ultraviolet excitation.

At the same time, in the technical field of PDP devices, in parallel with the study on improving the performance of phosphor materials, studies are being made to improve the PDP structure for the purpose of increasing the light emission efficiency of PDP devices as high-performance TV devices. Yes. As one of the methods, studies are actively made to increase the composition ratio of Xe gas in a discharge gas containing Ne as a main component and to actively use the generated Xe ₂ molecular beam. In general, studies have been made to achieve such high emission efficiency of the PDP in a composition ratio region larger than the xenon gas composition ratio (about 5%) in the discharge gas. In that case, the green light emitting phosphor in the phosphor layer of the PDP is a Xe ₂ molecular beam that becomes a main phosphor excitation light source when the PDP is made to have a high xenon concentration, in addition to vacuum ultraviolet rays having a wavelength of 146 nm generated by discharge. That is, it is necessary to be a phosphor that is efficiently excited by vacuum ultraviolet light having a wavelength of 172 nm and emits light with high color purity.

  An object of the present invention is to provide a green light-emitting phosphor having better color purity under vacuum ultraviolet excitation. Another object of the present invention is to provide a plasma display device with better color purity by forming a green phosphor film using a green phosphor with better color purity. The above and other objects and novel features of the present invention will become apparent from the description of this specification and attached drawings.

The object of the present invention is achieved by a vacuum ultraviolet ray excited phosphor characterized by having a composition represented by the following general formula (I) and emitting light under vacuum ultraviolet ray excitation.
_{Li 5 Zn 8-x Al 5} (MO 4) 9: Mn x ··· (I)
In the formula (I), M is at least one element of Ge and Si. Further, x is suitably a value in the range of 0.001 ≦ x ≦ 0.5. A more preferable range of x is a range of 0.01 ≦ x ≦ 0.3.

  Another object of the present invention is to provide a pair of substrates opposed to each other with a space therebetween, a partition wall provided between the pair of substrates and formed between the pair of substrates, and the pair of substrates opposed to each other. A pair of electrodes disposed on at least one of the surfaces; a discharge gas sealed in a space formed by the partition walls; and generating ultraviolet rays by a discharge caused by a voltage applied to the electrode pairs; and the pair of the spaces in the space A phosphor layer is formed on at least one of the opposing surface of the substrate and the wall surface of the partition wall and contains a phosphor layer that emits light when excited by the ultraviolet rays. This is achieved by a plasma display device comprising a phosphor represented by the following formula.

In addition, the plasma display device according to the present invention can be used in place of manganese (Mn) -activated zinc silicate phosphor Zn ₂ SiO ₄ : Mn, which has insufficient chromaticity characteristics, or a part of which is mixed and mixed with it. Since the phosphor represented by the general formula (I), which is a green light-emitting phosphor having better color purity, is used, excellent color purity can be achieved.

  Moreover, the plasma display device according to the present invention has good color purity not only under vacuum ultraviolet excitation conditions with a wavelength of 146 nm but also under optical excitation conditions with vacuum ultraviolet radiation with a wavelength of 172 nm, which plays a major role as an excitation source in a high xenon-concentrated PDP. Since a phosphor having a composition represented by the general formula (I) is used, excellent chromaticity characteristics can be achieved.

  Further, the plasma display device according to the present invention has a Xe composition ratio of 10%, for example, in which the Xe composition ratio is 6% or more, more preferably, the 172 nm ultraviolet component intensity ratio is strong with respect to the 146 nm component, in addition to the vacuum ultraviolet excitation condition of wavelength 146 nm. In the high xenon-concentrated PDP using the discharge gas configured to contain the Xe gas in the amount as described above, the color purity is good even under the photoexcitation condition with vacuum ultraviolet light having a wavelength of 172 nm, which plays a major role as an excitation source. Since a phosphor characterized by having a composition represented by the general formula (I) is used, excellent chromaticity characteristics can be achieved.

  ADVANTAGE OF THE INVENTION According to this invention, the green light emission fluorescent substance which was more excellent in color purity under vacuum ultraviolet-ray excitation can be provided. In addition, by forming a green phosphor film using a green phosphor with better color purity, a plasma display device with better color purity can be provided.

  The present inventor has found a green light-emitting Mn-activated germanate phosphor having good color purity under vacuum ultraviolet excitation. By using this phosphor as a green component in the phosphor film, a plasma display device with better color purity could be obtained.

This inventor is Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : Mn _0.03 and Li ₅ Zn _7.95 Al ₅ (examples of Mn-activated germanate phosphors constituting the present invention. SiO ₄ ) ₉ : Mn _0.05 was synthesized. And the light emission characteristic under vacuum ultraviolet-ray excitation was investigated. First, using them, the emission spectrum was measured using a vacuum ultraviolet excimer lamp having a central emission wavelength of 146 nm as a light source according to a conventional method so as to be compared with a conventional Mn-activated zinc silicate phosphor Zn ₂ SiO ₄ : Mn phosphor. did.

FIG. 1 shows [Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : Mn _0.03 and Li ₅ Zn _7.95 Al ₅ (SiO ₄ ) _{9 of} the Mn-activated germanate phosphor constituting the present invention. : Mn _0.05 ] and a conventional phosphor example Zn ₂ SiO ₄ : Mn emission spectrum under a wavelength of 146 nm under vacuum ultraviolet light excitation conditions.

FIG. 2 is a table summarizing the chromaticity point x value and y value in the CIE chromaticity coordinates of the Mn-activated germanate phosphor constituting the present invention and Zn ₂ SiO ₄ : Mn as a conventional phosphor example. .

By examining the results, as shown in FIGS. 1 and 2, the Mn-activated germanate phosphor exhibited good green light emission under the condition of 146 nm vacuum ultraviolet light excitation. In addition, as compared with the emission spectrum of the obtained conventional phosphor Zn ₂ SiO ₄ : Mn, the emission spectrum peak wavelength of each of the Mn-activated germanate phosphors of the present embodiment is shifted to the short wavelength side. I understand that.

As a result, as shown in FIG. 2, the chromaticity point in the CIE chromaticity coordinate indicating the emission color of the phosphor has an x value and a y value of (x, y) in the conventional phosphor Zn ₂ SiO ₄ : Mn, respectively. ) = (0.250, 0.697), whereas the x, y chromaticity value of Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : Mn _0.03 is (x, y) = ( 0.219, 0.714), and the x, y chromaticity value of Li ₅ Zn _7.95 Al ₅ (SiO ₄ ) ₉ : Mn _0.05 is (x, y) = (0.230, 0. 693). The chromaticity coordinates of the NTSC standard green light emitting phosphor are (x, y) = (0.21, 0.71). Mn-activated germanate phosphors phosphor of this embodiment is _Zn 2 _SiO 4: close to the NTSC standard green point than Mn, the conventional phosphor, _Zn 2 _SiO 4: superior to Mn, have high chromaticity characteristics I understand. The CIE chromaticity coordinates shown in FIG. 2 are coordinates relating to green. NTSC is a standard value for color broadcasting. In the CIE chromaticity coordinate x and y values, the green chromaticity coordinate is represented by (x, y) = (0.21, 0.71).

Then, when the emission spectrum was measured in the same manner using a vacuum ultraviolet excimer lamp having a center wavelength of 172 nm as a light source, the emission spectrum peak wavelength of each of the Mn-activated germanate phosphors of the present embodiment is also as follows. It turned out that it shifted to the short wavelength side. As a result, as shown in FIG. 2, the chromaticity point in the CIE chromaticity coordinates indicating the emission color of the phosphor has an x value and a y value in the conventional phosphor Zn ₂ SiO ₄ : Mn (x , Y) = (0.250, 0.697), whereas the x, y chromaticity value of Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : Mn _0.03 is (x, y). = (0.220, 0.707) and the x, y chromaticity value of Li ₅ Zn _7.95 Al ₅ (SiO ₄ ) ₉ : Mn _0.05 is (x, y) = (0.232, 0.692). The chromaticity coordinates of the NTSC standard green light emitting phosphor are (x, y) = (0.21, 0.71). Mn-activated germanate phosphors phosphor phosphor of the present embodiment is _Zn 2 _SiO 4: close to the NTSC standard green point than Mn, the conventional phosphor, _Zn 2 _SiO 4: having a good chromaticity characteristics compared to Mn I understand that.

As a result, the Mn-activated germanate phosphor phosphor according to the present invention has an emission spectrum on a shorter wavelength side when compared with the conventional phosphor Zn ₂ SiO ₄ : Mn when excited with vacuum ultraviolet rays having wavelengths of 146 nm and 172 nm. It has been found that higher color purity is possible.

  With respect to the Mn concentration which is an activator in the Mn-activated germanate phosphor according to the present invention, the amount that can sufficiently exhibit the effect as the luminescence center is set as the lower limit, and the amount that can avoid the decrease in luminous efficiency due to concentration quenching is set. The upper limit. That is, regarding the Mn concentration x, according to the notation of the above formula (I), x indicating the Mn concentration is preferably 0.001 ≦ x ≦ 0.5. A more preferable range of x is a range of 0.01 ≦ x ≦ 0.3.

  Regarding the relationship between the discharge gas composition of the plasma display panel and the ultraviolet component generated by the discharge, it is known that the higher the Xe (xenon) composition ratio, the stronger the ultraviolet component intensity at 172 nm with respect to the 146 nm component. Therefore, when the Mn-activated germanate phosphor according to the present invention is used, good light emission characteristics are obtained in the phosphor by photoexcitation with a wavelength of 172 nm. For example, the Xe composition ratio is more preferably 6% or more. Furthermore, high Xenon-concentrated PDP using a discharge gas composed of Xe gas in an amount of 10% or more of Xe composition in which the intensity of ultraviolet component at 172 nm with respect to 146 nm component becomes strong, and higher color purity is possible. It is.

  Hereinafter, examples corresponding to the best mode for carrying out the present invention will be described. First, a typical phosphor of the present invention is synthesized as follows. As phosphor materials, lithium compounds such as lithium carbonate, zinc compounds such as zinc carbonate, aluminum compounds such as aluminum hydroxide, germanium compounds such as germanium oxide, silicon compounds such as silicon oxide, and manganese such as manganese carbonate are used. These raw materials are weighed and collected in accordance with the composition formula, and mixed sufficiently well by wet or dry methods. This mixture is filled in a heat-resistant container such as a fused alumina crucible and fired. Firing is performed at a temperature around 1000 ° C. in a neutral gas atmosphere such as nitrogen or argon, or in a reducing atmosphere such as a hydrogen-mixed nitrogen gas. The fired product is pulverized, washed with water and dried to obtain the phosphor of the present invention.

  Based on the above, the PDP according to the embodiment of the present invention using the Mn-activated germanate phosphor according to the present invention can be configured as follows. FIG. 3 is an exploded perspective view of the main part showing the structure of the PDP of the general surface discharge type color PDP apparatus according to the present embodiment. A PDP 100 according to an embodiment of the present invention includes a pair of substrates 1 and 6 that are arranged to face each other at a distance, and a substrate 1 and a substrate 6 that are provided on the substrate 6 and overlapped with each other. , A discharge gas (not shown) which is enclosed in a space formed between the pair of substrates 1 and 6 and generates ultraviolet rays by discharge, and the pair of substrates 1 and 6. The electrodes 2 and 9 are disposed on the opposing surfaces of the two.

  The line 3 shown in FIG. 3 is a bus line 3 made of silver or Cu—Cr provided integrally with the electrode 2 to reduce the electrode resistance. The dielectric layers 4 and 8 and the reference numeral 5 are protective films 5 provided for electrode protection. The Mn-activated germanate phosphor according to the present invention forms the phosphor layer 10 on one of the pair of substrates 6 and the surface of the partition wall 7. Then, the Mn-activated germanate phosphor according to the present invention constituting the phosphor layer 10 is excited by vacuum ultraviolet rays having wavelengths of 146 nm and 172 nm generated from the discharge gas by discharge, and is configured to emit visible light. It is characterized by that.

  Here, the manufacturing method and emission characteristics of the vacuum ultraviolet-excited phosphor of the present invention, and each characteristic of the plasma display device including the phosphor will be described in detail. The following examples embody the present invention. This is an example, and does not restrict the present invention.

FIG. 2 shows the composition of the phosphor according to one embodiment of the present invention and the x and y values of CIE chromaticity coordinates. Among these, the phosphor of sample number 1 was synthesized as follows. That is, for the purpose of synthesizing Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : Mn _0.03 , 0.4618 g of lithium carbonate (Li ₂ CO ₃ ), 2.4986 g of zinc carbonate (ZnCO ₃ ), 0.9750 g of aluminum hydroxide [(Al (OH) ₃ )], 2.3537 g of germanium oxide (GeO ₂ ), and 0.0086 g of manganese carbonate (MnCO ₃ ) were weighed out in an agate mortar. Mixed. Thereafter, the mixed raw material was filled in an alumina crucible and fired at 1000 ° C. for 1 hour in a reducing atmosphere. The obtained fired product was pulverized, washed with water, and dried to obtain a phosphor having the above composition.

Next, using a vacuum ultraviolet excimer lamp having a central wavelength of 146 nm as a light source according to a conventional method, the synthesized phosphor Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : Mn _0.03 and Zn ₂ SiO which is an example of a conventional phosphor ₄ : The emission spectrum of Mn was measured. The results are shown in FIG. It was found that the emission spectrum peak wavelength of Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : Mn _0.03 was shifted to the short wavelength side as compared with the conventional phosphor example Zn ₂ SiO ₄ : Mn. As a result, in the conventional phosphor Zn ₂ SiO ₄ : Mn, (x, y) = (0.250, 0.697), whereas Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : The Mn _0.03 x, y chromaticity value is (x, y) = (0.219,0.714), and the chromaticity coordinate of the NTSC standard green light emitting phosphor is (x, y) = Since it is (0.21, 0.71), Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : Mn _0.03 phosphor is closer to the NTSC standard green point than Zn ₂ SiO ₄ : Mn, It was found to be superior to phosphor Zn ₂ SiO ₄ : Mn and to have high chromaticity characteristics.

Similarly, an emission spectrum of the phosphor Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : Mn _0.03 was measured using a vacuum ultraviolet excimer lamp having an emission center wavelength of 172 nm as a light source according to a conventional method. Conventional phosphor Example _Zn 2 _SiO 4: it was found that as compared with Mn is shifted to the short wavelength side. As a result, in the conventional phosphor Zn ₂ SiO ₄ : Mn, (x, y) = (0.250, 0.697), whereas Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : Mn _0.03 x, y chromaticity value is (x, y) = (0.220,0.707), and the chromaticity coordinate of NTSC green light emitting phosphor is (x, y) = (0.21, 0.71), Li ₅ Zn _7.97 Al ₅ (GeO ₄ ) ₉ : Mn _0.03 phosphor is closer to the NTSC reference green point than Zn ₂ SiO ₄ : Mn, It was found to be superior to the conventional phosphor Zn ₂ SiO ₄ : Mn and to have high chromaticity characteristics. Similarly, phosphors of sample numbers 2 to 4 were synthesized. The x and y values of the CIE chromaticity coordinates under vacuum ultraviolet (wavelength 146 nm, 172 nm) excitation of these phosphors showed good values, respectively.

FIG. 4 shows how the x value of the CIE chromaticity coordinate is obtained under the condition of 146 nm wavelength vacuum ultraviolet excitation when the value of Mn concentration x is changed in Li ₅ Zn ₈ -xAl ₅ (GeO ₄ ) ₉ : Mn _x . It is the result of investigating whether it changes. It was found that when the value of the Mn concentration x is 0.001 ≦ x ≦ 0.5, it can be used as a green light emitting phosphor for a plasma display panel. The x value of the CIE chromaticity coordinate of the NTSC standard green point is 0.21, and the x value of the CIE chromaticity coordinate of the conventional phosphor example Zn ₂ SiO ₄ : Mn is 0.25. As can be seen from FIG. 4, when the value of Mn concentration x in the phosphor of the present invention Li ₅ Zn _{8 -x} Al ₅ (GeO ₄ ) ₉ : Mn _x is 0.01 ≦ x ≦ 0.3, the conventional phosphor Zn It was found to be superior to ₂ SiO ₄ : Mn and to have high chromaticity characteristics. _Further, Zn 2 _SiO 4: maintains a value very close to the NTSC standard green point than Mn. Then, when the x value of CIE chromaticity coordinates was measured in the same manner using a vacuum ultraviolet excimer lamp having a center wavelength of 172 nm as a light source, the Mn-activated germanate phosphor of the present embodiment still has high chromaticity characteristics. It was found to have

From the above, when the Mn-activated germanate phosphor according to the present invention is used in a PDP using a discharge gas containing an Xe composition, higher color purity can be achieved by excitation with ultraviolet light having a wavelength of 146 nm and 172 nm. From this, it was found that the Xe ₂ molecular beam by discharge can be used with high efficiency, and a PDP device with more excellent chromaticity characteristics becomes possible.

  Furthermore, the Mn-activated germanate phosphor according to the present invention has an Xe gas content of, for example, an Xe composition ratio of 6% or more, more preferably an Xe composition ratio of 10% or more with a strong 172 nm ultraviolet component intensity ratio to the 146 nm component. It has been found that excellent chromaticity characteristics can be achieved even in a high xenon-concentrated PDP using a discharge gas composed of

A phosphor (sample number 5) partially substituted with Si shown in FIG. 2 was synthesized according to a similar synthesis process. That is, for the purpose of synthesizing Li ₅ Zn _7.95 Al ₅ (SiO ₄ ) ₉ : Mn _0.05 , 0.4618 g of lithium carbonate (Li ₂ CO ₃ ), 2.4923 g of zinc carbonate (ZnCO ₃ ), 0.9750 g of aluminum hydroxide [(Al (OH) ₃ )], 1.3519 g of silicon oxide (SiO ₂ ), and 0.0143 g of manganese carbonate (MnCO ₃ ) were weighed out and fully placed in an agate mortar. Mixed. Thereafter, the mixed raw material was filled in an alumina crucible and fired at 1000 ° C. for 1 hour in a reducing atmosphere. The obtained fired product was pulverized, washed with water, and dried to obtain a phosphor having the above composition. This phosphor was found to have high chromaticity characteristics under excitation with vacuum ultraviolet light at 146 nm and 172 nm.

From the above, when Li ₅ Zn _7.95 Al ₅ (SiO ₄ ) ₉ : Mn _0.05 according to the present invention is used in a PDP using a discharge gas containing a Xe composition, it is excited by ultraviolet light having a wavelength of 146 nm and 172 nm. Since it is possible to achieve higher color purity, it has been found that the Xe ₂ molecular beam by discharge can also be used with high efficiency, and a PDP device with more excellent chromaticity characteristics can be realized.

Furthermore, Li ₅ Zn _7.95 Al ₅ (SiO ₄ ) ₉ : Mn _0.05 according to the present invention has, for example, an Xe composition ratio of 6% or more, more preferably a strong 172 nm ultraviolet component intensity ratio with respect to the 146 nm component. It has been found that excellent chromaticity characteristics can be achieved even in a high xenon-concentrated PDP using a discharge gas configured to contain Xe gas in an amount of 10% or more.

  A plasma display panel (PDP) was produced using the Mn-activated germanate phosphor according to the present invention as a green phosphor constituting the green phosphor film. A plasma display panel composed of the discharge cells shown in FIG. 3 was produced. In the PDP 100 of the surface discharge type color PDP as in this embodiment, for example, a negative voltage is applied to one of the pair of display electrodes (electrodes 2) (generally referred to as scanning electrodes), and the address electrodes (electrodes 9). A discharge is generated by applying a positive voltage (a positive voltage compared to the voltage applied to the display electrode) to one of the remaining display electrodes (electrode 2). As a result, a wall charge is formed to assist in starting the discharge (this is called writing). When an appropriate reverse voltage is applied between the pair of display electrodes in this state, a discharge is generated in the discharge space between the electrodes 2 via the dielectric layer 4 (and the protective film 5). When the voltage applied to the pair of display electrodes (electrode 2) is reversed after the discharge is completed, a new discharge is generated. By repeating this, a discharge is continuously generated (this is called a sustain discharge or a display discharge).

  In the PDP 100 according to the present embodiment, an address electrode (electrode 9) made of silver or the like and a dielectric layer 4 made of a glass-based material are formed on a rear substrate (substrate 6). The partition wall 7 made of a glass-based material is printed on a thick film, and the partition wall 7 is formed by blast removal using a blast mask.

Next, red, green and blue phosphor layers 10 are sequentially formed in stripes on the barrier ribs 7 so as to cover the groove surfaces between the corresponding barrier ribs 7. Here, each phosphor layer 10 corresponds to red, green and blue, and 35 parts by weight of red phosphor particles (65 parts by weight of vehicle) and 35 parts by weight of green phosphor particles (65 parts by weight of vehicle). And 35 parts by weight of the blue phosphor particles (65 parts by weight of the vehicle), mixed with the vehicle to form a phosphor paste, applied by screen printing, and then evaporated and evaporated of the volatile components in the phosphor paste. It is formed by burning off organic matter. As for the phosphor materials other than green, the red phosphor is a (Y, Gd) BO ₃ : Eu phosphor, and the blue phosphor is a BaMgAl ₁₀ O ₁₇ : Eu phosphor.

Next, the front substrate (substrate 1) on which the display electrode (electrode 2), bus line 3, dielectric layer 4 and protective film 5 are formed and the rear substrate (substrate 6) are frit-sealed, and the inside of the panel is vacuumed After exhausting, discharge gas is injected and sealed. Next, using the phosphors synthesized in Examples 1 and 2, the same materials were used for the red and blue phosphors, and plasma display devices filled in the respective phosphor layers 10 were produced, and the light emission characteristics were examined. This panel was found to have better chromaticity characteristics than a conventional product prepared by replacing only the green-emitting phosphor with a Mn-activated zinc silicate phosphor.

In the PDP according to the present invention, the Mn-activated germanate phosphor constituting the present invention is used and mixed with Zn ₂ SiO ₄ : Mn to replace a part of the green phosphor. It is also possible to construct a PDP having excellent chromaticity characteristics.

  In this embodiment, regarding the discharge gas, it is possible to constitute a PDP having excellent chromaticity characteristics in the form of use of a gas composed of xenon (Xe) gas having a composition ratio of 6% and 10%. It was possible.

It is explanatory drawing which shows the emission spectrum in wavelength 146nm vacuum ultraviolet-excitation conditions in the fluorescent substance of this invention, and the conventional fluorescent substance. It is the table | surface which put together the data which analyzed the light emission characteristic and light emission spectrum in Mn activated germanate fluorescent substance which is one embodiment of this invention, and the conventional fluorescent substance. It is a principal part disassembled perspective view which shows the structure of the plasma display panel which is the light-emitting device of one embodiment of this invention. It is a figure which shows the change of x value of the CIE chromaticity coordinate at the time of changing Mn density | concentration x of the Mn activation germanate fluorescent substance which is the form of one Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,6 ... Board | substrate 2, 9 ... Electrode 3 ... Bus line 4, 8 ... Dielectric layer 5 ... Protective film 7 ... Partition 10 ... Phosphor layer 100 ...・ PDP

Claims (6)

A pair of substrates opposed to each other with a gap, a partition provided between the pair of substrates and formed between the pair of substrates, and an electrode pair disposed on at least one of the opposing surfaces of the pair of substrates A discharge gas that is enclosed in a space formed by the partition walls and generates ultraviolet rays by a discharge due to a voltage applied to the electrode pair, and on the opposing surfaces of the pair of substrates in the space and the wall surfaces of the partition walls And a phosphor layer containing a phosphor that emits light when excited by the ultraviolet rays, and the phosphor includes a phosphor represented by the following general formula (I) A plasma display device.
_{Li 5 Zn 8-x Al 5} (MO 4) 9: Mn x ··· (I)
(However, in the formula (I), M represents at least one element of Ge and Si, and x is a value in the range of 0.001 ≦ x ≦ 0.5.) The plasma display apparatus according to claim 1, wherein the phosphor is represented by the following general formula (II).
_{Li 5 Zn 8-x Al 5} (GeO 4) 9: Mn x ··· (II)
(However, in the formula (II), x is in the range of 0.001 ≦ x ≦ 0.5.) The plasma display apparatus according to claim 2, wherein the phosphor is represented by the following general formula (III).
_{Li 5 Zn 8-x Al 5} (GeO 4) 9: Mn x ··· (III)
(However, in the formula (II), x is in the range of 0.001 ≦ x ≦ 0.3.)   A phosphor composed of any one of a red light-emitting phosphor, a green light-emitting phosphor, and a blue light-emitting phosphor is formed for each space, and the green light-emitting phosphor is a phosphor represented by the general formula (I). The plasma display device according to claim 1, comprising: 5. The plasma display device according to claim 4, wherein the green light emitting phosphor includes a Zn ₂ SiO ₄ : Mn phosphor together with the phosphor represented by the general formula (I).   6. The plasma display device according to claim 1, wherein the discharge gas is a gas containing Xe in an amount that causes a composition cost of 6% or more.

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