JP5094246B2 - Plasma display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve color characteristics and efficiency, in a plasma display apparatus constituted by using a phosphor. <P>SOLUTION: A plasma display panel 100 constituting a plasma display apparatus is equipped with a discharge gas which emits ultraviolet light by electric discharge and a phosphor layer 10 containing a phosphor emitting light by being excited by ultraviolet light. The phosphor comprises a new Eu-activated silicate phosphor represented by the formula: (Ba<SB>x</SB>Sr<SB>1-x</SB>)<SB>2-e</SB>-M1-Si<SB>2</SB>O<SB>7</SB>:Eu<SB>e</SB>(wherein M1 is at least one element selected from the group consisting of Mg and Zn; "x" exhibiting a composition ratio of the component Ba and "e" exhibiting a composition ratio of Eu each satisfy the formulas 0&lt;x&le;0.5 and 0.001&le;e&le;0.2). <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a plasma display device as a display device, and more particularly to a plasma display device configured using an Eu-activated silicate phosphor that emits light when excited by ultraviolet rays in a vacuum ultraviolet region.

  In recent years, there has been an increasing demand for thinning a display device represented by a monitor of a TV or a personal computer, which does not require a large installation space. In addition, plasma display devices (PDP (Plasma Display Panel) devices), field emission display (FED) devices, and backlights and thin liquid crystal panels can be used as devices that can cope with such thinning. Liquid crystal display (LCD) devices that constitute display devices have been actively developed.

  Among them, the PDP device is a display device using a plasma display panel (PDP) as a light emitting device. The plasma display panel (PDP) excites ultraviolet rays generated in a negative glow region in a minute discharge space containing a rare gas (when Xe (xenon) is used as a rare gas, the central wavelengths of main emission are 147 nm and 173 nm). Luminescence in the visible region is obtained by exciting the phosphor in the phosphor layer disposed in the minute discharge space as a source and urging the phosphor to emit light. The PDP device controls the amount and color of light emission in the PDP and uses it for display. Therefore, the phosphor is a very important main component for constituting the PDP device. Examples of documents related to this type of material and technology include Patent Document 1, Non-Patent Document 1, Non-Patent Document 2, and Non-Patent Document 3.

Japanese Patent Laid-Open No. 2003-142004 “Phosphor Handbook” edited by Phosphors Society of Japan Ohmsha 1987 Chapter III Chapter 7 330-335 G. Blasse, W. L. Wanmaker, J. W. ter Vrugt and A. Bril, Philips Res. Repts. 23, p189-200 (1968) Taisho Tokusaku, Tanaka Province, Hiroshi Kobayashi, Takashi Kunimoto, Jasco Report Vol. 45, no. 1, p10-15 (2003)

  In recent years, PDP devices have been recognized for their high performance, and their use as large-sized flat panel displays and thin TVs are rapidly expanding, replacing monitors and televisions (TVs) that use cathode ray tubes. As a result, further improvement in performance has been demanded. Specifically, high brightness to satisfy the display function as a TV, high luminous efficiency to achieve high brightness, wide color display performance to express video beautifully, movie content such as movies There is a demand for improved moving image characteristics for viewers to appreciate comfortably and high reliability that enables use as home appliances.

  As the performance of a PDP device is improved, the improvement of its characteristics plays a major role in improving the design and structure of the device and the members constituting them, particularly the performance of the phosphor used. Therefore, phosphors are required to have improved luminous efficiency, improved color characteristics of emitted light, that is, improved color purity, improved response characteristics in light emission, and improved degradation resistance that leads to improved reliability. It has been.

Conventionally, phosphors of surface discharge type color display AC-PDP devices use red (R), green (G) and blue (B) phosphors corresponding to light emission of red, green and blue colors. However, Eu-activated aluminate phosphor: BaMgAl ₁₀ O ₁₇ : Eu (hereinafter referred to as BAM) is generally used as the blue phosphor. Although this BAM is excellent in characteristics such as light emission efficiency, since it is easily deteriorated, its reliability is low and its life is short. Therefore, improvement in stability and long life are required. Further, improvement of color characteristics has been pointed out as a problem, and further improvement is similarly demanded.

  In order to improve the color characteristics, specifically, it is required to emit a deeper blue color. By emitting light of a deeper blue color, it is possible to improve the color specification performance realized by phosphor emission, and thus to further improve the performance of image display of the PDP device.

Under such circumstances, silicate phosphors can be used as blue light-emitting phosphors that can improve color characteristics compared to BAM, which is a conventional blue phosphor, and have high reliability and long life. Proposed. As a specific example, use of Ca _1-x MgSi ₂ O ₆ : Eu _x (hereinafter referred to as CMS) has been proposed (see Patent Document 1).

  However, the CMS, which is a representative example, has been pointed out as lacking in luminance as compared with BAM and the like, and its improvement is demanded.

  At the same time, in the technical field of PDP devices, a plasma display panel (PDP) structure for the purpose of increasing the luminous efficiency of PDP devices as a high-performance TV device is being developed in parallel with the study of higher performance phosphor materials. Consideration of improvement is underway.

As one of the methods, the composition ratio of Xe (xenon) contained in the discharge gas containing Ne (neon) as a main component is increased, and the Xe ₂ molecular beam (wavelength 173 nm) generated by the discharge is actively used. The technology to be tried has been actively studied. Although it is a technical trend of “high xenon concentration” in so-called PDP, the composition ratio region is usually larger than the Xe gas composition ratio (about 4%) in the discharge gas, for example, 6% or higher or higher composition of 10% or higher. Studies have been made to achieve such high efficiency of the PDP in the specific range.

  As a result of this technological development, PDP devices that have become more efficient can be used more and more as flat TV devices that replace TV devices using CRTs instead of simple thin display devices. . The demand for image quality is becoming increasingly high, and the color characteristics of phosphors that have not been regarded as a problem in the past have come to attract more attention. In particular, there is a strong demand for improving the color characteristics of the above-mentioned blue phosphors. It has become a situation.

CMS, which is an example of the silicate phosphor, exhibits relatively high emission luminance and good color purity when ultraviolet light in a wavelength region of 147 nm is used as an excitation source. However, it has been clarified as excitation characteristics that there is almost no excitation band at wavelengths of 160 nm to 210 nm (Non-patent Document 3). Therefore, the intensity of light emission caused by excitation by vacuum ultraviolet rays (Xe ₂ molecular beam) near a wavelength of 173 nm, which is important in PDP, is extremely low. As a result, it has been pointed out that the light emission luminance is insufficient when compared with the conventional BAM when the PDP is applied. Furthermore, CMS has a low luminance efficiency for Xe ₂ molecular beam having a wavelength of 173 nm, which is a technology trend of increasing the efficiency of PDP. The efficiency improvement effect cannot be obtained. Therefore, in addition to pointing out the lack of brightness at present, CMS has another improvement for practical use, especially when considering the future trend of high efficiency technology for PDP, especially the luminous efficiency in the 173 nm wavelength excitation band. Improvement is needed. Therefore, development of a new blue phosphor has been demanded.

In that case, the new blue phosphor has an Xe ₂ molecular beam that becomes a main phosphor excitation light source when the PDP device is made to have a high xenon concentration in addition to the ultraviolet ray having a wavelength of 147 nm generated by the discharge in the PDP device, that is, a wavelength of 173 nm. It is necessary to be a phosphor that is excited efficiently by ultraviolet rays and emits fluorescence of good color.

  From the above, one of the problems to be solved by the present invention is to improve the light emission color characteristics of a blue phosphor typified by BAM. In particular, it is to improve the color characteristics of light emission of the blue phosphor in the 173 nm wavelength excitation band in response to the trend toward higher efficiency of PDP.

In addition, another object of the present invention is to provide a silicate phosphor that is proposed as an alternative mainly from the viewpoint of improving its reliability with respect to BAM, which is a phosphor for a conventional PDP device. The brightness performance is insufficient. Furthermore, CMS has a low luminous efficiency for Xe ₂ molecular beam having a wavelength of 173 nm, so that it has a sufficient brightness improvement effect and efficiency improvement effect against the trend of high efficiency technology of PDP in the technical field of PDP devices. It cannot be obtained.

  Accordingly, an object of the present invention is to develop a new composition of a silicate phosphor, improve the luminance characteristics of the silicate phosphor, and a PDP device using the silicate phosphor, particularly a PDP device with a high xenon concentration. Is to improve luminance characteristics.

In addition, another object of the present invention is to realize a novel composition phosphor with high color purity that can respond to the trend of high efficiency technology of PDP by developing an effective novel matrix composition for silicate phosphor, An object of the present invention is to provide a PDP device having excellent color characteristics by using this.
The above and other problems, objects and novel features of the present invention should become apparent from the description of the present specification and the accompanying drawings.

  Among the inventions disclosed in the present application, effects obtained by typical ones will be briefly described as follows.

A plasma display device according to the present invention includes a pair of substrates opposed to each other with a gap therebetween, a partition wall provided between the pair of substrates and forming a space between the pair of substrates, and the pair of substrates opposed to each other. An electrode pair disposed on at least one of the surfaces; a discharge gas sealed in a space formed by the partition wall; and generating ultraviolet rays by a discharge caused by a voltage applied to the electrode pair; and the space in the space A phosphor layer is formed on at least one of the opposing surfaces of a pair of substrates and on the wall surface of the partition wall and contains a phosphor that is excited by the ultraviolet rays and emits light, and the discharge gas has a composition ratio of 6% or more. , Preferably 10% or more, and more preferably 12% or more. The phosphor is composed of Xe gas, and the phosphor is Eu-activated silica represented by the following general formula (1). In the following formula (1), M1 is one or more elements selected from the group consisting of Mg and Zn, and x indicating the composition ratio of the component Ba is 0 <x ≦ 0. 5, preferably 0.2 ≦ x ≦ 0.5, more preferably 0.25 ≦ x ≦ 0.4, still more preferably 0.3 ≦ x0.4, and e indicating the composition ratio of Eu is 0 .001 ≦ e ≦ 0.2.

(Ba _x Sr _1-x ) _2-e · M1 · Si ₂ O ₇ : Eu _e (1)

Then, the phosphor layer together with Eu-activated silicate phosphor represented by the above general formula _{(1), BaMgAl 10 O 17} : Eu, CaMgSi 2 O 6: Eu and _Sr 3 MgSi ₂ O _8: Eu One or more phosphors selected from the group consisting of:

  Among the inventions disclosed in the present application, effects obtained by typical ones will be briefly described as follows.

  The plasma display (PDP) device according to the present invention uses a Eu-activated silicate phosphor having a good light emission efficiency under a light excitation condition of a wavelength of 173 nm in addition to a light excitation condition of a wavelength of 147 nm, and thus achieves good light emission efficiency. be able to.

  Moreover, since the PDP device according to the present invention uses an Eu activated silicate phosphor having good color purity under the photoexcitation condition of wavelength 173 nm in addition to the photoexcitation condition of wavelength 147 nm, the PDP device with high Xe concentration is used. Excellent color characteristics can be achieved even in an environment.

  Further, since the plasma display device according to the present invention is excellent in color characteristics and efficiency, it is possible to realize excellent video display.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Note that components having the same function are denoted by the same reference symbols throughout the drawings for describing the embodiment, and the repetitive description thereof will be omitted.

Regarding the relationship between the composition of the discharge gas and the intensity of each ultraviolet ray generated by the discharge in the plasma display panel (PDP) constituting the PDP device, the Xe component contained in the discharge gas mainly containing Ne (neon) It is known that the larger the composition ratio, the higher the intensity of the entire vacuum ultraviolet rays emitted by the discharge, and the ratio of the constituent components in the emitted vacuum ultraviolet rays changes. Specifically, the intensity ratio (I ₁₇₃ / I ₁₄₇ ) between the ultraviolet ray component having a wavelength of 147 nm and the ultraviolet ray component having a wavelength of 173 nm (Xe ₂ molecular beam) contained in the vacuum ultraviolet ray generated due to the change in the Xe composition ratio in the discharge gas. It is known that the intensity ratio (I ₁₇₃ / I ₁₄₇ ) increases as it changes, that is, as the Xe composition ratio increases.

  In the present invention, a novel silicate phosphor capable of achieving light emission with high color purity and high efficiency under light excitation conditions with a wavelength of 173 nm in addition to light excitation conditions with a wavelength of 147 nm has been realized. As a result, a novel PDP device that achieves excellent color characteristics and high efficiency could be realized using this novel silicate phosphor.

The newly activated Eu activated silicate phosphor constituting the present invention is an Eu activated silicate phosphor represented by the following general formula (1).

(Ba _x Sr _1-x ) _2-e · M1 · Si ₂ O ₇ : Eu _e (1)

In the above formula (1), M1 is one or more elements selected from the group consisting of Mg and Zn, and x indicating the composition ratio of the component Ba and e indicating the composition ratio of Eu are each 0 <x ≦ 0.5, 0.001 ≦ e ≦ 0.2.

  The newly realized Eu-activated silicate phosphor is capable of forming a matrix skeleton that is a composite oxide containing Sr and Ba as the matrix skeleton components, in accordance with the notation of the above formula (1). . At the same time, when the notation of the above formula (1) is followed, it is possible to form a matrix skeleton that is a composite oxide containing at least one of Mg and Zn as the matrix skeleton component M1.

By activating Eu ²⁺ in the above composition ratio range as an Eu component in the thus formed host skeleton, it is possible to configure a blue phosphor as a complex oxide that emits light efficiently. Furthermore, as a base skeleton component, the Ba component is controlled to be contained within an optimal amount range, so that the color purity can be remarkably improved as compared with the conventional one while maintaining the light emission efficiency and the luminance at a good level. It becomes possible.

  Here, regarding the content of Ba, the composition ratio (x) of the phosphor component (Ba) is 0 <x ≦ 0.5 when the notation of the above formula (1) is followed. However, in accordance with the evaluation results and considerations of the phosphor characteristics described later, the effect of increasing the color purity is more remarkable particularly when the composition ratio (x) of Ba is 0.2 ≦ x ≦ 0.5, More preferred. Further, considering that the color purity of emitted light is better, the composition ratio (x) of Ba is preferably 0.25 ≦ x ≦ 0.4. Further, considering that the color purity of light emission is more stable and good, the composition ratio (x) of Ba is most preferably 0.3 ≦ x ≦ 0.4.

  Hereinafter, characteristics and evaluation results of the novel Eu activated silicate phosphor constituting the present invention will be described in comparison with corresponding measurement data of a phosphor such as CMS as a comparative example.

As a study supporting the above technique, the present inventor is an example of a new phosphor constituting the present invention (Ba _0.5 Sr _0.5 ) _{1 as} will be described in detail in the description of Examples below. _.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.4 Sr _0.6 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.3 Sr _{0.7 1.97} · Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.25 Sr _0.75 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.2 Sr _{0) .8} ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 and (Ba _0.1 Sr _0.9 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 and phosphor Sr _{1.97 · Mg · Si 2 O 7} : was synthesized _{Eu 0.03,} available by purchasing commercially available C As a comparative example S, Luminescent characteristics were evaluated by using a vacuum ultraviolet excimer lamp central emission wavelength of 147nm and 173nm in the excitation light source according to a conventional method.

  Regarding emission characteristics, first, emission spectra under excitation conditions with wavelengths of 147 nm and 173 nm were evaluated, and the phosphors were compared. FIG. 1 is an emission spectrum of the main phosphors in the examples of the novel phosphors constituting the present invention under the excitation condition of wavelength 147 nm. FIG. 2 is an emission spectrum of the main phosphor among the examples of the novel phosphor constituting the present invention under an excitation condition at a wavelength of 173 nm. FIG. 3 is a table summarizing the wavelength values (maximum wavelengths (nm)) of spectral peaks in the emission spectra of the examples of the novel phosphor constituting the present invention under both excitation wavelengths of 147 nm and 173 nm.

  As can be seen from the comparison of the spectra of the main phosphor examples shown in FIG. 1 and FIG. 2, in the new Eu-activated silicate phosphor constituting the present invention, the Ba composition ratio in the host skeleton increases. In (1), x indicating the composition ratio of the component Ba is 0 (phosphor indicating that the Ba component is not included in the composition formula) to 0.1, 0.2, 0.25, 0.3, 0.4. It can be seen that the peak of the emission spectrum shifts to the short wavelength side under both excitation conditions of wavelengths 147 nm and 173 nm as the number increases sequentially to 0.5.

  Note that when the above spectral maximum is shifted to the short wavelength side, the spectral shape does not show any significant spectral shape difference such as the formation of a new peak except for a slight broadening of the shape.

  In addition, when the emission characteristics under both excitation conditions of wavelengths 147 nm and 173 nm are compared, the change in the maximum wavelength value of the spectrum is gentle when the Ba composition ratio (x) increases from 0 to 0.2 under any condition. Although it is relatively small, a large decrease in the emission maximum wavelength appears when increasing from 0.2 to 0.5. That is, when the Ba composition ratio (x) is increased from 0.2 to 0.5, the emission maximum wavelength is suddenly shifted to the lower wavelength side from 464 nm to 432 nm.

  Looking at this in more detail, under the excitation condition of wavelength 147 nm, when the Ba composition ratio (x) increases from 0.25 to 0.3, the emission maximum wavelength greatly decreases from 452 nm to 436 nm, that is, greatly increases. In contrast to the shift to the lower wavelength side, when the Ba composition ratio (x) increases from 0.25 to 0.3 under the excitation condition of wavelength 173 nm, the maximum emission wavelength decreases from 452 nm to 440 nm. Is small, and the shift of the spectrum to the lower wavelength side is gentle. Therefore, in the new phosphor constituting the present invention, although the emission characteristic changes greatly when the Ba composition ratio (x) increases from 0.2 to 0.5, it is compared with the excitation condition at the wavelength of 147 nm. Thus, it can be seen that, under the excitation condition of wavelength 173 nm, the abrupt change in the light emission characteristics that occurs particularly when the Ba composition ratio (x) is 0.2 to 0.4 is relatively gradual.

  Next, regarding the chromaticity in the CIE (International Commission on Illumination) color system representing the emission color of the phosphor, and the x value and y value in the (x, y) coordinates of the chromaticity, the excitation conditions at wavelengths of 147 nm and 173 nm are used. And evaluated.

  FIG. 4 is a table summarizing the x value and the y value of the chromaticity (x, y) of light emission under both excitation conditions of wavelengths 147 nm and 173 nm of the examples of the novel phosphor constituting the present invention. FIG. 5 shows x of chromaticity (x, y) of light emission obtained under both excitation conditions of wavelengths 147 nm and 173 nm with respect to the Ba composition ratio (x) in the example of the novel phosphor constituting the present invention. It is the graph which plotted the value and y value, respectively.

  As shown in the table shown in FIG. 4 and FIG. 5, the Ba composition ratio in the matrix increases, that is, in the above formula (1), x indicating the composition ratio of the component Ba is 0 (Ba component is the composition formula) (Both phosphors not including the above) from 0.1 to 0.2, 0.25, 0.3, 0.4, and 0.5 in order, under both excitation conditions of wavelengths 147 nm and 173 nm, It can be seen that the emission color characteristics change.

  At that time, the x value of the chromaticity (x, y) of light emission does not change so much from about 0.13 to about 0.16 under both excitation conditions of wavelengths 147 nm and 173 nm, whereas the chromaticity It can be seen that the y value of (x, y) varies greatly from about 0.17 to about 0.03. Such changes indicate that the new phosphor constituting the present invention has an increased depth in the blue color of the emitted light as the composition ratio (x) of Ba increases, and that the blue is highly purified. Represents.

  In more detail, when the Ba composition ratio (x) is increased from 0 to 0.2, the change in the y value of the chromaticity (x, y) of the emission is While a comparatively gentle decrease is shown, when the value increases from 0.2 to 0.3, a large decrease in the y value of the chromaticity (x, y) of light emission occurs. When the Ba composition ratio (x) exceeds 0.3, the y value of the chromaticity (x, y) gradually decreases again. That is, it can be seen that, when the Ba composition ratio (x) is increased from 0.2 to 0.3, the blue light emission color is highly purified.

  It is inferred that the above results closely correspond to the peak accompanying the increase in the Ba composition ratio (x) found in the emission spectrum and the low wavelength side shift of the entire spectrum. In addition, when considering the emission characteristics of the new phosphor constituting the present invention, in particular, the color characteristics, the Ba composition ratio (x), like the y value of the chromaticity (x, y) of emission, Since a phenomenon in which the performance changes suddenly appears, it can be understood that the selection of the composition region of the Ba composition ratio (x) is very important in improving the performance of the PDP device.

  Further, under the excitation condition of wavelength 147 nm, when the Ba composition ratio (x) increases from 0.2 to 0.3, the chromaticity y value of light emission greatly decreases from 0.136 to 0.038. In other words, a large color change occurs, but under the 173 nm wavelength excitation condition, when the Ba composition ratio (x) increases from 0.2 to 0.3, the emission chromaticity (x, y) The y value decreases from 0.136 to 0.051, and the color change is gentler than the excitation condition at a wavelength of 147 nm.

  Therefore, in the new phosphor constituting the present invention, although the emission characteristic changes greatly when the Ba composition ratio (x) increases from 0.2 to 0.3, it is compared with the excitation condition at the wavelength of 147 nm. In particular, under the wavelength 173 nm excitation condition, it can be seen that the abrupt change in the color characteristics that occurs particularly when the Ba composition ratio (x) is 0.2 to 0.3 is relatively gradual as compared with the wavelength 147 nm excitation condition.

  Therefore, to summarize the results of the study, in the new phosphor constituting the present invention, although there is a composition region in which the performance changes sharply with respect to the Ba composition ratio (x), the steepness is in the excitation condition at the wavelength of 147 nm. The evaluation was different from the evaluation under the 173 nm excitation condition, and it was found that the 173 nm excitation condition was gentler.

  Therefore, when the color characteristic control of the light emission is realized by selecting the composition of the phosphor used in the PDP apparatus according to the embodiment of the present invention, the degree of change is gentler in the wavelength 173 nm excitation condition than in the wavelength 147 nm excitation condition. It can be seen that more stable and highly accurate color characteristic control can be performed.

  From the above, it can be seen that the new Eu-activated silicate phosphor constituting the present invention is easier to control the color characteristics under the excitation condition of wavelength 173 nm than under the excitation condition of wavelength 147 nm. In addition, after fully understanding the excitation wavelength dependence of such a characteristic expression, the composition region having the optimum Ba composition ratio (x) in the Eu activated silicate phosphor is carefully selected, and as a result of the PDP apparatus configured as a result, Controlling performance such as color characteristics is a very important matter.

  Next, CMS was selected as a comparative example, and the x value and y value in the (x, y) coordinates of the chromaticity under the excitation conditions of wavelengths 147 nm and 173 nm, as in the new phosphor constituting the present invention described above. The result of having evaluated about is shown. The evaluation results of CMS are x value = 0.152 and y value = 0.047 under the wavelength 147 nm excitation condition, and x value = 0.182 and y value = 0.108 under the wavelength 173 nm excitation condition.

Therefore, when evaluated under the excitation condition at a wavelength of 173 nm, in the example of the new phosphor constituting the present invention, the composition of Ba composition ratio (x) = 0.25 (Ba _0.25 Sr _0.75 ) _1.97. Considering that the y value of the chromaticity (x, y) of the emission color under the excitation condition of wavelength 173 nm at Mg · Si ₂ O ₇ : Eu _0.03 is 0.101, the Ba composition ratio (x) By setting the composition range to 0.25 or more, it is possible to exhibit a y value lower than that of CMS, that is, excellent blue purity under the condition of excitation at a wavelength of 173 nm.

  That is, considering the color characteristic comparison with the conventional CMS under the wavelength 173 nm excitation condition, it is preferable to select Ba composition ratio (x) = 0.25 or more. By setting the Ba composition ratio (x) = 0.25 and the value or more, the above-described novel phosphor constituting the present invention has a chromaticity of blue light emission from the CMS as a comparative example under a wavelength 173 nm excitation condition ( A value smaller than the y value of x, y) can be realized.

  Next, the performance of the novel Eu activated silicate phosphor constituting the present invention as a PDP application will be considered from the viewpoint of color characteristics.

  When using a PDP device for color TV applications, the color characteristics and color range of the display can be accommodated by considering the chromaticity of each color of R (red), G (green), and B (blue) for each broadcasting system. Desired. In the NTSC (National Television System Committee) standard, which is a conventional broadcasting system, for example, the blue chromaticity (x, y) is x value = 0.14, y value = 0.08, and the NTSC ratio as the colorimetric range It is desired to realize a wider color reproducibility such as ensuring 100% or more. As a result, the blue phosphor responsible for B (blue) display in the PDP device has a y value of the chromaticity of the emitted color close to 0.08 or a value smaller than 0.08 that can also express deeper blue. Desired.

  In the HDTV (High Definition TeleVision) standard, which is expected to become the mainstream in the future, the blue chromaticity (x, y) is x value = 0.15 and y value = 0.06. In the case of a blue phosphor that carries B (blue) display in a PDP device, the y value of the chromaticity of the emitted color can be close to 0.06, or a deeper high-purity blue can be expressed. A smaller value is required.

  Therefore, in order to be used for the PDP device that can be used for color TV in the above-described novel phosphor constituting the present invention, the color performance, particularly the y value of chromaticity (x, y) is required. It is preferably near 0.08 or less.

Therefore, when considering based on the result of the color characteristic evaluation described above, the Eu-activated silicate fluorescence of the present invention represented by the general formula (Ba _x Sr _1-x ) _{2 -e} · M 1 · Si ₂ O ₇ : Eu _e In the body, the composition of Ba composition ratio (x) = 0.25 (Ba _0.25 Sr _0.75 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , the emission color under the excitation condition of wavelength 147 nm Considering that the y value of chromaticity (x, y) is 0.079, it is preferable to select a range of Ba composition ratio (x) that can include the composition. That is, in the present invention according to the present study, it is preferable to select a Ba composition ratio (x) = 0.2 or more.

  Further, by making the composition ratio of the Ba composition ratio (x) = 0.25 or more, more reliable color performance can be realized, which is more preferable.

  In addition, by setting Ba composition ratio (x) = 0.25 or more, the above-described new phosphor constituting the present invention is simultaneously blue as compared with CMS as a comparative example under the wavelength 173 nm excitation condition as described above. A value smaller than the y value of the chromaticity (x, y) of light emission can be realized.

Therefore, the above general formula _{(Ba x Sr 1-x)} 2-e · M1 · Si 2 O 7: In Eu-activated silicate phosphor of the present invention represented by Eu _e, Ba composition ratio (x) is x ≧ 0.2 is preferable, and x ≧ 0.25 is more preferable.

Further, in the Eu activated silicate phosphor of the present invention represented by the general formula (Ba _x Sr _1-x ) _2-e · M1 · Si ₂ O ₇ : Eu _e , the Ba composition ratio (x) is 0.3. The phosphor (Ba _0.3 Sr _0.7 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 is the y value of the chromaticity (x, y) of the emission color, and the wavelength 147 nm excitation condition 0.038 and 0.051 at a wavelength of 173 nm excitation condition. That is, the y value of blue chromaticity (x, y) defined by the NTSC system is smaller than 0.08, and the y value of blue chromaticity (x, y) defined by the HDTV system is smaller than 0.06.

Therefore, when a PDP device configured using this phosphor (Ba _0.3 Sr _0.7 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 is used as a color TV application, the NTSC system is used. It can be seen that it can sufficiently cope with the expansion of the color specification range, and further supports the HDTV system and can expand the color specification range.

  Further, as described above, both are smaller than the y values (0.047 and 0.108) under both excitation conditions of wavelengths 147 nm and 173 nm indicated by the CMS as a comparative example.

Therefore, in the Eu activated silicate phosphor of the present invention represented by the general formula (Ba _x Sr _1-x ) _2-e · M1 · Si ₂ O ₇ : Eu _e , the Ba composition ratio (x) is x ≧ 0. .3 is more preferable.

  Next, the upper limit of the Ba composition ratio (x) in the Eu activated silicate phosphor of the present invention will be considered.

As described above, in the Eu activated silicate phosphor of the present invention, x indicating the composition ratio of the component Ba is 0 to 0.1, 0.2, 0.25, 0.3, 0.4, 0.5. It is known that the emission color characteristics change, particularly the y value of the chromaticity (x, y) of the emission color decreases, under both excitation conditions of wavelengths 147 nm and 173 nm. In the Eu-activated silicate phosphor of the present invention represented by the general formula (Ba _x Sr _1-x ) _2-e · M1 · Si ₂ O ₇ : Eu _e , the Ba composition ratio (x) is 0.5. The phosphor (Ba _0.5 Sr _0.5 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 has a chromaticity (x, y) of the emission color of 0 when the wavelength is 147 nm. 0.036 at 0.030 wavelength 173 nm excitation condition. That is, the y value is 0.04 or less under any condition, and there is a concern that the value is slightly too small beyond the good blue expression range. That is, there is a possibility that the blue color indicated by the phosphor emission is too deep.

  Then, when the Ba composition ratio (x) exceeds 0.5, it can be estimated that the y value of the chromaticity (x, y) of the emission color is further reduced, and the y value is a value of 0.03 or less. Can easily be guessed.

  When trying to use a PDP device for color TV applications, it realizes each color of R (red), G (green), and B (blue) for each NTSC broadcasting system, and faithfully follows the color range specified for each broadcasting system. In view of the blue chromaticity (x, y) of the NTSC system and the blue chromaticity (x, y) of the HDTV system, the y value becomes 0.03 or less. It is likely that it is unnecessary to reduce the size.

  For example, if the y value of the chromaticity (x, y) of blue, which is the above-mentioned luminescent color, is set to a value that is significantly smaller than 0.08, and further 0.06, the color range of blue is difficult to control. There is a concern that unfavorable side effects such as a decrease in luminance may be caused as a price, and such a decrease in y value is considered to be virtually unnecessary.

Therefore, the y value of the chromaticity (x, y) of the emitted color is preferably about 0.04 or more, and the phosphor (Ba _0.5 Sr ₀ ) having a Ba composition ratio (x) of 0.5. _.5 ) Since the y value of the chromaticity (x, y) of the emission color under the excitation condition of _1.97 · Mg · Si ₂ O ₇ : Eu _{0.03 at} a wavelength of 173 nm is 0.036, In the Eu activated silicate phosphor, the Ba composition ratio (x) preferably has a value of x ≦ 0.5. The Ba composition ratio (x) is more preferably x ≦ 0.4 so that the y value of the chromaticity (x, y) of the emission color is about 0.04 or more even under the excitation condition of wavelength 147 nm. preferable.

At this time, as described above, for example, (Ba _0.4 Sr _0.6 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 and (Ba _0.3 Sr _0.7 ) _1. The y value of the chromaticity (x, y) of the emission color indicated by ₉₇ · Mg · Si ₂ O ₇ : Eu _0.03 is 0.036 and 0.038 under the wavelength 147 nm excitation condition, and under the wavelength 173 nm excitation condition. 0.046 and 0.051 are shown.

  That is, under the wavelength 173 nm excitation condition, the Eu activated silicate phosphor of the present invention has a higher color purity than CMS and the y value does not become too small.

Therefore, it can be seen that the Eu activated silicate phosphor of the present invention exhibits more preferable color characteristics under the excitation condition of a wavelength of 173 nm.
Therefore, it can be seen that when the color characteristic control of light emission is realized by selecting the composition of the phosphor used in the PDP apparatus, the control is easier in the wavelength 173 nm excitation condition than in the wavelength 147 nm excitation condition. That is, it can be seen that the novel Eu-activated silicate phosphor constituting the present invention can control the color characteristics in a preferable range under the excitation condition of wavelength 173 nm as compared with the excitation condition of wavelength 147 nm.

According to the above consideration, in the Eu activated silicate phosphor of the present invention represented by the general formula (Ba _x Sr _1-x ) _2-e · M1 · Si ₂ O ₇ : Eu _e , Since it is possible to reduce the y value of the chromaticity (x, y) of the emission color, it is preferable to intentionally contain a Ba component.

  Further, in order not to cause the above-mentioned concerns such as a decrease in luminance due to the y value becoming too small, the upper limit value is determined according to the above, and the Ba composition ratio (x) is set to 0 <x ≦ 0.5. Is preferred.

  Further, considering the preferable range of the y value of the chromaticity (x, y) of the emission color under the excitation condition of the wavelength 147 nm in the Eu activated silicate phosphor of the present invention, the Ba composition ratio (x) is 0.2 ≦ Preferably x ≦ 0.5, and more preferably 0.25 ≦ x ≦ 0.5 in accordance with the above.

  Considering the preferable range of the y value of the chromaticity (x, y) of the emission color under the wavelength 173 nm excitation condition, and when the PDP device of the present invention is used for a color TV application, HD- In consideration of the compatibility with the TV system, in the Eu activated silicate phosphor of the present invention, the Ba composition ratio (x) is more preferably 0.3 ≦ x ≦ 0.5, more preferably as described above. In consideration of the upper limit, it is most preferable that 0.3 ≦ x ≦ 0.4.

  Furthermore, the Eu-activated silicate phosphor of the present invention is more preferably used under a wavelength 173 nm excitation condition as compared with a wavelength 147 nm excitation condition.

  Note that the lower limit of the Ba composition ratio (x) is defined as 0 <x. In the present application, assuming that Ba is added, setting the lower limit of the composition ratio (x) of Ba to be greater than 0 (0 <x) is conscious that the Ba composition is contained during the synthesis of the phosphor. This means that the raw material of the Ba component is used. That is, at the time of synthesizing the Eu-activated silicate phosphor constituting the present invention in which the Ba component is composed, the raw material of the Ba component is clearly mixed with other raw materials to synthesize the phosphor. Means.

  On the other hand, for example of another phosphor made of Sr, Mg or Eu, an Mg raw material for phosphor synthesis used as a normal raw material when a phosphor containing a normal Mg component or Eu component is synthesized. A compound, Eu raw material compound, etc. may contain a Ca component raw material as a trace amount of impurities. That is, the phosphor composed of Mg or Eu component that is not intended to contain the Ca component may contain a trace amount of Ca component such as several ppm to several tens of ppm. Therefore, even in a phosphor that does not intend to contain a Ca composition and whose content is not specified in the composition formula, if the details of the composition are analyzed by a technique such as analysis, it may be found that the Ca component is contained.

  Therefore, the inclusion of such an unintended component, that is, a case where a characteristic component is contained in the phosphor as an impurity, and the purpose of improving the performance such as light emission luminance, the intention of clearly including the Ba component is further intended. It should be clearly distinguished from the novel Eu-activated silicate phosphor constituting the present invention in which the optimum range of the composition ratio is clarified. For this distinction, in the new phosphor constituting the present invention, when the composition of the Ba component is intended by the phosphor synthesis operation, the amount that can be substantially controlled is set as the lower limit of the Ba component content. Is preferred.

  Therefore, in the novel Eu-activated silicate phosphor constituting the present invention, even when a high-purity synthetic raw material having a purity of 99.9% or more is used, the amount that the specific component can be contained as an impurity is several ppm to several Considering the order of 10 ppm (several mg to several tens of mg in 1000 g), the lower limit of the amount that can be substantially controlled even when synthesizing a small amount of phosphor at a so-called laboratory level of about 10 g Including the Ba component, taking into account the fact that the amount is about 0.1 mg (10 ppm), that there is no significant difference in molecular weight between the starting compounds, and that the molecular weight order is comparable. The lower limit of the amount will be set again.

  That is, in the novel Eu activated silicate phosphor constituting the present invention, assuming that the content of the Ba component is about 100 ppm or more, the lower limit of the composition ratio (x) of Ba is x = 0.0001. It can be.

  And in order to realize clear distinction, considering clearly enabling it to be excluded even when it is contained unintentionally, and even when using a phosphor material with lower purity, Preferably, the lower limit of the component content is about 10 times the above value, and the lower limit of the composition ratio (x) of Ba is x = 0.001.

  Furthermore, considering the amount that can be unintentionally contained when using a phosphor material with lower purity, in order to realize a clear distinction, the lower limit of the content of the Ba component is about 100 times the above And the lower limit of the composition ratio (x) of Ba is preferably x = 0.01.

  That is, in the novel phosphor constituting the present invention, when the Ba component is added in consideration of the color characteristics and chromaticity of light emission and the optimum range of the composition ratio of Ba is clarified, the composition ratio (x) of Ba The lower limit of x can be set to x = 0.0001. Further, the composition ratio (x) of Ba is preferably 0.001 ≦ x, and more preferably 0.01 ≦ x.

As described above, descriptions such as 0 <x, other 0.01 <x, and the like in this application are disclosed including any of the above lower limit settings. Therefore, for example, from the result of luminance evaluation under an ultraviolet excitation condition with a wavelength of 173 nm, in the Eu-activated silicate phosphor constituting the present invention, the Ba composition ratio (x) is set to 0.01 for a desirable Ba content. More preferably, ≦ x ≦ 0.5.
In addition, for the content of the Eu component that is an activator, the lower limit is set in consideration of the amount that can be included unintentionally, and the purpose is to control self-quenching to obtain desired light emission characteristics. By defining the upper limit, e indicating the composition ratio of Eu in the composition formula (1) is preferably 0.001 ≦ e ≦ 0.2.

  Next, a vacuum ultraviolet excimer lamp with a wavelength of 173 nm was studied in order to examine the improvement of the low emission efficiency under the excitation condition of a wavelength of 173 nm, which was a problem of CMS, with the novel Eu-activated silicate phosphor constituting the present invention. Is used as an excitation light source, and the results of comparing and evaluating the luminous efficiency based on CMS are considered.

  As described in detail below, the evaluation method of the luminous efficiency is a value obtained by dividing the luminance (Br) of light emission, which is known as a parameter reflecting the luminous efficiency, by the y value of chromaticity (x, y) of light emission. That is, the (Br / y) value is calculated, and based on the Br / y value of CMS, how many times the Br / y value indicated by the new Eu-activated silicate phosphor constituting the present invention is increased, Conduct a comparative study.

As a result of the study, in the example of the novel Eu activated silicate phosphor constituting the present invention based on CMS, (Ba _0.5 Sr _0.5 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 1.8 times, (Ba _0.4 Sr _0.6 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 1.7 times, (Ba _0.3 Sr _0.7 ) _1.97 Mg · Si ₂ O ₇ : 1.9 times for Eu _0.03 , (Ba _0.25 Sr _0.75 ) _1.97 · Mg · Si ₂ O ₇ : 1.5 times for Eu _0.03 , ( Ba _0.2 Sr _0.8 ) _1.97 · Mg · Si ₂ O ₇ : 2.1 times in Eu _0.03 , (Ba _0.1 Sr _0.9 ) _1.97 · Mg · Si ₂ O ₇ : in _{Eu 0.03,} 1.5 times, and the phosphor _{Sr 1.97 · Mg · Si 2 O} 7: Eu 0.0 In it it can be seen that is 3.9 times.

It can be seen that any of the new phosphors constituting the present invention has improved luminous efficiency compared with CMS under the excitation condition of wavelength 173 nm.
From the above, by configuring the PDP device of the present invention using the new Eu-activated silicate phosphor whose Ba composition ratio range is optimized as described above, the PDP device having high efficiency and wide color reproducibility can be obtained. It can be seen that this is possible.

  Note that the novel Eu-activated silicate phosphor constituting the present invention represented by the general formula (1) is a light emitting device other than a PDP, for example, a planar rare gas discharge fluorescent lamp or a three-wavelength white fluorescent lamp. It can also be used as a blue-emitting phosphor. That is, by using the novel Eu-activated silicate phosphor constituting the present invention represented by the above general formula (1), a high-reliability planar type rare earth element having high luminance, high efficiency, and wide color reproducibility. A light emitting device such as a gas discharge fluorescent lamp or a three-wavelength white fluorescent lamp can be realized.

Next, the relationship between the effect of increasing the Xe concentration in the PDP and the present invention will be described. As described above, in the PDP, as the Xe composition ratio in the discharge gas increases, the total amount of generated vacuum ultraviolet rays increases, and an ultraviolet component having a wavelength of 147 nm and ultraviolet rays having a wavelength of 173 nm contained in the generated vacuum ultraviolet rays (Xe ₂ molecules). It is known that the intensity ratio (I ₁₇₃ / I ₁₄₇ ) with the (line) component is increased.

FIG. 6 is a graph showing the relationship between the Xe composition ratio (%) in the discharge gas and the intensity ratio (I ₁₇₃ ) / I ₁₄₇ ) in the AC type PDP.

As a result of the examination, in the AC type PDP, when the Xe composition ratio is 4%, I ₁₇₃ / I ₁₄₇ (4%) = 1.2. In a normal specification PDP with a Xe composition ratio of 1 to 4%, the intensity ratio of the ultraviolet component with a wavelength of 147 nm and the ultraviolet component with a wavelength of 173 nm contained in the vacuum ultraviolet rays generated by the discharge is from the degree that the intensity of the component with a wavelength of 173 nm is slightly higher It has been found that the intensity of the 173 nm component tends to be small or equal.

As a result of further studies, the Xe composition ratio of 6% increases the overall intensity of vacuum ultraviolet rays generated by discharge, and the ratio of I ₁₇₃ and I ₁₄₇ is as large as I ₁₇₃ / I ₁₄₇ (6%) = 1.9. Become bigger. When the Xe composition ratio is 10%, the intensity of the vacuum ultraviolet rays generated by the discharge is further increased, and I ₁₇₃ / I ₁₄₇ (10%) = 3.1 is significantly increased. Further, it was found that when the Xe composition ratio is 12%, the intensity of vacuum ultraviolet rays generated by the discharge is further increased, and I ₁₇₃ / I ₁₄₇ (12%) = 3.8 is significantly increased.

  Therefore, in a PDP with a high xenon specification that has a Xe composition ratio in the discharge gas larger than that of the normal specification PDP, for example, 6%, the contribution of the characteristics of the phosphor used to the 173 nm vacuum ultraviolet ray contributes. growing. Therefore, it is preferable to use a phosphor exhibiting light emission with better characteristics such as higher luminance with respect to ultraviolet rays having a wavelength of 173 nm.

Further, when the Xe composition ratio is set to 10% or higher and more efficient light emission is required, there is a demand for the phosphor performance to exhibit light emission with better characteristics such as higher luminance with respect to ultraviolet light having a wavelength of 173 nm. Will be bigger. When the Xe composition ratio is higher than 12% and more efficient light emission is required, I ₁₇₃ / I ₁₄₇ (12%) = 3.8, which is remarkably large. Further, the demand for the performance of the phosphor to exhibit light emission with better characteristics such as higher luminance is further increased.

As described above, when the novel Eu-activated silicate phosphor constituting the present invention represented by the general formula (1) is used in a PDP using a discharge gas containing an Xe composition, excitation of light having a wavelength of 147 nm In addition to the above, good light emission characteristics can be obtained in the phosphor by excitation of light having a wavelength of 173 nm, so that the generated Xe ₂ molecular beam can be used effectively, and a high-performance PDP can be provided.

Further, the new Eu-activated silicate phosphor constituting the present invention represented by the general formula (1) has, for example, an Xe composition ratio of 6% or more, more preferably a strong 173 nm ultraviolet component intensity ratio with respect to the 147 nm component ( Xe actively utilizing ₂ molecular beams) Xe composition ratio is 10% or more, more preferably Xe in an amount of _{I 173 / I 147 (12%} ) = 3.8 and significantly greater Xe composition ratio is 12% or more It is also well suited to the so-called “PDP for high Xe concentration” that uses a discharge gas that contains a gas. And it becomes possible to implement | achieve the high performance PDP using the discharge gas by which Xe concentration was made high.

  The novel Eu-activated silicate phosphor constituting the present invention represented by the above formula (1) shows a dependence on the color performance of light emission, particularly the color purity depending on the Ba component content, but the ultraviolet ray having a wavelength of 147 nm. Compared with the excitation, the wavelength changes more gradually within the range of the preferred color characteristic value in the case of the wavelength 173 nm excitation, the optimum range of the Ba content is clearer, and the color characteristics can be easily controlled by the Ba content. . Therefore, under conditions where excitation is mainly caused by vacuum ultraviolet rays having a wavelength of 173 nm, more significant effects and remarkable features appear in terms of color characteristics and efficiency.

Therefore, the new Eu-activated silicate phosphor constituting the present invention represented by the above formula (1) is Xe in such an amount that the composition ratio is 6% or more, more preferably 10% or more, and further preferably 12% or more. When used in a PDP using a discharge gas containing a composition, the Xe ₂ molecular beam generated in the PDP is more effectively used to exhibit excellent light emission characteristics, thereby providing a high-performance PDP. As a result, it is possible to provide a high-performance PDP device.

  Based on the above examination, one embodiment of the AC type PDP using the Eu activated silicate phosphor constituting the present invention represented by the above formula (1) is configured as follows.

FIG. 7 is an exploded perspective view of main parts showing an example of the structure of the main part of the PDP. A PDP 100 according to an embodiment of the present invention has a structure for dealing with so-called counter discharge, and is provided on a pair of substrates 1 and 6 that are arranged to face each other at an interval, and on a facing surface of the substrate 6, When the substrates 1 and 6 are overlaid, a partition wall 7 that maintains a space between the substrates 1 and 6 to form a space between the substrates 1 and 6, and electrodes 2 and 9 disposed on opposing surfaces of the substrates 1 and 6, And a discharge gas (not shown) which is enclosed in a space formed between the substrates 1 and 6 and generates ultraviolet rays by a discharge caused by a voltage applied to the electrode 2 or the electrodes 2 and 9. 8 shows one cross section along the extending direction of the electrode 2, FIG. 9 shows another cross section along the extending direction of the electrode 2, and FIG. A cross section along the extending direction of the electrode 9 is shown.
A phosphor containing an Eu activated silicate phosphor represented by the above formula (1) on one of the opposing surfaces of the pair of substrates 1 and 6 (substrate 6 side) and on the wall surface of the partition wall 7. Layer 10 is formed.

  The phosphor layer 10 is usually made of a phosphor corresponding to light emission of three colors of red, blue, and green, that is, a red light emitting phosphor, a blue light emitting phosphor, or a green light emitting phosphor, and is generated from the discharge gas by discharge. The Eu-activated silicate phosphor represented by the above formula (1) constituting blue in the phosphor layer 10 by vacuum ultraviolet rays having wavelengths of 147 nm and 173 nm, and phosphors constituting other colors (red and green) Is excited to emit visible light.

  7 is a bus line made of Ag or Cu—Cr that is integrated with the electrode 2 to reduce the electrode resistance, and each layer of the signs 4 and 8 is The dielectric layer 5 is a protective film provided for electrode protection. Examples corresponding to the best mode for carrying out the present invention will be described below.

Example 1
In order to make a plasma display panel (PDP) according to the first embodiment of the present invention, first, an Eu activated silicate phosphor, which is a main component of the present invention, was synthesized. What was synthesized was an Eu activated silicate phosphor represented by the following general formula (1), and x indicating the composition ratio of the component Ba was x = 0.5, x = 0.4, X = 0.3, x = 0.25, x = 0.2, and x = 0.1 (Ba _0.5 Sr _0.5 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.4 Sr _0.6 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.3 Sr _0.7 ) _1.97 · Mg · Si ₂ O ₇ : Eu _{0. 03} , (Ba _0.25 Sr _0.75 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.2 Sr _0.8 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 and _{(Ba 0.1 Sr 0.9) 1.97 ·} Mg · Si 2 O 7: a _{Eu 0.03,} the phosphor _{Sr 1.97} is x = 0 Mg _· Si ₂ O _7: a _{Eu 0.03.}

(Ba _x Sr _1-x ) _2-e · M1 · Si ₂ O ₇ : Eu _e (1)

The phosphor of the composition formula (Ba _0.5 Sr _0.5 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 was first synthesized by 0.973 g (4.925 mmol) of BaCO ₃ and SrCO _3. 0.727 g (4.925 mmol), MgCO ₃ 0.481 g (5.00 mmol), SiO ₂ 0.601 g (10.00 mmol), Eu ₂ O ₃ 0.0265 g (0.075 mmol), and melted As an auxiliary agent, 0.196 g (2.00 mmol) of NH ₄ Br was weighed out and thoroughly mixed in an agate mortar. Thereafter, the obtained mixture was filled in a heat-resistant container and baked at 900 ° C. in the air for 3 hours, and then baked at 900 ° C. in a reducing atmosphere for 3 hours. The obtained fired product was pulverized, washed with water, and dried to obtain a silicate phosphor having the above composition.

A phosphor having a composition formula (Ba _0.4 Sr _0.6 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 was first synthesized by adding 0.778 g (3.94 mmol) of BaCO ₃ and SrCO _3. 0.872 g (5.91 mmol), MgCO ₃ 0.481 g (5.00 mmol), SiO ₂ 0.601 g (10.00 mmol), Eu ₂ O ₃ 0.0265 g (0.075 mmol), and melted As an auxiliary agent, 0.196 g (2.00 mmol) of NH ₄ Br was weighed out and thoroughly mixed in an agate mortar. Thereafter, the obtained mixture was filled in a heat-resistant container and baked at 900 ° C. in the air for 3 hours, and then baked at 900 ° C. in a reducing atmosphere for 3 hours. The obtained fired product was pulverized, washed with water, and dried to obtain a silicate phosphor having the above composition.

The synthesis of the phosphor having the composition formula (Ba _0.3 Sr _0.7 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 was carried out by first adding 0.583 g (2.95 mmol) of BaCO ₃ and SrCO _3. 1.018 g (6.90 mmol), MgCO ₃ 0.481 g (5.00 mmol), SiO ₂ 0.601 g (10.00 mmol), Eu ₂ O ₃ 0.0265 g (0.075 mmol), and melted As an auxiliary agent, 0.196 g (2.00 mmol) of NH ₄ Br was weighed out and thoroughly mixed in an agate mortar. Thereafter, the obtained mixture was filled in a heat-resistant container and baked at 900 ° C. in the air for 3 hours, and then baked at 900 ° C. in a reducing atmosphere for 3 hours. The obtained fired product was pulverized, washed with water, and dried to obtain a silicate phosphor having the above composition.

The synthesis of the phosphor of the composition formula (Ba _0.25 Sr _0.75 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 was carried out by first adding 0.486 g (2.46 mmol) of BaCO ₃ and SrCO _3. 1.091 g (7.39 mmol), MgCO ₃ 0.481 g (5.00 mmol), SiO ₂ 0.601 g (10.00 mmol), Eu ₂ O ₃ 0.0265 g (0.075 mmol), and melted As an auxiliary agent, 0.196 g (2.00 mmol) of NH ₄ Br was weighed out and thoroughly mixed in an agate mortar. Thereafter, the obtained mixture was filled in a heat-resistant container and baked at 900 ° C. in the air for 3 hours, and then baked at 900 ° C. in a reducing atmosphere for 3 hours. The obtained fired product was pulverized, washed with water, and dried to obtain a silicate phosphor having the above composition.

The synthesis of the phosphor having the composition formula (Ba _0.2 Sr _0.8 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 was performed by first adding 0.389 g (1.97 mmol) of BaCO ₃ and SrCO _3. 1.163 g (7.88 mmol), MgCO ₃ 0.481 g (5.00 mmol), SiO ₂ 0.601 g (10.00 mmol), Eu ₂ O ₃ 0.0265 g (0.075 mmol), and melted As an auxiliary agent, 0.196 g (2.00 mmol) of NH ₄ Br was weighed out and thoroughly mixed in an agate mortar. Thereafter, the obtained mixture was filled in a heat-resistant container and fired at 900 ° C. in the air for 3 hours, and then fired at 1000 ° C. in a reducing atmosphere for 3 hours. The obtained fired product was pulverized, washed with water, and dried to obtain a silicate phosphor having the above composition.

The synthesis of the phosphor having the composition formula (Ba _0.1 Sr _0.9 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 is performed by first adding 0.194 g (0.98 mmol) of BaCO ₃ and SrCO _3. 1.309 g (8.87 mmol), MgCO ₃ 0.481 g (5.00 mmol), SiO ₂ 0.601 g (10.00 mmol), Eu ₂ O ₃ 0.0265 g (0.075 mmol), and melted As an auxiliary agent, 0.196 g (2.00 mmol) of NH ₄ Br was weighed out and thoroughly mixed in an agate mortar. Thereafter, the obtained mixture was filled in a heat-resistant container and fired at 900 ° C. in the air for 3 hours, and then fired at 1000 ° C. in a reducing atmosphere for 3 hours. The obtained fired product was pulverized, washed with water, and dried to obtain a silicate phosphor having the above composition.

Composition formula _{Sr 1.97 · Mg · Si 2 O} 7: Synthesis of the phosphor of _{Eu 0.03,} first, a SrCO ₃ 1.454g (9.85mmol), the MgCO ₃ 0.481g (5.00mmol) , SiO ₂ 0.601 g (10.00 mmol), Eu ₂ O ₃ 0.0265 g (0.075 mmol), and NH ₄ Br 0.196 g (2.00 mmol) as a melting aid were weighed, respectively, Mix thoroughly in a mortar made of steel. Thereafter, the obtained mixture was filled in a heat-resistant container and baked at 900 ° C. in the air for 3 hours, and then baked at 1200 ° C. in a reducing atmosphere for 3 hours. The obtained fired product was pulverized, washed with water, and dried to obtain a silicate phosphor having the above composition.

(Example 2)
Next, the phosphor (Ba _0.5 Sr _0.5 ) _1.97 · Mg · Si synthesized in Example 1 above using a vacuum ultraviolet excimer lamp having central emission wavelengths of 147 nm and 173 nm as an excitation light source according to a conventional method. ₂ O ₇ : Eu _0.03 , (Ba _0.4 Sr _0.6 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.3 Sr _0.7 ) _1.97 · Mg _{· Si 2 O 7: Eu 0.03} , (Ba 0.25 Sr 0.75) 1.97 · Mg · Si 2 O 7: Eu 0.03, (Ba 0.2 Sr 0.8) 1.97 Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.1 Sr _0.9 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 and Sr _1.97 · Mg · Si ₂ O ₇ : Luminescence characteristics were evaluated using Eu _0.03 . As a comparative example, a commercially available CMS that was available for purchase was used, and the emission characteristics were also measured.

First, using a vacuum ultraviolet excimer lamp having central emission wavelengths of 147 nm and 173 nm as an excitation light source, emission spectra under excitation conditions of wavelengths of 147 nm and 173 nm were evaluated according to a conventional method. As a result, emission spectra of main phosphors under excitation conditions of wavelengths 147 nm and 173 nm are summarized in FIGS. And the wavelength value (maximum wavelength (nm)) of the spectrum peak in the emission spectrum of the phosphors under both excitation conditions of wavelengths 147 nm and 173 nm is summarized in the table of FIG.
As can be seen from the comparison of the spectra of the main phosphor examples shown in FIG. 1 and FIG. 2, in the Eu-activated silicate phosphor constituting the present invention, the Ba composition ratio in the host skeleton increases, that is, In the formula (1), x indicating the composition ratio of the component Ba is from 0 (phosphor indicating that the Ba component is not included in the composition formula) to 0.1, 0.2, 0.25, 0.3,. It was found that the peak of the emission spectrum shifts to the short wavelength side under both excitation conditions of wavelengths 147 nm and 173 nm as it increases successively to 4, 0.5.

  When the above spectral maximum was shifted to the short wavelength side, there was no significant difference in spectral shape such as formation of a new peak, except for a slight broadening of the spectral shape.

Next, the phosphor (Ba _0.5 Sr _0.5 ) _1.97 · Mg · Si synthesized in Example 1 above using a vacuum ultraviolet excimer lamp having central emission wavelengths of 147 nm and 173 nm as an excitation light source according to a conventional method. ₂ O ₇ : Eu _0.03 , (Ba _0.4 Sr _0.6 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.3 Sr _0.7 ) _1.97 · Mg _{· Si 2 O 7: Eu 0.03} , (Ba 0.25 Sr 0.75) 1.97 · Mg · Si 2 O 7: Eu 0.03, (Ba 0.2 Sr 0.8) 1.97 Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.1 Sr _0.9 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 and Sr _1.97 · Mg · Si ₂ O ₇ : CIE (International Co) representing the emission color of Eu _0.03 mmission on Illumination) The chromaticity in the color system and the x and y values in the (x, y) coordinates of the chromaticity were measured. As a comparative example, the above-mentioned CMS which is commercially available and can be obtained by purchase was used and measured together.

As a result of the measurement, in the case of excitation condition of wavelength 147 nm, (Ba _0.5 Sr _0.5 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 (x, y) = (0.161, 0. 030), (Ba _0.4 Sr _0.6 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (x, y) = (0.160, 0.037), (Ba _0.3 Sr _0.7 ) _1.97 · Mg · Si ₂ O ₇ : For Eu _0.03 , (x, y) = (0.159, 0.038), (Ba _0.25 Sr _0.75 ) _1.97 Mg · Si ₂ O ₇ : For Eu _0.03 , (x, y) = (0.160, 0.079), (Ba _0.2 Sr _0.8 ) _1.97 · Mg · Si ₂ O ₇ : In Eu _0.03 , (x, y) = (0.141, 0.136), (Ba _0.2 Sr _0.8 ) _1.97 · Mg · Si _{In 2} O ₇ : Eu _0.03 , (x, y) = (0.150, 0.144), and in Sr _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (x, y) = (0 132, 0.172).

  CMS as a comparative example showed (x, y) = (0.152, 0.047) in the case of the excitation condition of wavelength 147 nm.

Next, as a result of the measurement, in the case of the excitation condition of wavelength 173 nm, (Ba, _0.5 Sr _0.5 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 (x, y) = (0.166 , 0.036), (Ba _0.4 Sr _0.6 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (x, y) = (0.164, 0.046), (Ba _0.3 Sr _0.7 ) _1.97 · Mg · Si ₂ O ₇ : For Eu _0.03 , (x, y) = (0.163, 0.051), (Ba _0.25 Sr _0.75 ) _1.97 · Mg · Si ₂ O ₇ : For Eu _0.03 , (x, y) = (0.162, 0.101), (Ba _0.2 Sr _0.8 ) _1.97 · Mg · Si ₂ In O ₇ : Eu _0.03 , (x, y) = (0.140, 0.136), (Ba _0.2 Sr _0.8 ) _1.97 · Mg · _Si 2 _{O 7:} In _{Eu 0.03 (x, y) =} (0.143,0.127), Sr 1.97 · Mg · Si 2 O 7: In _{Eu 0.03} (x, y) = (0.133, 0.171).

  CMS as a comparative example showed (x, y) = (0.182, 0.108) in the case of the excitation condition of wavelength 147 nm.

  The measurement results are summarized in the table of FIG. Based on the measurement result of the phosphor synthesized in Example 1 above, the chromaticity (x, y) of light emission obtained under both excitation conditions of wavelengths 147 nm and 173 nm with respect to the Ba composition ratio (x). The x and y values were plotted and summarized in FIG.

  As shown in the table shown in FIG. 4 and FIG. 5, in the phosphor synthesized in Example 1 above, the Ba composition ratio in the host skeleton increases, that is, the composition of component Ba in the above formula (1). As x indicating the ratio increases from 0 (phosphor indicating that the Ba component is not included in the composition formula) to 0.1, 0.2, 0.25, 0.3, 0.4, and 0.5 sequentially, It was found that the emission color characteristics changed under both excitation conditions of wavelengths 147 nm and 173 nm.

  And by setting Ba composition ratio (x) = 0.25 and the value or more, in the phosphor synthesized in Example 1 above, the color of blue light emission from CMS as a comparative example under the excitation condition of wavelength 173 nm. It was found that a value smaller than the y value of the degree (x, y) can be realized.

  Next, the luminous efficiency of the phosphor synthesized in Example 1 was evaluated using a vacuum ultraviolet excimer lamp with a wavelength of 173 nm as an excitation light source and using CMS as a reference. As a method for evaluating the luminous efficiency, the luminance (Br) of the phosphor synthesized in Example 1 above was measured under the excitation condition of the wavelength 173, and the y value of the chromaticity (x, y) of the light emission was measured. Using the result, a value obtained by dividing the luminance (Br) of light emission, which is known as a parameter reflecting the luminous efficiency, by the y value of chromaticity (x, y) of light emission, that is, a (Br / y) value is calculated. Based on the Br / y value of CMS, a comparison method was adopted in which the Br / y value exhibited by the phosphor synthesized in Example 1 was increased.

As a result, on the basis of CMS, in the phosphor synthesized in Example 1 above, (Ba _0.5 Sr _0.5 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 is 1.8 times as large. , (Ba _0.4 Sr _0.6 ) _1.97 · Mg · Si ₂ O ₇ : 1.7 times in Eu _0.03 , (Ba _0.3 Sr _0.7 ) _1.97 · Mg · Si ₂ 1.9 times for O ₇ : Eu _0.03 , (Ba _0.25 Sr _0.75 ) _1.97 · Mg · Si ₂ O ₇ : 1.5 times for Eu _0.03 , (Ba _0.2 Sr _0.8 ) 2.1 times in _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 , (Ba _0.1 Sr _0.9 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 in, 1.5 fold _{and, Sr 1.97 · Mg · Si 2} O 7: was 3.9 times the _{Eu 0.03}

In any of the phosphors synthesized in Example 1 described above, it was found that the emission efficiency was improved as compared with CMS under the wavelength 173 nm excitation condition, which was 1.5 times or more.
(Example 3)
Next, the phosphor phosphor (Ba _0.3 Sr _0.7 ) _1.97 · Mg · Si ₂ O ₇ : Eu ₀ synthesized in Example 1 as the blue phosphor constituting the blue phosphor layer. _0.03 was used to _{make PDP100} , which is a plasma display panel shown in FIG.

  FIG. 7 is an exploded perspective view of the main part showing the structure of the PDP according to the embodiment of the present invention. 8 to 10 are cross-sectional views showing the main part of the structure of the PDP according to the embodiment of the present invention.

  In order to manufacture the PDP 100, first, the address electrode 9 made of Ag or the like and the dielectric layer 4 made of a glass-based material are formed on the back substrate 6, and then the glass-based material is also used. The partition wall 7 is formed by thick-film printing the configured partition wall material and performing blast removal using a blast mask.

  Next, phosphor layers 10 of red, green, and blue were sequentially formed in stripes on the partition walls 7 so as to cover the groove surfaces between the corresponding partition walls 7.

  Here, each phosphor layer 10 corresponds to red, green and blue, and 40 parts by weight of red phosphor particles (60 parts by weight of vehicle), 40 parts by weight of green phosphor particles (60 parts by weight of vehicle), and blue phosphor. 35 parts by weight of the particles (65 parts by weight of the vehicle) are mixed with the vehicle to form a phosphor paste, applied by screen printing, and then evaporated and volatile components in the phosphor paste are evaporated and removed by burning. Form. The phosphor layer 10 used in this example is composed of each phosphor particle having a median particle diameter of about 3 μm.

As for the materials of the phosphors other than blue, the red phosphor is a mixture of (Y, Gd) BO ₃ : Eu phosphor and Y ₂ O ₃ : Eu phosphor 1: 1, and the green phosphor is Zn ₂ SiO ₄ : Mn phosphor.

Next, the front substrate 1 and the rear substrate 6 on which the display electrode 2, the bus line 3, the dielectric layer 4 and the protective film 5 are formed are frit-sealed, the inside of the panel is evacuated, and then a discharge gas is injected. Seal. The discharge gas is a gas composed mainly of neon (Ne) and containing xenon (Xe) gas in such an amount that the composition ratio becomes 10%.
The PDP 100 according to this embodiment has a size of 3 type and a pitch of one pixel of 1000 μm × 1000 μm.

  In the PDP 100 of the surface discharge type color PDP apparatus as in the present embodiment, for example, a negative voltage is applied to one of the pair of display electrodes 2 (generally called a scan electrode), and the address electrode 9 and the other display electrode 2 are applied. By applying a positive voltage (a positive voltage compared to the voltage applied to the display electrode 2), a discharge is generated, thereby assisting in starting discharge between the pair of display electrodes 2. A wall charge is formed (this is called writing). When an appropriate reverse voltage is applied between the pair of display electrodes 2 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 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).

Next, the PDP 100 using the phosphor (Ba _0.3 Sr _0.7 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 constituting the above-described present invention is used in combination with a drive circuit. A PDP device configured to perform discharge and lighting driving and to perform image display was manufactured.

  This PDP apparatus can display an image with a deep blue color, has a beautiful image color, and has excellent display performance. The color PDP device produced in this way has a wide color reproducibility and high efficiency.

Further, in this example, detailed examination results for red and green phosphors are not shown, but PDPs can be similarly produced using phosphors having the following compositions. For example, the red phosphor is a kind selected from the group consisting of (Y, Gd) BO ₃ : Eu, (Y, Gd) ₂ O ₃ : Eu, (Y, Gd) (P, V) O ₄ : Eu. The above phosphors can be used. Also, as the green _{phosphor, Zn 2 SiO 4: Mn,} (Y, Gd, Sc) 2 SiO 5: Tb, (Y, Gd) 3 (Al, Ga) 5 O 12: Tb, (Y, Gd) One or more phosphors selected from the group consisting of ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Gd) B ₃ O ₆ : Tb, and (Y, Gd) PO ₄ : Tb are available. is there. Furthermore, combinations with phosphors not shown here are also applicable.

For the blue phosphor, the above Ba _0.3 Sr _0.7 ) _1.97 · Mg · Si ₂ O ₇ : Eu _0.03 or the like is used in order to realize desired characteristics in consideration of color characteristics and the like. In addition to Eu activated silicate phosphors represented by the general formula (1), the conventional blue light emitting phosphors BaMgAl ₁₀ O ₁₇ : Eu, CaMgSi ₂ O ₆ : Eu and Sr ₃ MgSi ₂ O ₈ : Eu A combination of one or more phosphors selected from the group can also be used. In this case, the mixing ratio can be adjusted and controlled in consideration of a composition that can express a preferable blue color in the design of the PDP device, and further considering the luminance performance. Furthermore, combinations with phosphors not shown here are also applicable.

  As mentioned above, the invention made by the present inventor has been specifically described based on the embodiment. However, the present invention is not limited to the embodiment, and various modifications can be made without departing from the scope of the invention. It is.

  INDUSTRIAL APPLICABILITY The present invention can be used for a PDP using an Eu-activated silicate phosphor that emits light when excited by ultraviolet rays, and a PDP device that displays an image by accompanying a drive circuit and an image source for driving the PDP. Can be used.

It is the emission spectrum in wavelength 147nm excitation conditions of the main fluorescent substance among the examples of the novel fluorescent substance which comprises this invention. It is the emission spectrum in wavelength 173nm excitation conditions of the main fluorescent substance among the examples of the novel fluorescent substance which comprises this invention. It is the table | surface which put together the wavelength value of the spectrum peak in the emission spectrum of the example of the novel fluorescent substance which comprises this invention in both wavelength 147nm and 173nm excitation conditions. It is the table | surface which put together the x value and y value of chromaticity (x, y) of light emission under the excitation conditions of wavelength 147nm and 173nm of the novel fluorescent substance which comprises this invention. The graph which plotted the x value and y value of the chromaticity (x, y) of light emission obtained under both excitation conditions of wavelength 147 nm and 173 nm with respect to Ba composition ratio (x) in the novel phosphor constituting the present invention. It is. It is a graph which shows the relationship between Xe composition ratio in discharge gas and intensity ratio in an AC type plasma display panel. It is a disassembled perspective view which shows the structure of the plasma display panel which is one embodiment of this invention. It is a principal part exploded sectional view which shows the structure of the plasma display panel which is one embodiment of this invention. It is a principal part exploded sectional view which shows the structure of the plasma display panel which is one embodiment of this invention. It is a principal part exploded sectional view which shows the structure of the plasma display panel which is one embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Electrode 3 Bus line 4 Dielectric layer 5 Protective film 6 Substrate 7 Partition 8 Dielectric layer 9 Electrode 10 Phosphor layer 100 Plasma display panel.

Claims (9)

A pair of substrates opposed to each other at an interval;
A partition provided between the pair of substrates and forming a space between the pair of substrates;
An electrode pair disposed on at least one of the opposing surfaces of the pair of substrates;
A discharge gas enclosed in a space formed by the partition walls and generating ultraviolet rays by a discharge caused by a voltage applied to the electrode pair;
Formed on at least one of the opposing surfaces of the pair of substrates in the space and the wall surface of the partition wall, and is composed of a phosphor layer containing a phosphor that emits light when excited by the ultraviolet rays,
The discharge gas is a gas that includes Xe gas in an amount such that the composition ratio is 6% or more,
The said fluorescent substance contains Eu activated silicate type | system | group fluorescent substance represented by following General formula (1), The plasma display apparatus characterized by the above-mentioned.
(Ba _x Sr _1-x ) _2-e · M1 · Si ₂ O ₇ : Eu _e (1)
(In the formula, M1 is one or more elements selected from the group consisting of Mg and Zn, and x indicating the composition ratio of component Ba and e indicating the composition ratio of Eu are 0 <x ≦ 0. 5, 0.001 ≦ e ≦ 0.2)   2. The plasma display device according to claim 1, wherein x indicating the composition ratio of the component Ba of the Eu activated silicate phosphor represented by the general formula (1) is 0.2 ≦ x ≦ 0.5. A plasma display device.   3. The plasma display device according to claim 2, wherein x indicating the composition ratio of the component Ba is 0.25 ≦ x ≦ 0.5.   4. The plasma display device according to claim 3, wherein x indicating the composition ratio of the component Ba is 0.3 ≦ x ≦ 0.4.   5. The plasma display device according to claim 1, wherein the discharge gas is a gas containing Xe in an amount such that a composition ratio is 10% or more. 6. apparatus.   6. The plasma display device according to claim 5, wherein the discharge gas is a gas containing Xe in an amount such that the composition ratio is 12% or more.   The plasma display device according to any one of claims 1 to 6, wherein a phosphor layer made of any one of a red phosphor, a green phosphor, and a blue phosphor is formed for each of the spaces, and the blue fluorescence The plasma display device, wherein the body includes an Eu activated silicate phosphor represented by the general formula (1). 8. The plasma display device according to claim 7, wherein the blue phosphor includes, together with the Eu activated silicate phosphor represented by the general formula (1), BaMgAl ₁₀ O ₁₇ : Eu, CaMgSi ₂ O ₆ : Eu and Sr. A plasma display device comprising at least one phosphor selected from the group consisting of ₃ MgSi ₂ O ₈ : Eu. 9. The plasma display device according to claim 7, wherein the red phosphor is (Y, Gd) BO ₃ : Eu, Y ₂ O ₃ : Eu, (Y, Gd) ₂ O ₃ : Eu, and (Y, Gd). ) (P, V) O ₄ : One or more phosphors selected from the group consisting of Eu, and the green phosphor is Zn ₂ SiO ₄ : Mn, (Y, Gd, Sc) ₂ SiO ₅ : Tb. , (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Tb, (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Gd) B ₃ O ₆ : Tb and (Y, Gd) A plasma display device comprising one or more phosphors selected from the group consisting of PO ₄ : Tb.

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