JP2009001699A - Red-emitting phosphor, fed device, and eld device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a red-emitting phosphor containing ZnGa<SB>2</SB>S<SB>4</SB>as a matrix material, in particular, a red-emitting phosphor which exhibits a light emission of high brightness in a red area with high visual sensitivity. <P>SOLUTION: The red-emitting phosphor contains ZnGa<SB>2</SB>S<SB>4</SB>as the matrix material and contains Mn (manganese) and La (lanthanum). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a phosphor used in a display device, a lighting device, and the like, and particularly relates to a red light emitting phosphor. The present invention also relates to an FED device and an ELD device having such a red light emitting phosphor.

  Conventionally, powders or thin film phosphors using rare earth elements have been widely used in the field of display devices such as field emission display (FED) and lighting devices.

In particular, M ^II M ₂ ^III S ₄ (where M ^II is Mg, Ca, Sr, Ba, Zn, or a combination thereof, and M ^III is Ga, In, or a combination thereof. A material obtained by adding a rare earth ion to the base material is used as a phosphor for many light emission such as photoluminescence, electroluminescence, and cathodoluminescence. For example, in a phosphor using SrGa ₂ S ₄ and CaGa ₂ S ₄ as a base material, a blue light emitting phosphor that emits light in a blue region (wavelength of about 420 nm to 460 nm) can be obtained by adding Ce ³⁺ ions as an emission center. Can be produced. Further, when Eu ²⁺ ions are added to the above-described base material, a green light-emitting phosphor that emits light in a green region (wavelength of about 530 nm to 570 nm) can be manufactured (for example, Patent Document 1).

On the other hand, as phosphors emitting at a wavelength of about 600 nm to 750 nm, which is a red region, some studies have been conducted on BaIn ₂ S ₄ : Eu, CaIn ₂ S ₄ : Eu, SrIn ₂ S ₄ : Eu, and the like. However (Non-Patent Document 1), this material has many problems to be solved such as low emission luminance and poor color purity, and has not been put into practical use at present. Therefore, generally, when obtaining red light emission, phosphors other than M ^II M ₂ ^III S ₄ system such as Y ₂ O ₃ : Eu or CaS: Eu system are used.
JP 2006-124552 A Georgobiani AN, Dzhabbrarov RB, Izzatov BM et al., INORGANIC MATERIALS, 33 (2), p148-152, 1997 Miura, Hidaka, Takizawa, “Emission spectrum of SrGa2S4 with double addition of Mn and Ce”, 67th JSAP Scientific Lecture Proceedings p29-H6, p. 1311 Bird G, Vecht A. et al. Smith P .; J. et al. F. Electrochem. Soc. Meeting, San Francisco, Abstr. 92 (1974)

Here, for example, when manufacturing a phosphor for an FED device, it is necessary to emit light of three primary colors, that is, blue, green, and red. Therefore, the M ^II M ₂ ^III S ₄ system material and the others However, such phosphors may have the following problems caused by different base materials.

  In the FED apparatus, since the intensity of the electron beam irradiated to each color phosphor as an excitation energy source is constant, the behavior of charge-up by the electron beam differs between red and other color phosphors. In addition, due to this influence, the balance of light emission of each phosphor is lost, and color adjustment is required between red and other colors in order to maintain color development appropriately. Further, since the base materials are different, the lifetimes of the phosphors of the respective colors are different, and if any one of the phosphors is deteriorated, the apparatus cannot be used even if the characteristics of the remaining phosphors are not deteriorated. Furthermore, the manufacturing process of the phosphor becomes complicated, and the manufacturing cost increases.

Recently, it has been reported that a phosphor obtained by simultaneously adding Ce and Mn ions to a SrGa ₂ S ₄ base material emits red light (Non-patent Document 2). In addition, it has been reported that light is obtained in a red region (wavelength of 630 to 670 nm) in a material system in which Mn is added to ZnGa ₂ S ₄ (Non-patent Document 3).

  However, the light emission of the former material has a peak wavelength in the vicinity of 700 nm, and there is a problem that in this region, the visibility is extremely low and the luminance is low. In addition, the latter material has a problem of low emission luminance.

In the present invention, it is an object to provide a red light-emitting phosphor using ZnGa ₂ S ₄ as a base material in order to eliminate the problems of color adjustment due to the difference in charge-up, the difference in life and the problem of manufacturing cost as described above. And In particular, the red light emitting phosphor according to the present invention can emit light with high luminance in a red region having high visibility. Another object of the present invention is to provide an FED device and an ELD device using such a red light-emitting phosphor.

The present invention provides a red light-emitting phosphor containing ZnGa ₂ S ₄ as a base material and containing Mn (manganese) and La (lanthanum).

In particular, in the red light emitting phosphor, Mn is contained 0.006 to 0.09 per Zn ion,
La may be contained in an amount of 0.001 to 1.3 per Zn ion.

In the present invention,
A cold cathode device installed on the cathode layer and having a plurality of electron emitters installed in the opening; and
An anode provided with a phosphor layer on the side facing the cold cathode element;
Have
A field emission display (FED) device in which a phosphor emits light by electrons emitted from the cold cathode device,
An FED device is provided in which the phosphor layer includes the above-described red light-emitting phosphor.

Furthermore, in the present invention,
An electroluminescent display (ELD) device having an insulating layer on one side or both sides of a phosphor layer and further having electrodes to which a voltage can be applied on both sides of the insulating layer,
An ELD device is provided in which the phosphor layer includes the aforementioned red light-emitting phosphor.

In the present invention, a red light-emitting phosphor having ZnGa ₂ S ₄ as a base material and exhibiting high-luminance light emission can be obtained. In addition, it is possible to provide an FED device and an ELD device including such a red light emitting phosphor.

  Hereinafter, the features of the present invention will be described in more detail.

In the present invention, there is provided a red light emitting phosphor using ZnGa ₂ S ₄ as a base material and containing Mn and La.

  Here, the term “red light-emitting phosphor” refers to a phosphor that, when excited, has a red color, that is, a peak of emission intensity in a wavelength range of 600 nm to 750 nm.

In general, it is known that Mn does not emit light even when added to a phosphor having M ^II M ₂ ^III S ₄ as a base material. Recently, it has been reported that red light emission can be obtained by adding Mn and Ce to an M ^II M ₂ ^III S ₄ base material, but this phosphor has low visibility. Since light emission occurs only in the region (near the wavelength of 700 nm), there is a problem that luminance is low and practical application is difficult.

In contrast, the inventors of the present application added color purity to a region where the visibility is increased by adding Mn and La to the ZnGa ₂ S ₄ system, which is a kind of M ^II M ₂ ^III S ₄ system. It was found that red light emission with good brightness and high luminance can be obtained.

Note that the clear cause of high-luminance red light emission by adding Mn and La to the ZnGa ₂ S ₄ system is unknown at present. However, addition of Mn alone does not cause light emission in the red region, so it is considered that La plays a role in promoting light emission of Mn, which is the light emission center of this material system. For example, when Mn is added to a SrGa ₂ S ₄ matrix material, it is considered that Ga atoms in the phosphor matrix material are replaced with Mn atoms as dopants. However, this substitution alone does not provide an activity enough to emit Mn even when an excitation energy source such as an electron beam is applied. On the other hand, when La is further added to SrGa ₂ S ₄ , it is considered that Sr atoms in the host material of the phosphor are replaced with La atoms, and thereby Mn is more easily activated.

  The phosphor according to the present invention can be manufactured, for example, by the following method.

First, a mixed powder of ZnGa ₂ S ₄ base material powder, a predetermined amount of Mn source powder, and a predetermined amount of La source powder is prepared. Instead of ZnGa ₂ S ₄ base material powder, powders of sulfides, oxides, carbonates, oxalates, and the like of Zn and Ga may be used. The average diameter of the ZnGa ₂ S ₄ base material powder is not particularly limited, but is, for example, in the range of 0.1 μm to 20 μm. As the Mn source powder, any form of metal Mn can be used as long as it can be sulfided with hydrogen sulfide gas, such as sulfide, oxide, carbonate, oxalate. The particle size of the Mn source powder is, for example, in the range of 0.1 μm to 20 μm. Similarly, the La source powder may be in any form as long as it can be sulfided with hydrogen sulfide gas, such as sulfides, oxides, carbonates, and oxalates, in addition to metals. The average diameter of the La source powder is, for example, in the range of 0.1 μm to 20 μm. For powder mixing, either a dry method or a wet method may be used. In the case of a dry method, for example, a ball mill may be used for pulverization and mixing.

Next, the obtained mixed powder is fired. Firing is performed, for example, by putting the above-described mixed powder into a quartz boat, heat-treating it in an electric furnace, and then rapidly cooling it. Usually, the heat treatment atmosphere is an inert gas atmosphere such as argon or a mixed atmosphere containing about 5 vol% of H ₂ S (hydrogen sulfide) gas. In normal cases, the firing temperature is about 600 ° C. to 1200 ° C., and preferably about 1000 ° C. to 1050 ° C. The firing time is, for example, about 30 minutes to 3 hours.

  The fired body obtained by the firing treatment may be used as it is, or may be used after pulverization.

  On the other hand, the red light emitting phosphor of the present invention can be provided as a thin film in addition to the powder.

  When the red light-emitting phosphor of the present invention is manufactured as a thin-film phosphor, this phosphor is a vapor deposition method including CVD (chemical vapor deposition), PVD (physical vapor deposition) and electron beam vapor deposition, Alternatively, it can be formed by sputtering or the like.

For example, when a red light emitting phosphor using ZnGa ₂ S ₄ as a base material, Mn as a light emission center and La as a co-additive is added using a vapor deposition method, metal Zn, _Ga 2 _{S 3,} metal Mn, respective materials of _La 2 Cl ₃ is prepared. Next, the phosphor according to the present invention can be formed by depositing these evaporation sources on the substrate while maintaining the substrate temperature at 500 ° C. or higher. The thickness of the thin film can be freely adjusted by changing the deposition time.

In addition, in the case where a red light emitting phosphor in which ZnGa ₂ S ₄ is used as a base material and Mn as a light emission center and La as a co-additive are added by an electron beam evaporation method, ZnS is used. Two types of evaporation sources are used: an evaporation source obtained by mixing and pressing a Mn compound, and a Ga ₂ S ₃ evaporation source containing La. That is, by simultaneously evaporating these evaporation sources and supplying them on a substrate maintained at a temperature of 500 ° C. or higher, the phosphor according to the present invention can be formed into a thin film. Also in this case, the thickness of the thin film can be freely adjusted by changing the deposition time.

  After film formation, as a post-heat treatment, lamp heating or laser heating may be performed in an inert gas atmosphere or a mixed gas atmosphere of an inert gas and hydrogen sulfide (for example, 5 vol%). This makes it possible to improve the characteristics of the thin film phosphor.

On the other hand, in the sputtering method, a mixed material obtained by adding Mn and La to a base material of ZnGa ₂ S ₄ is used as a target. Argon gas or a mixed gas of argon gas and hydrogen sulfide gas (5 vol%) is used as a sputtering gas source. That is, a thin film phosphor is formed on a substrate by sputtering the sputtering gas at a gas pressure of 0.1 to several Pa on a substrate heated in a range of room temperature to about 600 ° C. The thickness of the thin film can be freely adjusted by changing the sputtering time. Thereafter, as post-heat treatment, lamp heating or laser heating may be performed in an inert gas atmosphere or a mixed gas atmosphere of an inert gas and hydrogen sulfide (for example, 5%). This makes it possible to improve the characteristics of the thin film phosphor.

  Such a phosphor according to the present invention can be used as a phosphor for a FED (field emission display) device, for example, as a light emitting phosphor in a red region.

  FIG. 1 shows an example of an FED apparatus to which the red light emitting phosphor of the present invention can be applied.

  The FED apparatus 100 shown in FIG. 1 has two glass substrates 10A and 10B arranged at a predetermined interval and substantially parallel to each other, and a vacuum chamber is provided between these glass substrates. Is formed.

  The cathode layer 20 and the cold cathode element 30 are laminated in this order on the inner surface (that is, the vacuum side surface) of one glass substrate 10A. The cold cathode element 30 includes a silicon substrate 60, an insulating layer 50 disposed on the silicon substrate 60, and a gate electrode 40 disposed on the insulating layer 50. The insulating layer 50 is provided with openings 80 at a predetermined periodic interval, and the insulating layer 50 and the gate electrode 40 are not present in the opening 80. Instead, a cone-shaped electron emitter 70 is formed in the opening 80 so that the tip protrudes from the height level position of the insulating layer 50. However, the tip of the electron emitter 70 is at a height level equivalent to the height level of the gate electrode 40 and does not protrude from the opening 80. The bottom surface of the electron emitter 70 is in contact with the surface of the silicon substrate 60.

  An anode layer 90 and a phosphor layer 120 are laminated in this order on the inner surface (that is, the vacuum side) of the other glass substrate 10B. The phosphor layer 120 includes three types of phosphors that emit light in the blue, green, and red regions, and these phosphors are arranged on the anode layer 90 in a regular arrangement, that is, corresponding to each pixel. Is installed.

  In the FED device 100 configured as described above, when a potential V1 is applied between the cathode layer 20 and the gate electrode 40, a strong electric field is generated at the tip of the electron emitter 70, and thereby, from the tip of the electron emitter 70. Electrons are emitted toward the glass substrate 10B.

  Further, a potential V2 is also applied between the anode layer 90 and the cathode layer 20, and the emitted electrons e are accelerated by the electric field generated by this potential V2, and emit light of each color of blue, green and red. It collides with the phosphor layer 120 provided with the phosphor shown. Due to this electron collision, the phosphor contained in the phosphor layer 120 emits light, and blue, green, and red light emission corresponding to each pixel is generated. Thus, a color image can be obtained.

Here, in the conventional FED device, the phosphor layer is a light emitting phosphor in each of the blue, green, and red regions, and M ^II M ₂ ^III S ₄ : Ce, M ^II M ₂ ^III S ₄ : Eu, respectively. (Wherein M ^II is any one of Mg, Ca, Sr, Ba, Zn, or a combination thereof, and M ^III is any one of Ga, In, or a combination thereof), and Y ₂ It has O ₃ : Eu or CaS: Eu.

  However, when the phosphor layer is composed of such a different material system of the host material, even if the phosphor layer is irradiated with the electron beam under the same conditions, the charge-up behavior of the phosphor is different. A phenomenon occurs in which the color balance shifts with time. Accordingly, it is necessary to appropriately monitor such a color balance shift and adjust the color balance shift. In addition, since the material system is different, the service life may be greatly different for each color phosphor. In such a case, even if the phosphor that emits light of a certain color is not deteriorated, the entire phosphor layer cannot be used due to the deterioration of one material, resulting in a short device life. Problems arise. Furthermore, it is necessary to individually adjust a plurality of materials when manufacturing the phosphor layer, which causes a problem that the manufacturing cost of the phosphor layer and further the phosphor of the FED device increases.

On the other hand, in the FED device of the present invention, the phosphor layer 120 has M ^II M ₂ ^III S ₄ : Ce and M ^II M ₂ ^III S as the light emitting phosphors in the blue, green and red regions, respectively. ₄ : Eu and ZnGa ₂ S ₄ as a base material, and having a red light emitting phosphor in which La and Mn are added thereto (where M ^II is any one of Mg, Ca, Sr, Ba, Zn, Or a combination thereof, and ^MIII is either Ga or In, or a combination thereof).

In this case, since the phosphor layers 120 for light emission of each color are made of the same base material, that is, a material of M ^II M ₂ ^III S ₄ system, the degree of charge-up of the phosphors of each color is almost equal. The lifetimes of the phosphors of the respective colors can be made substantially the same. Therefore, the problem of adjusting the color balance due to charge-up and the problem that the difference in the life of each phosphor is increased are unlikely to occur in the phosphor device of the conventional FED device. Furthermore, when the phosphor layer 120 is manufactured, the phosphors for the three primary colors can be easily obtained by simply changing the elements to be added based on the same base material, thereby significantly reducing the manufacturing cost. it can.

  In the above-described example, the application example of the present invention has been described using the FED device including the red light-emitting phosphor according to the present invention in the phosphor layer as an example. However, it will be apparent to those skilled in the art that the red light-emitting phosphor according to the present invention can be applied to other display devices such as an ELD (electroluminescent display) device and a lighting device.

  As known to those skilled in the art, an ordinary ELD device includes a transparent electrode 220, an insulating layer 230, a phosphor layer 240, an insulating layer 250, and a metal electrode 260 on a transparent substrate 210 as shown in FIG. It is configured by stacking in this order. However, in the ELD device 200 according to the present invention, the red light emitting phosphor according to the present invention is installed in the phosphor layer 240. In the figure, 270 represents electroluminescent light emission.

Examples of the present invention will be described below.
Example 1
In Example 1, a phosphor containing ZnGa ₂ S ₄ as a base material, containing Mn as an emission center and La as a co-additive was produced by the following method.

First, ZnGa ₂ S ₄ powder having an average particle diameter of 1 μm (purity 99.99%, manufactured by High Purity Chemical Co., Ltd.) and MnCO ₃ powder having an average particle diameter of 1 μm (purity 99.99%, high purity chemical). And a La ₂ S ₃ powder (99.9%, high purity chemical) with an average particle diameter of 1 μm, and a mill mixer (model number 8000: Specs) ) For 30 minutes to obtain a mixed raw material powder. Here, La ₂ S ₃ was added so that x in the following formula (1) was 0.0005. Further, MnCO _3, to the ZnGa ₂ S ₄ powder and _La 2 _{S 3} powder mixed powder was added at a ratio of 2 mol%.

(1-x) ZnGa ₂ S ₄ + xLa ₂ S ₃ +0.02 MnCO ₃ Formula (1)

Next, about 4 g of this mixed raw material powder was placed in a quartz boat and placed in an electric furnace. Next, the atmosphere in the electric furnace was changed to an argon + 5 vol% hydrogen sulfide atmosphere, the quartz boat was held at 1000 ° C. for 1 hour, and the mixed raw material powder was fired.

The obtained powder was pulverized to an average particle size of about 1 μm using a mortar to obtain a phosphor powder according to Example 1.
(Examples 2-9)
A phosphor containing ZnGa ₂ S ₄ as a base material, containing Mn as an emission center and La as a co-additive was produced by the same method as in Example 1 described above. However, in these examples, x (that is, La ₂ S ₃ ) in the formula (1) was changed in the range of 0.0015 to 0.4. Further, MnCO _3, to the ZnGa ₂ S ₄ powder and _La 2 _{S 3} powder mixed powder was added at a ratio of 2 mol%. Table 1 shows the value of x in each example.

（実施例１０〜１２）
前述の実施例１と同様の方法により、ＺｎＧａ_２Ｓ_４を母体材料とし、これに発光中心としてＭｎを含み、共添加剤としてＬａを含む蛍光体を作製した。ただしこれらの実施例では、式（１）のｘ（すなわちＬａ_２Ｓ_３）は、０．６から１の範囲で変化させた。また、ＭｎＣＯ_３は、ＺｎＧａ_２Ｓ_４粉末とＬａ_２Ｓ_３粉末の混合粉末に対して、２ｍｏｌ％添加した。それぞれの実施例におけるｘの値を表１に示した。
（比較例１）
前述の実施例１と同様の方法により、ＺｎＧａ_２Ｓ_４を母体材料とし、これに発光中心としてＭｎを含む蛍光体を作製した。ただしこの比較例では、Ｌａ_２Ｓ_３は、添加していない（すなわちｘ＝０）。なお、ＭｎＣＯ_３は、ＺｎＧａ_２Ｓ_４粉末に対して、２ｍｏｌ％添加した。
（蛍光体の特性評価１）
前述の方法で製作された実施例１〜１２および比較例１の粉末蛍光体に、紫外線（波長約３６５ｎｍ）を照射して発光特性を評価した。

(Examples 10 to 12)
A phosphor containing ZnGa ₂ S ₄ as a base material, containing Mn as an emission center and La as a co-additive was produced by the same method as in Example 1 described above. However, in these examples, x (that is, La ₂ S ₃ ) in the formula (1) was changed in the range of 0.6 to 1. Further, 2 mol% of MnCO ₃ was added to the mixed powder of ZnGa ₂ S ₄ powder and La ₂ S ₃ powder. Table 1 shows the value of x in each example.
(Comparative Example 1)
In the same manner as in Example 1, a phosphor containing ZnGa ₂ S ₄ as a base material and containing Mn as an emission center was produced. However, in this comparative example, La ₂ S ₃ is not added (that is, x = 0). Note that 2 mol% of MnCO ₃ was added to the ZnGa ₂ S ₄ powder.
(Characteristic evaluation of phosphor 1)
The powder phosphors of Examples 1 to 12 and Comparative Example 1 manufactured by the method described above were irradiated with ultraviolet rays (wavelength of about 365 nm) to evaluate the light emission characteristics.

Table 1 shows the emission luminance obtained with each phosphor. Further, FIG. 1 shows a change in emission luminance with respect to the amount of La ₂ S ₃ contained in the phosphor (value of x in formula (1)). From these results, when x is 0.0005 (Example 1) to 0.4 (Example 9), the light emission luminance is the value of the phosphor not containing La (Comparative Example 1) (approximately 2. 1 cd / m ² ). In particular, when x is in the range of 0.05 (Example 5) to 0.2 (Example 8), the light emission luminance is extremely high. The emission spectra of the phosphors according to Examples 1 to 9 have a peak at about 645 nm. For example, in the phosphor according to Example 8, CIE chromaticity coordinates (x, y) = (0.658, 0.341) (red region).

From the formula (1), the number of La ions per Zn ion is represented by 2x / (1-x). Therefore, when x is in the range of 0.0005 (Example 1) to 0.4 (Example 9), the number of La ions per Zn ion is in the range of 0.001 to 1.3.
(Examples 13 to 16)
In Example 13, the phosphor according to Example 2 described above was prepared by firing again at 1050 ° C. for 1 hour. The firing atmosphere was an argon + 5 vol% hydrogen sulfide atmosphere. In the same manner, the phosphors according to Examples 4, 7 and 8 were refired to obtain phosphors according to Examples 14, 15 and 16, respectively.
(Characteristic evaluation of phosphor 2)
The powder phosphors of Examples 13 to 16 manufactured by the above-described method were irradiated with ultraviolet rays (wavelength of about 365 nm) to evaluate the light emission characteristics. Table 1 shows the emission luminance obtained with each phosphor. Further, FIG. 3 shows a change in emission luminance with respect to the amount of La ₂ S ₃ added to the mixed powder (the value of x in formula (1)). From these results, it can be seen that the brightness of the emission spectrum is increased by baking at 1050 ° C. except for Example 16 where the value of x is 0.2.

Considering the above results and the results of the phosphor property evaluation 2, when the amount of La ₂ S ₃ , that is, the value of x in the formula (1) is in the range of 0.1 to 0.13, the phosphor powder is 1000 It can be said that it is preferable to perform the baking at a baking temperature of 1050C.
(Example 17)
In Example 17, a phosphor containing ZnGa ₂ S ₄ as a base material, containing Mn as the emission center and La as a co-additive was produced by the following method.

First, ZnGa ₂ S ₄ powder having an average particle diameter of 1 μm (purity 99.99%, manufactured by High Purity Chemical Co., Ltd.) and MnCO ₃ powder having an average particle diameter of 1 μm (purity 99.99%, high purity chemical). And a La ₂ S ₃ powder (99.9%, high purity chemical) with an average particle diameter of 1 μm, and a mill mixer (model number 8000: Specs) ) For 30 minutes to obtain a mixed raw material powder. Here, MnCO ₃ was added so that y in the following formula (2) was 0.005. Further, ZnGa ₂ S ₄ powder and _La 2 _{S 3} powder, the molar ratio therebetween, respectively, were added to a 0.87 and 0.13.

0.87ZnGa ₂ S ₄ + 0.13La ₂ S ₃ + yMnCO ₃ formula (2)

Next, about 4 g of this mixed raw material powder was placed in a quartz boat and placed in an electric furnace. Next, the atmosphere in the electric furnace was changed to an argon + 5 vol% hydrogen sulfide atmosphere, the quartz boat was held at 1050 ° C. for 2 hours, and the mixed raw material powder was fired.

The obtained powder was pulverized to an average particle size of about 1 μm using a mortar to obtain a phosphor powder according to Example 17.
(Examples 18 to 21)
A phosphor containing ZnGa ₂ S ₄ as a base material, containing Mn as an emission center and La as a co-additive was produced in the same manner as in Example 17 described above. However, in these examples, y in Formula (2) (that is, MnCO ₃ ) was changed in the range of 0.01 to 0.08. Further, ZnGa ₂ S ₄ powder and _La 2 _{S 3} powder, the molar ratio therebetween, respectively, were added to a 0.87 and 0.13. The value of y in each example is shown in Table 2.

（蛍光体の特性評価３）
前述の方法で製作された実施例１７〜２１の粉末蛍光体に、紫外線（波長約３６５ｎｍ）を照射して発光特性を評価した。表２には、各蛍光体で得られた発光輝度を示す。また、図４には、混合粉末に添加したＭｎＣＯ_３量（式（２）のｙの値）に対する発光輝度の変化を示す。これらの結果から、ｙが０．００５〜０．０８の範囲にある蛍光体による発光は、いずれも高い輝度を示すことがわかる。なお、式（２）より、このｙの範囲では、Ｚｎイオン１個当たり、Ｍｎイオンは、０．００６〜０．０９個含まれることになる。

(Characteristic evaluation of phosphor 3)
The powder phosphors of Examples 17 to 21 manufactured by the above-described method were irradiated with ultraviolet rays (wavelength: about 365 nm) to evaluate the light emission characteristics. Table 2 shows the light emission luminance obtained with each phosphor. In addition, FIG. 4 shows changes in emission luminance with respect to the amount of MnCO ₃ added to the mixed powder (the value of y in formula (2)). From these results, it can be seen that light emitted by the phosphor having y in the range of 0.005 to 0.08 exhibits high luminance. In addition, from Formula (2), 0.006-0.09 Mn ion is contained per Zn ion in this y range.

  The red light-emitting phosphor of the present invention emits light by irradiating the phosphor with an excitation energy source such as an electron beam, ultraviolet light, X-rays, or an electric field. For example, a red light-emitting phosphor for display devices such as FED and EL, or illumination Can be used as

It is an example of the FED apparatus with which the red light emission fluorescent substance which concerns on this invention was installed as a part of fluorescent substance layer. It is an example of the ELD device in which the red light emitting phosphor according to the present invention is installed as a part of the light emitting layer. It is a graph showing the effect of light emission luminance with respect to the amount of La ₂ S ₃ contained in the phosphor according to the present invention (the value of x in formula (1)). Is a graph showing the effect of light emission luminance with respect to the amount of MnCO ₃ contained in the phosphor according to the present invention (the value of y in equation (2)).

Explanation of symbols

10A, 10B Glass substrate 20 Cathode layer 30 Cold cathode element 40 Gate electrode 50 Insulating layer 60 Silicon substrate 70 Electron emitter 80 Opening 90 Anode layer 100 FED device 120 Phosphor layer 200 ELD device 210 Transparent substrate 220 Transparent electrode 230 Insulating layer 240 Phosphor layer 250 Insulating layer 260 Metal electrode.

Claims (4)

A red light-emitting phosphor containing ZnGa ₂ S ₄ as a base material and containing Mn (manganese) and La (lanthanum). Mn is contained 0.006 to 0.09 per Zn ion,
The red light emitting phosphor according to claim 1, wherein La is contained in an amount of 0.001 to 1.3 per Zn ion. A cold cathode device installed on the cathode layer and having a plurality of electron emitters installed in the opening; and
An anode provided with a phosphor layer on the side facing the cold cathode element;
Have
A field emission display (FED) device in which a phosphor emits light by electrons emitted from the cold cathode device,
The FED device according to claim 1, wherein the phosphor layer includes the red light-emitting phosphor according to claim 1. An electroluminescent display (ELD) device having an insulating layer on one side or both sides of a phosphor layer and further having electrodes to which a voltage can be applied on both sides of the insulating layer,
The ELD device according to claim 1, wherein the phosphor layer includes the red light-emitting phosphor according to claim 1.

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