TWI397572B - Blue emitting zns phosphors doped with an activator and a manufacturing method therefor - Google Patents

Description

Blue zinc sulfide fluorescent material doped with activator and preparation method thereof

The invention relates to a blue zinc sulfide fluorescent material doped with an activator and a preparation method thereof; in particular to a zinc sulfide fluorescent material and a preparation method thereof, which utilize a first activator (for example: barium fluoride or The cerium chloride] and a second activator (for example, manganese dioxide) are doped to the zinc sulfide fluorescent material, so that the zinc sulfide fluorescent material can be mixed to emit blue light and yellow orange light to form white light.

In general, phosphors are widely used as luminescent materials for illumination devices, imaging devices, and display devices. The use of a suitable activator doping dopant material is quite common for improving the luminescent properties of fluorescent materials.

In fact, the use of appropriate materials (such as: transition metal and rare earth material) to activate the doping technology, can change the luminescent wavelength characteristics of the fluorescent material, in order to achieve the purpose of adjusting its luminescent color, Or improve the other luminescent properties of the fluorescent material to achieve the purpose of gain luminous efficiency.

For example, U.S. Patent No. 4,733,128, Electroluminescence display device containing a zinc sulfide emission layer with rare earth elements and halides thereof and phosphorus, reveals that the zinc sulfide emitting layer contains a first activator selected from the group consisting of rare earth elements. [eg: Pr [鐠], Sm [钐], Eu [铕], 镝 [Dy], 鈥 [Ho], 铒 [Er], 銩 [Tm], etc.), manganese [Mn], copper [Cu], Silver [Ag], magnesium [Mg], aluminum [Al] and its halides. The first activator is used to determine the color of the emitted light of the luminescent layer. Further, the zinc sulfide light-emitting layer further comprises a second activator selected from the group consisting of nitrogen [N], phosphorus [P], arsenic [As] and bismuth [Sb]. In fact, the second activator serves to increase the brightness of the zinc sulfide light-emitting layer.

In the case of a zinc sulfide phosphor (ZnS phosphor), the host material can be doped by a suitable activated dopant to change or gain its optical properties to obtain a zinc sulfide fluorescent material having different optical properties, for example, A zinc sulfide or fluorescent material of blue or other wavelength light. However, U.S. Patent No. 4,733,128 does not disclose how the color of the light emitted by the zinc sulfide luminescent layer forms blue or white light depending on the material selected for the second activator.

The technology of blue fluorescent materials is disclosed in the technical content of some domestic patents. For example, the Republic of China Invention Patent Publication No. 200842184 can be excited by ultraviolet light to generate blue light fluorescent material components and a preparation method thereof. The above-mentioned domestic patent publications are only for reference to the technical background of the present invention and the state of the art is not limited to the scope of the present invention.

Additionally, the art of zinc sulfide fluorescent materials is also disclosed in the technical content of many U.S. patents. For example, US Patent No. 7,153,485, Method for preparing single crystalline zinc sulfide powder for phosphor, US Patent No. 6,641,756, Method for preparing zinc sulfide based phosphor having effective emission at low voltages, US Patent No. 5,309,071 The method of making zinc sulfide precursor material for a copper-activated, and the method of making zinc sulfide electroluminescent phosphor particles, US Patent No. 5, 269, 776, and the method of making zinc sulfide precursor material for a copper-activated Process of imparting stir-in capabilities to a silver activated zinc sulfide phosphor〞, US Patent No. 4,272,397, Method of preparing flake-like ceramic particle of zinc sulfide phosphor〞, US Patent No. 4,859,497 Method of preparing zinc sulfide phosphor coactivated with copper and gold〞 and the United States, U.S. Patent No. 4,208,299 The first Patent No. 4,088,921 "Zinc sulfide phosphor coactivated with copper and aluminum". The above-mentioned U.S. patents are only for the purpose of the technical background of the present invention and are intended to limit the scope of the present invention.

Therefore, there is still a need for the conventional zinc sulfide fluorescent material to further change the wavelength characteristics of the fluorescent material, or to further improve the other light-emitting characteristics of the fluorescent material. Thus, the zinc sulfide fluorescent material is doped with a suitable activated dopant to meet the potential need for the aforementioned zinc sulfide fluorescent materials that provide different optical properties.

In view of the above, the present invention provides a blue zinc sulfide fluorescent material doped with an activator and a preparation method thereof, which is doped with at least one activator [cerium fluoride or cerium chloride] in order to meet the above needs. Zinc sulfide fluorescent material for the purpose of preparing blue zinc sulfide fluorescent material.

The main object of the present invention is to provide a blue zinc sulfide fluorescent material doped with an activator and a preparation method thereof, which is doped with zinc sulfide by using at least a first activator [for example: barium fluoride or barium chloride] Fluorescent materials for the purpose of preparing blue zinc sulfide fluorescent materials.

Another object of the present invention is to provide a blue zinc sulfide fluorescent material doped with an activator and a preparation method thereof, and utilize a first activator [for example: barium fluoride or barium chloride] and a second activator [For example: manganese dioxide] is doped into a zinc sulfide fluorescent material, so that the zinc sulfide fluorescent material can be mixed to emit blue light and yellow orange light to form white light, so as to achieve the purpose of preparing white zinc sulfide fluorescent material.

In order to achieve the above object, the blue zinc sulfide fluorescent material doped with an activator of the present invention comprises a zinc sulfide fluorescent material and a first activator, and the first activator is doped with the zinc sulfide fluorescent material, and The first activator is selected from the group consisting of barium fluoride or barium chloride.

The concentration of the cesium fluoride in the preferred embodiment of the invention is from 0.5 to 7 mole percent.

The concentration of the cesium fluoride in the preferred embodiment of the invention is 1 mole percent.

The preferred concentration of the cerium chloride in the preferred embodiment of the invention is from 0.5 to 7 mole percent.

The concentration of the cerium chloride in the preferred embodiment of the invention is 4 mole percent.

In the preferred embodiment of the present invention, the first activator is sintered in a solid state sintering manner to the zinc sulfide fluorescent material, and the sintering temperature of the zinc sulfide fluorescent material is between 800 ° C and 1200 ° C.

In the preferred embodiment of the present invention, the zinc sulfide fluorescent material is further doped with a second activator, so that the zinc sulfide fluorescent material can be mixed to emit blue light and yellow orange light to form white light to further form a white zinc sulfide fluorescent material.

The second activator of the preferred embodiment of the invention is selected from the group consisting of manganese dioxide.

In the preferred embodiment of the present invention, when the first activator is doped with the zinc sulfide fluorescent material, a flux is additionally added.

In the preferred embodiment of the present invention, when the second activator is doped with the zinc sulfide fluorescent material, a flux is additionally added.

The fluxing agent of the preferred embodiment of the invention is selected from the group consisting of potassium chloride.

The method for preparing a blue zinc sulfide fluorescent material doped with an activator according to the present invention comprises the steps of: first mixing a zinc sulfide fluorescent material and a first activator [yttrium fluoride or barium chloride] at a predetermined ratio Forming a preliminary mixed material, and dissolving the preliminary mixed material in a deionized water; grinding the preliminary mixed material; drying the preliminary mixed material; grinding the preliminary mixed material; sintering the preliminary mixed material to obtain a Sintering the mixed material; and re-grinding the sintered mixed material to obtain the blue zinc sulfide fluorescent material.

The preparation method of the preferred embodiment of the present invention performs sintering of the preliminary mixed material at a predetermined heating rate.

The preparation method of the preferred embodiment of the present invention performs sintering of the preliminary mixed material in nitrogen.

The flow rate of the nitrogen gas in the preferred embodiment of the invention is 20 m ³ /h.

In the preferred embodiment of the present invention, the zinc sulfide fluorescent material is further doped with a second activator, so that the zinc sulfide fluorescent material can be mixed to emit blue light and yellow orange light to form white light to further form a white zinc sulfide fluorescent material.

The second activator of the preferred embodiment of the invention is selected from the group consisting of manganese dioxide.

In the preferred embodiment of the present invention, when the first activator is doped with the zinc sulfide fluorescent material, a flux is additionally added.

In the preferred embodiment of the present invention, when the second activator is doped with the zinc sulfide fluorescent material, a flux is additionally added.

The fluxing agent of the preferred embodiment of the invention is selected from the group consisting of potassium chloride.

In order to fully understand the present invention, the preferred embodiments of the present invention are described in detail below and are not intended to limit the invention.

The blue zinc sulfide fluorescent material doped with an activator according to a preferred embodiment of the present invention and the preparation method thereof are applicable to various equivalent activators, ranges of sintering temperatures, and ranges of sintering time, which may be different according to preferred embodiments of the present invention. The requirements of the product and the process are appropriately adjusted for the activator, the sintering temperature and the sintering time, but they are not intended to limit the scope of application of the present invention.

The blue zinc sulfide fluorescent material doped with an activator according to a preferred embodiment of the present invention can be applied to a luminescent material of a lighting device, an image device, and a display device, or related technical field, and the related art field is not departing from the present invention. The scope of the spirit and technology. The blue zinc sulfide fluorescent material doped with an activator according to a preferred embodiment of the present invention is suitable for a field emission display [FED], a vacuum fluorescent display [VFD], an electroluminescent display [ELD], etc., but it is not used The invention is defined.

The blue zinc sulfide fluorescent material doped with an activator according to a preferred embodiment of the present invention comprises a zinc sulfide phosphor [ZnS phosphors] and a first activator [activator], and the first activator is doped with the sulfide a zinc phosphor material, and the first activator is selected from the group consisting of strontium fluoride [DyF ₃ ] or cesium chloride [PrCl ₃ ], and the dopant material of cesium fluoride or cesium chloride may be used without departing from the scope of the invention. Selected from other equivalent materials. The blue zinc sulfide fluorescent material mixes the zinc sulfide fluorescent material and the first activator in various ratios. The zinc sulfide fluorescent material is used as a host material, and the first activator is doped as a dopant material to the zinc sulfide fluorescent material. In the preferred embodiment of the present invention, when the first activator is doped with the zinc sulfide fluorescent material, a flux is additionally added, and the flux is selected from potassium chloride, but it is not intended to limit the present invention.

The concentration of the cesium fluoride in the preferred embodiment of the invention is preferably from 0.5 to 7 mole percent [mol%], more preferably 1 mole percent, but it is not intended to limit the scope of the invention. In the preferred embodiment of the present invention, the cesium fluoride is sintered in the solid state sintering manner to the zinc sulfide fluorescent material, and the sintering temperature of the zinc sulfide fluorescent material is preferably between 800 ° C and 1200 ° C, and more preferably 1000 ° C. However, it is not intended to limit the scope of the invention.

The concentration of the cerium chloride in the preferred embodiment of the invention is preferably from 1 to 5 mole percent [mol%], more preferably 4 mole percent, but it is not intended to limit the scope of the invention. In the preferred embodiment of the present invention, the cerium chloride is sintered in a solid state sintering manner to the zinc sulfide fluorescent material, and the sintering temperature of the zinc sulfide fluorescent material is preferably between 800 ° C and 1200 ° C, and more preferably 900 ° C. However, it is not intended to limit the scope of the invention.

In the preferred embodiment of the present invention, the zinc sulfide fluorescent material is further doped with a second activator, so that the zinc sulfide fluorescent material can be mixed to emit blue light and yellow orange light to form white light to further form a white zinc sulfide fluorescent material; The second activator is selected from manganese dioxide [MnO ₂ ], but it is not intended to limit the invention. In the preferred embodiment of the present invention, when the second activator is doped with the zinc sulfide fluorescent material, a flux is additionally added, and the flux is selected from potassium chloride, but it is not intended to limit the present invention.

1 is a schematic block diagram showing a method for preparing a blue zinc sulfide fluorescent material doped with an activator according to a first preferred embodiment of the present invention. The method for preparing the blue zinc sulfide fluorescent material according to the first preferred embodiment of the present invention is merely a preferred manufacturing method, but the manufacturing method is not intended to limit the scope of the present invention. The method for preparing a blue zinc sulfide fluorescent material according to the first preferred embodiment of the present invention has eight execution steps S1A, S1B, S2, S3, S4, S5, S6 and S7, and the eight execution steps S1A to S7 are not deviated from the present The eight execution steps S1A to S7 are not intended to limit the production process of the present invention, as appropriate.

Referring to FIG. 1 , a method for preparing a blue zinc sulfide fluorescent material according to a first preferred embodiment of the present invention is first prepared in step 1A of step 1A by using a suitable technical means as a zinc sulfide fluorescent material. Source material of blue zinc sulfide fluorescent material [source material].

Referring to FIG. 1 again, the method for preparing a blue zinc sulfide fluorescent material according to the first preferred embodiment of the present invention is further prepared by using a suitable technique to prepare barium fluoride or barium chloride in the first step S1B. The first activator is such that the first activator is doped to the zinc sulfide fluorescent material in a subsequent step [compare step 1A to perform step S1A].

Referring to FIG. 1 again, the method for preparing a blue zinc sulfide fluorescent material according to the first preferred embodiment of the present invention is followed by the second step S2, the zinc sulfide fluorescent material and the first activator [fluorine] Plutonium or barium chloride] is initially mixed at a predetermined ratio by a suitable mixing technique [for example, mixing] to form an initially mixed material. Next, the preliminary mixed material is dissolved in a suitable solution, such as deionized water, but it is not intended to limit the scope of the invention.

Referring to FIG. 1 again, the method for preparing a blue zinc sulfide fluorescent material according to the first preferred embodiment of the present invention is followed by the third step S3, wherein the preliminary mixed material is ground by a suitable grinding device or method. The preliminary mixed material is further uniformly mixed, but the grinding technique is not intended to limit the invention. For example, a ball mill machine can be used to grind and mix the preliminary mixed material.

Referring to FIG. 1 again, the method for preparing a blue zinc sulfide fluorescent material according to the first preferred embodiment of the present invention is then in a fourth execution step S4, in a suitable drying apparatus or manner at an appropriate temperature [eg: 80 The preliminary mixed material is dried under °C to dehydrate the preliminary mixed material, but the drying technique is not intended to limit the present invention.

Referring to FIG. 1 again, the method for preparing a blue zinc sulfide fluorescent material according to the first preferred embodiment of the present invention is followed by the fifth step S5, wherein the preliminary mixed material is reground by a suitable grinding apparatus or method. In order to further uniformly mix the preliminary mixed material after drying, the grinding technique is not intended to limit the invention.

Referring to FIG. 1 again, the method for preparing a blue zinc sulfide fluorescent material according to the first preferred embodiment of the present invention is followed by a sixth sintering step S6 by a suitable sintering technique [eg, solid state sintering method [solid-state] Sintering the preliminary mixed material to obtain a sintered mixed material, but the sintering technique is not intended to limit the present invention.

In the sintering process, the method for preparing a blue zinc sulfide fluorescent material according to the first preferred embodiment of the present invention sinters the preliminary mixed material at a predetermined heating rate [for example, 20 ° C / min], but it is not intended to limit the present invention. The scope. In addition, the method for preparing a blue zinc sulfide fluorescent material according to the first preferred embodiment of the present invention may be characterized in that the preliminary mixed material is sintered in a nitrogen gas or an inert gas, and the flow rate of the nitrogen gas is preferably 20 m ³ /h, but it is not It is intended to limit the scope of the invention.

Referring to FIG. 1 again, the method for preparing a blue zinc sulfide fluorescent material according to the first preferred embodiment of the present invention is finally re-polished in a seventh step S7 by a suitable grinding apparatus or method. In order to achieve uniform mixing of the sintered mixed material after sintering, the grinding technique is not intended to limit the invention. At this time, the first preferred embodiment of the present invention has completed the preparation of the blue zinc sulfide fluorescent material.

2 is a graph showing the relationship between the photoluminescence intensity and the wavelength of a blue zinc sulfide fluorescent material doped with an activator according to a first preferred embodiment of the present invention at various doping concentrations of an activator [yttrium fluoride]. Figure. Referring to FIG. 2, the zinc sulfide fluorescent material of the first preferred embodiment of the present invention is 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, respectively, at a sintering temperature of 1000 °C. The concentration of 7 mol% of lanthanum fluoride was doped, and the main emission wavelength of the spectrum was 456 nm [blue light wave]. When the cesium fluoride doping concentration is increased from 0.5 mol% to 1 mol%, the luminescence intensity can be enhanced; and when the cesium fluoride doping concentration is 1 mol%, a strong luminescence intensity can be obtained.

Attachment 1 discloses that a blue zinc sulfide fluorescent material doped with an activator [yttrium fluoride] according to a first preferred embodiment of the present invention is sintered at a sintering temperature of 1000 ° C, and is respectively 0.5 mol%, 1 mol%, and 2 mol%. The SEM image of the doping concentration of 3 mol%, 4 mol%, 5 mol%, and 7 mol% has a fine particle size ranging from 1 μm to 2 μm.

Fig. 3 is a view showing the relationship between the intensity of photoluminescence (PL) and the wavelength of the blue zinc sulfide fluorescent material doped with an activator [yttrium fluoride] according to the first preferred embodiment of the present invention at various sintering temperatures. The graph. Referring to FIG. 3, the zinc sulfide fluorescent material of the first preferred embodiment of the present invention is doped at a concentration of 1 mol% of cesium fluoride, and is respectively sintered at 800 ° C, 900 ° C, 1000 ° C, 1100. Sintering was carried out at ° C and 1200 ° C. When the sintering temperature reaches 1000 ° C, a strong luminescence intensity can be obtained.

Attachment 2 discloses that a blue zinc sulfide fluorescent material doped with an activator [1 mol% lanthanum fluoride] according to a first preferred embodiment of the present invention is sintered at 800 ° C, 900 ° C, 1000 ° C, 1100 ° C, and 1200 ° C, respectively. SEM image of temperature. When the sintering temperature is increased at 800 ° C, 900 ° C, 1000 ° C, and 1100 ° C, the fine particle size gradually increases. When the sintering temperature is 1200 ° C, the fine particle size is between 3 μm and 5 μm.

Attachment 3 discloses that a blue zinc sulfide fluorescent material doped with an activator [yttrium fluoride] according to a first preferred embodiment of the present invention is doped at a concentration of 1 mol% of lanthanum fluoride and sintered at a sintering temperature of 1000 ° C. CIE color map, with CIE color coordinates (0.16, 0.19) [CIE color coordinates of blue light], as indicated by the arrows.

Figure 4 is a view showing the second preferred embodiment of the present invention using an activator [1 mol% cesium fluoride] doped blue zinc sulfide fluorescent material to produce light at various doping concentrations [potassium chloride] A plot of fluorescence intensity versus wavelength. Referring to FIG. 4, the zinc sulfide fluorescent material of the first preferred embodiment of the present invention is 0 mol%, 2 mol%, 4 mol%, and 8 mol% potassium chloride at a sintering temperature of 1000 ° C, respectively. The concentration is fluxed and sintered. The potassium chloride doping concentration is increased from 0 mol% to 8 mol% doping concentration; and when the potassium chloride doping concentration is 4 mol%, a strong luminescence intensity can be obtained.

Attachment 4 discloses that a blue zinc sulfide fluorescent material doped with an activator [1 mol% barium fluoride] according to a second preferred embodiment of the present invention is sintered at a sintering temperature of 1000 ° C, and is respectively 0 mol%, 2 mol. SEM images of flux sintering at concentrations of %, 4 mol%, and 8 mol% potassium chloride. When doped with a concentration of 0 mol% potassium chloride [undoped with potassium chloride], the fine particle size is between 1 μm and 2 μm. When doped with a concentration of 2 to 8 mol% of potassium chloride, the fine particle size is about 2 μm to 4 μm.

Attachment 5 discloses a blue zinc sulfide fluorescent material doped with an activator [1 mol% cesium fluoride] simultaneously doped with a flux [4 mol% potassium chloride] at a sintering temperature according to a second preferred embodiment of the present invention. The CIE color map of the sintered at 1000 ° C has a CIE color coordinate of (0.16, 0.18) [CIE color coordinate position of blue light] as indicated by the arrow.

In addition, the blue zinc sulfide fluorescent material of the third preferred embodiment of the present invention may be doped with the zinc sulfide fluorescent material by using another activator, so that the zinc sulfide fluorescent material can be mixed to emit blue light and yellow orange light to form white light. To further form a white zinc sulfide fluorescent material, but it is not intended to limit the scope of the invention. In the third preferred embodiment of the present invention, the zinc sulfide fluorescent material is further doped with a second activator to adjust the light-emitting wavelength characteristic of the zinc sulfide fluorescent material and change the color of the light to further form white zinc sulfide. The material is not intended to limit the scope of the invention.

The second activator of the third preferred embodiment of the invention is selected from the group consisting of manganese dioxide [MnO ₂ ]. FIG. 5 is a view showing various doping concentrations of a yellow orange-zinc zinc sulfide fluorescent material doped with an activator in a first activator [yttrium fluoride] and a second activator [manganese dioxide] according to a third preferred embodiment of the present invention. It produces a plot of photoluminescence intensity versus wavelength at a ratio.

Referring to FIG. 5, in a third preferred embodiment of the present invention, yttrium fluoride [first activator] and manganese dioxide [second activator] are [1:0.2], [1:0.4]. The weight ratio of [1:0.6], [1:0.8], [1:1] is doped to the zinc sulfide fluorescent material. In a third preferred embodiment of the present invention, 1 mol% of lanthanum fluoride is sintered and doped at the sintering temperature of 1000 ° C to the zinc sulfide fluorescent material, and then 4 mol % of manganese dioxide is sintered and doped at a sintering temperature of 900 ° C. The zinc sulfide fluorescent material. Figure 5 shows that the two main emission wavelengths of the spectrum are 456 nm and 575 nm.

Attachment 6 discloses a yellow orange light zinc sulfide fluorescent material doped with an activator according to a third preferred embodiment of the present invention, wherein the first activator [DyF ₃ ] and the second activator [manganese dioxide] are After doping with a weight ratio of [1:0.2], [1:0.4], [1:0.6], [1:0.8], [1:1], it emits a CIE color map of white light. When the first activator [DyF ₃ ] and the second activator [manganese dioxide] are doped in a weight ratio of [1:0.6] and [1:0.8], the CIE color coordinates are (0.33). , 0.31) and (0.36, 0.33), as indicated by the arrows.

Figure 6 is a graph showing the relationship between the photoluminescence intensity and the wavelength of a blue zinc sulfide fluorescent material doped with an activator at various doping concentrations of various activators [cerium chloride] according to a fourth preferred embodiment of the present invention. Figure. Referring to FIG. 6, the zinc sulfide fluorescent material of the first preferred embodiment of the present invention is at a concentration of 1 mol%, 2 mol%, 3 mol%, 4 mol%, and 5 mol% of barium chloride at a sintering temperature of 1000 ° C, respectively. Doping is performed, and the main emission wavelength of the spectrum is shown to be between 450 nm and 455 nm [blue light wave]. When the doping ratio of barium chloride is 1 mol%, the main emission wavelength of the spectrum is between 450 nm and 455 nm [blue light wave]; and when the doping concentration of barium chloride is 4 mol%, strong luminescence can be obtained. The intensity, the main emission wavelength of the spectrum is 454 nm [blue light wave].

Figure 7 is a diagram showing the relationship between the intensity of photoluminescence (PL) and the wavelength of a blue-zinc sulfide phosphor doped with an activator [cerium chloride] according to a fourth preferred embodiment of the present invention at various sintering temperatures. The graph. Referring to FIG. 7, the zinc sulfide fluorescent material of the fourth preferred embodiment of the present invention is doped at a concentration of 4 mol% of cerium chloride, and is respectively sintered at 800 ° C, 900 ° C, 1000 ° C, and 1100. Sintering was carried out at ° C and 1200 ° C. When the sintering temperature reaches 900 ° C, a strong luminescence intensity can be obtained.

Attachment 7 discloses a fourth preferred embodiment of the present invention using an activator [4 mol% lanthanum chloride] doped blue zinc sulfide fluorescent material at 800 ° C, 900 ° C, 1000 ° C, 1100 ° C, 1200 ° C sintering temperature SEM image map. When the sintering temperature was 1200 ° C, the fine particle size was 5 μm.

Figure 8 is a view showing a fifth preferred embodiment of the present invention, which utilizes an activator [4 mol% of cerium chloride] doped blue zinc sulfide fluorescent material to produce photoluminescence under various flux [potassium chloride] doping concentrations. A plot of light intensity versus wavelength. Referring to FIG. 8, the zinc sulfide fluorescent material of the fifth preferred embodiment of the present invention is fluxed at a concentration of 0 mol%, 2 mol%, 4 mol%, and 6 mol% potassium chloride at a sintering temperature of 900 ° C, respectively. sintering. When the potassium chloride doping concentration is 2 mol%, a strong luminescence intensity can be obtained.

Attachment 8 discloses a blue zinc sulfide fluorescent material doped with an activator [4 mol% of cerium chloride] while being doped with a flux [2 mol% potassium chloride] at a sintering temperature of 900 ° C according to a fifth preferred embodiment of the present invention. The CIE color map of the sintering is performed, and the CIE color coordinates are (0.16, 0.2) [CIE color coordinates of the blue light] as indicated by the arrows.

FIG. 9 is a view showing various doping concentrations of a blue zinc sulfide fluorescent material doped with an activator in a first activator [cerium chloride] and a second activator [manganese dioxide] according to a sixth preferred embodiment of the present invention. A plot of the ratio of photoluminescence intensity to wavelength for a ratio and simultaneous doping flux.

Referring to FIG. 9, in a sixth preferred embodiment of the present invention, cerium chloride [first activator] and manganese dioxide [second activator] are [1:1], [1:2]. The weight ratio of [1:2.5], [1:2.8], [1:3], [1:4] is doped to the zinc sulfide fluorescent material. In the sixth preferred embodiment of the present invention, when the second activator is doped with the zinc sulfide fluorescent material, a flux [flux] is additionally added to increase the sintering rate of the zinc sulfide fluorescent material. The flux of the sixth preferred embodiment of the present invention is selected from the group consisting of potassium chloride [KCl].

Referring to FIG. 9 again, in a sixth preferred embodiment of the present invention, 4 mol% of barium fluoride and 2 mol% of potassium chloride are sintered and doped at the sintering temperature of 900 ° C to the zinc sulfide fluorescent material, and then 4 mol% of manganese dioxide was sintered and doped to the zinc sulfide fluorescent material at a sintering temperature of 900 °C. Figure 9 shows that the two main emission wavelengths of the spectrum are 458 nm and 578 nm.

Attachment 9 discloses a blue zinc sulfide fluorescent material doped with an activator according to a sixth preferred embodiment of the present invention, wherein the first activator [PrCl ₃ ] and the second activator [manganese dioxide] are [1:1], [1:2], [1:2.5], [1:3], [1:4] weight ratio doping and simultaneous doping of flux, it emits white light CIE color coordinates . When the first activator [PrCl ₃ ] and the second activator [ manganese dioxide] are doped in a weight ratio of [1:2], it can emit closer to white light, and its CIE color coordinate is (0.35). , 0.32), as indicated by the arrow.

Figure 10 is a view showing various doping concentrations of a blue zinc sulfide fluorescent material doped with an activator in a first activator [cerium chloride] and a second activator [manganese dioxide] according to a sixth preferred embodiment of the present invention. Another graph showing the relationship between photoluminescence intensity and wavelength under proportional and simultaneous doping flux [1 mol% potassium chloride].

Referring to FIG. 10, in a sixth preferred embodiment of the present invention, cerium chloride [first activator] and manganese dioxide [second activator] are [4:0.2], [4:0.3]. The weight ratio of [4:0.4], [4:0.5], [4:0.7], [4:1] is doped to the zinc sulfide fluorescent material while doping with 1 mol% of potassium chloride.

Referring to FIG. 10 again, in a sixth preferred embodiment of the present invention, 1 mol% of potassium chloride is sintered at a sintering temperature of 900 ° C to be doped with 4 mol % of lanthanum fluoride doped manganese dioxide. The material and the weight percentage of manganese dioxide were 0.2 mol%, 0.3 mol%, 0.4 mol%, 0.5 mol%, 0.7 mol%, and 1 mol%, respectively. Figure 10 shows that the two main emission wavelengths of the spectrum are 459 nm and 570 nm.

Attachment 10 discloses that a blue zinc sulfide fluorescent material doped with an activator according to a sixth preferred embodiment of the present invention is sintered at a sintering temperature of 900 ° C, and the first activator [cerium chloride] and the second activator are respectively respectively. [Manganese dioxide] in the weight ratio of [4:0.2], [4:0.3], [4:0.4], [4:0.5], [4:0.7], [4:1] and simultaneously doping flux An SEM image of [1 mol% potassium chloride] having a fine particle size ranging from 2 μm to 3 μm.

Attachment 11 discloses a blue zinc sulfide fluorescent material doped with an activator according to a sixth preferred embodiment of the present invention, wherein the first activator [PrCl ₃ ] and the second activator [manganese dioxide] are [4:0.2], [4:0.3], [4:0.4], [4:0.5], [4:0.7], [4:1] weight ratio doping and simultaneous doping flux [1 mol% chlorine After potassium, it emits another CIE color map of white light. When the first activator [PrCl ₃ ] and the second activator [ manganese dioxide] are doped in a weight ratio of [4:0.4], it can emit relatively close to white light, and its CIE color coordinate is (0.36). , 0.32), as indicated by the arrow.

The above experimental data is preliminary experimental results obtained under specific conditions, which are only used to easily understand or refer to the technical content of the present invention, and other experiments are still required. The experimental data and its results are not intended to limit the scope of the invention.

The foregoing preferred embodiments are merely illustrative of the invention and the technical features thereof, and the techniques of the embodiments can be carried out with various substantial equivalent modifications and/or alternatives; therefore, the scope of the invention is subject to the appended claims. The scope defined by the scope shall prevail.

S1A. . . Step 1A execution steps

S1B. . . Step 1B execution steps

S2. . . Second execution step

S3. . . Step 3

S4. . . Fourth execution step

S5. . . Step 5

S6. . . Step 6

S7. . . Step 7

Fig. 1 is a block diagram showing the flow of a method for preparing a blue zinc sulfide fluorescent material doped with an activator according to a first preferred embodiment of the present invention.

Fig. 2 is a graph showing the relationship between the intensity of photoluminescence and the wavelength of a blue zinc sulfide fluorescent material doped with an activator according to a first preferred embodiment of the present invention at various activator doping concentrations.

Fig. 3 is a graph showing the relationship between the intensity of photoluminescence and the wavelength at various sintering temperatures of a blue zinc sulfide fluorescent material doped with an activator according to a first preferred embodiment of the present invention.

Fig. 4 is a graph showing the relationship between the intensity of photoluminescence and the wavelength of a blue zinc sulfide fluorescent material doped with an activator according to a second preferred embodiment of the present invention at various flux doping concentrations.

Figure 5: A yellow orange light zinc sulfide fluorescent material doped with an activator in a third preferred embodiment of the present invention in a first activator [DyF ₃ ] and a second activator [MnO2 [MnO] ₂ ] The graph of the relationship between the photoluminescence intensity and the wavelength at various doping concentration ratios.

Fig. 6 is a graph showing the relationship between the intensity of photoluminescence and the wavelength of a blue zinc sulfide fluorescent material doped with an activator according to a fourth preferred embodiment of the present invention at various activator doping concentrations.

Fig. 7 is a graph showing the relationship between the photoluminescence intensity and the wavelength of a blue zinc sulfide fluorescent material doped with an activator according to a fourth preferred embodiment of the present invention at various sintering temperatures.

Figure 8 is a graph showing the relationship between the intensity of photoluminescence and the wavelength of a blue zinc sulfide fluorescent material doped with an activator in accordance with a fifth preferred embodiment of the present invention at various flux doping concentrations.

Figure 9 is a view of a sixth preferred embodiment of the present invention, an activator-doped yellow orange zinc sulfide fluorescent material in a first activator [PrCl ₃ ] and a second activator [MnO 2 [MnO] ₂ ] The various doping concentration ratios and the graphs showing the relationship between the photoluminescence intensity and the wavelength under the simultaneous doping of the flux.

Figure 10 is a diagram of a sixth preferred embodiment of the present invention, an activator-doped yellow orange zinc sulfide fluorescent material in a first activator [PrCl ₃ ] and a second activator [MnO2 [MnO] ₂ ] The various doping concentration ratios and the other relationship between the photoluminescence intensity and the wavelength at which the flux is simultaneously doped.

Attachment 1: An SEM image of a doping concentration of a blue zinc sulfide fluorescent material doped with an activator according to a first preferred embodiment of the present invention at various activators.

Attachment 2: SEM image of a blue zinc sulfide fluorescent material doped with an activator at various sintering temperatures in accordance with a first preferred embodiment of the present invention.

Attachment 3: C.I.E. color coordinates of a blue zinc sulfide fluorescent material doped with an activator according to a first preferred embodiment of the present invention.

Attachment 4: SEM image of a doping concentration of a blue-zinc-zinc-fluorescent material doped with an activator in various fluxes according to a second preferred embodiment of the present invention.

Attachment 5: C.I.E. color coordinate plot of a blue zinc sulfide fluorescent material doped with an activator and a doping flux simultaneously doped with an activator according to a second preferred embodiment of the present invention.

Attachment 6: The yellow orange light zinc sulfide fluorescent material doped with an activator according to the third preferred embodiment of the present invention, the first activator [DyF ₃ ] and the second activator [manganese dioxide [MnO] ₂ ]] After doping at various concentration ratios, it emits a CIE color map of white light.

Attachment 7: SEM image of a blue zinc sulfide fluorescent material doped with an activator at various sintering temperatures in accordance with a fourth preferred embodiment of the present invention.

Attachment 8: C.I.E. color coordinate plot of a blue zinc sulfide fluorescent material doped with an activator and a doping flux simultaneously doped with an activator according to a fifth preferred embodiment of the present invention.

Attachment 9: A yellow orange light zinc sulfide fluorescent material doped with an activator according to a sixth preferred embodiment of the present invention, a first activator [PrCl ₃ ] and a second activator [MnO 2 [MnO] ₂ ]] After doping with various concentration ratios and simultaneously doping the flux, it emits a CIE color map of white light.

Attachment 10: A yellow orange light zinc sulfide fluorescent material doped with an activator according to a sixth preferred embodiment of the present invention in a first activator [PrCl ₃ ] and a second activator [MnO 2 [MnO] ₂ ]] various doping concentration ratios and SEM images of the simultaneously doped flux.

Attachment 11: A yellow orange light zinc sulfide fluorescent material doped with an activator according to a sixth preferred embodiment of the present invention, a first activator [PrCl ₃ ] and a second activator [MnO 2 [MnO] ₂ ]] After being doped with various concentration ratios and simultaneously doped with a flux, it emits another CIE color map of white light.

S1A. . . Step 1A execution steps

S1B. . . Step 1B execution steps

S2. . . Second execution step

S3. . . Step 3

S4. . . Fourth execution step

S5. . . Step 5

S6. . . Step 6

S7. . . Step 7

Claims (30)

A blue zinc sulfide fluorescent material doped with an activator, comprising: a zinc sulfide fluorescent material as a host material; and a first activator as a doping material, the first activation The agent is doped to the zinc sulfide fluorescent material in a ratio, and the first activator is selected from the group consisting of barium fluoride or barium chloride, wherein the blue zinc sulfide fluorescent material is a powder. The blue zinc sulfide fluorescent material doped with an activator according to claim 1 of the patent application, wherein the concentration of the cesium fluoride is 0.5 to 7 mol%. The blue zinc sulfide fluorescent material doped with an activator according to claim 1 of the patent application, wherein the concentration of the cesium fluoride is 1 mole percent. The blue zinc sulfide fluorescent material doped with an activator according to claim 1 of the patent application, wherein the concentration of the cerium chloride is 0.5 to 7 mol%. The blue zinc sulfide fluorescent material doped with an activator according to claim 1 of the patent application, wherein the concentration of the cerium chloride is 4 mole percent. The blue zinc sulfide fluorescent material doped with an activator according to claim 1, wherein the first activator is sintered in a solid state sintering manner to the zinc sulfide fluorescent material, and the zinc sulfide fluorescent material is sintered. The temperature is between 800 ° C and 1200 ° C. The blue zinc sulfide fluorescent material doped with an activator according to claim 1, wherein the zinc sulfide fluorescent material is further doped with a second activator, so that the zinc sulfide fluorescent material can be mixed to emit blue light. And yellow orange light to form white light to further form white zinc sulfide fluorescent material. The blue zinc sulfide fluorescent material doped with an activator according to claim 7 of the patent application, wherein the second activator is selected from the group consisting of manganese dioxide. The blue zinc sulfide fluorescent material doped with an activator according to claim 1, wherein when the first activator is doped with the zinc sulfide fluorescent material, a flux is additionally added. The blue zinc sulfide fluorescent material doped with an activator according to claim 7 of the patent application, wherein when the second activator is doped with the zinc sulfide fluorescent material, a flux is additionally added. The blue zinc sulfide fluorescent material doped with an activator according to claim 9 or 10, wherein the flux is selected from potassium chloride. A method for preparing a blue zinc sulfide fluorescent material doped with an activator, comprising the steps of: initially mixing a zinc sulfide fluorescent material and a first activator [cerium fluoride or barium chloride] in a ratio to form a preliminary mixing material, and dissolving the preliminary mixed material in a deionized water; grinding the preliminary mixed material; drying the preliminary mixed material; grinding the preliminary mixed material; sintering the preliminary mixed material to obtain a sintered mixed material And re-grinding the sintered mixed material to obtain the blue zinc sulfide fluorescent material, wherein the blue zinc sulfide fluorescent material is a powder. A method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 12, wherein the preparation method sinters the preliminary mixed material at a heating rate. A method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 12, wherein the preliminary mixing material is sintered in nitrogen. A method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 14 of the patent application, wherein the flow rate of the nitrogen gas is 20 m ³ /h. The method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 12, wherein the zinc sulfide fluorescent material is further doped with a second activator, so that the zinc sulfide fluorescent material can be mixed. Blue light and yellow orange light are emitted to form white light to further form white zinc sulfide fluorescent material. The method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 16 of the patent application, wherein the second activator is selected from the group consisting of manganese dioxide. The method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 12, wherein when the first activator is doped with the zinc sulfide fluorescent material, a flux is further added. The method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 16 of the patent application, wherein when the second activator is doped with the zinc sulfide fluorescent material, a flux is additionally added. A method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 18 or 19, wherein the flux is selected from the group consisting of potassium chloride. The method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 16 of the patent application, wherein the second activator is selected from the group consisting of manganese dioxide, the cesium fluoride [first activator] and two Manganese oxide [second activator] is doped to the zinc sulfide fluorescent material in a weight ratio of [1:0.2] to [1:1]. The method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 16 of the patent application, wherein the second activator is selected from the group consisting of manganese dioxide, the cerium chloride [first activator] and two Manganese oxide [second activator] is doped to the zinc sulfide fluorescent material in a weight ratio of [1:1] to [1:4]. a method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 16 wherein the second activator is selected from the group consisting of manganese dioxide, the first activator [cerium chloride] and The second activator [manganese dioxide] is doped in a weight ratio of [4:0.2] to [4:1]. a method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 16 wherein the second activator is selected from the group consisting of manganese dioxide, the first activator [cerium chloride] and The second activator [manganese dioxide] is doped in a weight ratio of [4:0.2] to [4:1] and simultaneously doped with a flux [1 mol% potassium chloride]. The method for preparing a blue zinc sulfide fluorescent material doped with an activator according to claim 16 , wherein the second activator is selected from the group consisting of manganese dioxide, and the weight percentage of the manganese dioxide is 0.2 mol% to Between 1 mol%. The blue zinc sulfide fluorescent material doped with an activator according to claim 7 of the patent application, wherein the second activator is selected from the group consisting of manganese dioxide, the lanthanum fluoride [first activator] and manganese dioxide [Second activator] is doped to the zinc sulfide fluorescent material in a weight ratio of [1:0.2] to [1:1]. Blue light vulcanization doped with an activator as described in item 7 of the patent application scope a zinc fluorescent material, wherein the second activator is selected from the group consisting of manganese dioxide, the cerium chloride [first activator] and the manganese dioxide [second activator] are [1:1] to [1:4] The weight ratio is doped to the zinc sulfide fluorescent material. The blue zinc sulfide fluorescent material doped with an activator according to claim 7 of the patent application, wherein the second activator is selected from the group consisting of manganese dioxide, the first activator [cerium chloride] and the second activation The agent [manganese dioxide] is doped in a weight ratio of [4:0.2] to [4:1]. The blue zinc sulfide fluorescent material doped with an activator according to claim 7 of the patent application, wherein the second activator is selected from the group consisting of manganese dioxide, the first activator [cerium chloride] and the second activation The agent [manganese dioxide] is doped in a weight ratio of [4:0.2] to [4:1] and simultaneously doped with a flux [1 mol% potassium chloride]. The blue zinc sulfide fluorescent material doped with an activator according to claim 7, wherein the second activator is selected from the group consisting of manganese dioxide, and the manganese oxide has a concentration by weight of 0.2 mol% to 1 mol. %between.