KR100323403B1 - Process for Preparing Oxidized Fluorescent Particles Evolving Blue Light by Spray Pyrolysis - Google Patents

Abstract

The present invention can be widely used in plasma displays, field emission displays and cathode ray tubes (CRTs) and lamps by spray pyrolysis, which sprays a mixed solution of a desired composition into fine droplets and prepares fine powders by drying and pyrolysis. A method for producing a multicomponent blue light emitting oxide phosphor. In the present invention, the precursor solution is prepared by dissolving an activator entering a doping material in each host and the electric matrix in distilled water so as to meet the stoichiometric ratio of the multi-component oxide phosphor to be prepared, and then a filter droplet generator. expansion aerosol generator (FEAG) or an ultrasonic spray pyrolysis apparatus, and then spray the droplets into the reactor by drying-decomposing-reaction-crystallization and converting them into phosphor particles, and crystallization and By activating, a multicomponent blue light emitting oxide phosphor is prepared. According to the present invention, a multi-component blue light emitting oxide having excellent crystallinity and luminescent properties with no agglomeration between particles while maintaining a perfect spherical shape even after long-term heat treatment at high temperature by spray pyrolysis using FEAG or ultrasonic spray pyrolysis. Phosphors can be prepared.

Description

Process for Preparing Oxidized Fluorescent Particles Evolving Blue Light by Spray Pyrolysis

The present invention relates to a method for producing a multicomponent blue light emitting oxide phosphor by spray pyrolysis. More specifically, the present invention provides a plasma display, field emission display, cathode ray tube (CRT) and lamp by spray pyrolysis, which sprays a mixed solution of a desired composition into fine droplets and prepares fine powders by drying and pyrolysis. The present invention relates to a method for producing a multicomponent blue light emitting oxide phosphor which can be widely used.

As phosphors for displays and lamps, sulfide phosphors doped with a noble metal in a host such as ZnS, CdS, ZnCdS, etc. have been mainly used. These sulfide phosphors have been studied for decades and have evolved to the point where efficiency is now improved to a level where no further increase in efficiency is possible. Thus, until a few years ago, research on these phosphors had been done by very few research groups.

However, as interest in high definition television (HDTV) has recently increased, development of corresponding displays has been revived. Representative displays are flat panel displays and field emission displays (FEDs) which are recently represented by plasma displays (PDPs). Unlike conventional displays, these flat panel and field emission displays have the potential to be applied in various fields such as wall-mounted TVs, computers, camcorders, and auto navigation devices due to their light and thin characteristics. It becomes the target of. In the conventional cathode ray tube (CRT) display, since the sulfide phosphor has excellent light emission characteristics, there is no problem. However, in the flat panel display and the field emission display, there is a difficulty in using the conventional sulfide phosphor. That is, since the flat panel display and the field emission display emit light under high vacuum, when a conventional sulfide phosphor is used, problems such as a decrease in vacuum degree and a decrease in performance due to decomposition of sulfides occur. Unlike sulfide phosphors, oxide phosphors are very stable to ultraviolet rays or electron beams, which are energy sources for luminescence in displays, and thus are used as flat panel phosphors. Examples thereof include aluminates, silicates, Titanate or borate.

On the other hand, in all displays or lamps, since the characteristics of the blue-emitting phosphor is inferior, there is a problem of degrading the overall product quality. Recently, blue light emitting phosphors for displays and lamps have been studied abundantly in aluminate-based phosphors having a Ba _x Mg _y Al _z O _m : Eu ²⁺ structure (where x, y, z and m represents the variable of each element). Since phosphors having such a structure vary in their composition according to each composition change, many studies have been conducted to suit the field to be applied.

At present, most of these blue light-emitting oxide phosphors are produced by a solid phase method. In the solid phase method, the oxides of the respective components are mixed, and the desired multicomponent oxide phosphor is finally manufactured through repeated high temperature heat treatment and pulverization. Therefore, in order to obtain a pure composition by the solid phase method, a high temperature and a long process must be performed. In addition, impurities may be contained in the phosphor particles through repeated heat treatment and pulverization processes, and particles prepared by this method generally correspond to several microns in size, and have a rough surface and irregular shape. In particular, since the above-mentioned aluminate-based blue light emitting phosphors grow crystals in the form of a plate by a general heat treatment process, most of the particles produced by the solid state method or the liquid phase method have a plate shape. Phosphor particles have many problems when applied to a substrate by forming a slurry to form a display or a lamp. Therefore, a new manufacturing process has been required to maintain spherical shape while suppressing plate-shaped crystal growth characteristics and to obtain particles having good crystals. In addition, blue light emission with uniform size and shape and excellent light emission characteristics, which can be widely used for flat panel displays, field emission displays, and general-purpose displays including both conventional cathode ray tubes (CRTs) and lamps, is achieved. There is a constant need to develop a method for producing an oxide phosphor in a simpler process.

Accordingly, the present inventors have diligently researched to develop an efficient method for producing an oxide phosphor having a uniform size and shape. As a result, the present inventors have used droplet generators such as filter expansion aerosol generators (FEAG), ultrasonic waves or air nozzles. When the mixed solution is sprayed into fine droplets and spray pyrolysis method for preparing fine powders by drying and pyrolysis is applied, aluminate having blue crystals having excellent crystallinity and luminescence properties in a uniform form without spherical aggregation ( It was confirmed that the multi-component oxide phosphor of the aluminate series can be manufactured, and thus, the present invention was completed.

After all, the main object of the present invention is to provide a method for producing a multicomponent blue light emitting oxide phosphor which can be obtained by spray pyrolysis.

Another object of the present invention is to provide a multi-component blue light emitting oxide phosphor prepared by the electric method.

1 is a diagram schematically showing the configuration of a filter expansion aerosol generator (FEAG).

2 is a diagram schematically showing the configuration of an ultrasonic spray pyrolysis device.

FIG. 3 is an electron micrograph of particles of BaMgAl ₁₄ O ₂₂ : Eu ²⁺ particles prepared at 900 ° C. by ultrasonic spray pyrolysis at 1400 ° C. FIG.

4 is an electron micrograph of particles of BaMgAl ₁₄ O ₂₂ : Eu ²⁺ particles prepared at 1300 ° C. by ultrasonic spray pyrolysis at 1400 ° C. FIG.

FIG. 5 shows the results of X-ray diffraction analysis of BaMgAl ₁₄ O ₂₂ : Eu ²⁺ particles prepared at 900 ° C. by ultrasonic spray pyrolysis.

6 is an electron micrograph of particles of BaMgAl ₁₄ O ₂₂ : Eu ²⁺ particles prepared at 900 ° C. by heat treatment at 1400 ° C. using the FEAG process.

7 is an electron micrograph of particles of BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ particles prepared at 600 ° C. by ultrasonic spray pyrolysis at 1400 ° C. FIG.

8 is an electron micrograph of particles of BaMg ₂ Al ₁₆ O ₂₂ : Eu ²⁺ particles prepared at 900 ° C. by ultrasonic spray pyrolysis at 1400 ° C.

FIG. 9 is an X-ray diffraction analysis of BaMg ₂ Al ₁₆ O ₂₂ : Eu ²⁺ particles prepared at 900 ° C. by ultrasonic spray pyrolysis.

10 is an electron micrograph of particles of BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ particles prepared at 900 ° C. by heat treatment at 1400 ° C. using the FEAG process.

FIG. 11 is an electron micrograph of particles of Ba _0.91 Al ₁₂ O ₁₂ : Eu ²⁺ particles prepared at 600 ° C. by ultrasonic spray pyrolysis at 1400 ° C. FIG.

12 is an electron micrograph of particles of Ba _0.91 Al ₁₂ O ₁₂ : Eu ²⁺ particles prepared at 900 ° C. by ultrasonic spray pyrolysis at 1400 ° C.

FIG. 13 shows the results of X-ray diffraction analysis of Ba _0.91 Al ₁₂ O ₁₂ : Eu ²⁺ particles prepared at 900 ° C. by ultrasonic spray pyrolysis.

FIG. 14 is an electron micrograph of particles obtained by thermally treating BaMgAl ₁₀ O ₁₇ : Eu ²⁺ particles prepared at 900 ° C. by ultrasonic spray pyrolysis at 1400 ° C. FIG.

The multi-component blue light emitting oxide phosphor of the present invention can be prepared using a filter expansion aerosol generator (FEAG) or an ultrasonic spray pyrolysis apparatus as a spray pyrolysis apparatus (see FIGS. 1 and 2). The filter droplet generator FEAG has a characteristic of generating droplets at low pressure, unlike other conventional droplet generators, and includes a pneumatic nozzle for continuous solution supply; pressure gauge; Porous filters, which may be made of glass, metal, polymer or ceramic; High temperature reactor (furnace, tubular reactor) for particle formation reaction; A particle collector for recovering the produced particles; Liquid nitrogen traps; And a vacuum pump for vacuuming the inside of the system (see Korean Patent No. 144599, FIG. 1). In addition, the ultrasonic spray pyrolysis apparatus includes a peristaltic pump (peristaltic pump), a flow meter, an ultrasonic droplet nebulizer (ultrasonic nebulizer) for generating fine droplets for the transport of the raw material solution; High temperature reactor (tubular reactor) for particle formation reaction; And an electrostatic precipitator, including an electrostatic precipitator, a cold trap, a pump, a flow meter, and a filter (see FIG. 2).

In the present invention, a precursor is prepared by dissolving an activator doping each host and the electric matrix in distilled water or alcohol to meet the stoichiometric ratio of the multi-component phosphor to be prepared, and then using FEAG or ultrasonic spray pyrolysis apparatus. By spraying the droplets, and then converting the droplets introduced into the reactor into particles through a process of dry-decomposition-reaction-crystallization, and crystallization and activation through a post-treatment process such as heating, thereby providing Ba _x Mg _y Al _z O _m : Eu ²⁺ , where 0.9 <x <1.3, 1 <y <2, 10 <z <22; and m is determined to be an arbitrary value depending on the reaction that is continuous with the values of x, y, and z Aluminate-based blue light emitting oxide phosphor particles having a structure can be prepared, and the value of variable m is arbitrarily determined according to the molar ratio of x, y and z and the overall reaction.

Hereinafter, a method of manufacturing a multi-component blue light emitting oxide phosphor by spray pyrolysis using the FEAG and ultrasonic spray pyrolysis apparatus of the present invention will be described in more detail.

First Step : Obtaining a Phosphor Particle Precursor

Precursor solutions are prepared by dissolving each raw material component in distilled water so as to meet the stoichiometric ratio of the multicomponent blue light emitting oxide phosphor to be prepared by spray pyrolysis. In this case, each raw material is composed of an activator that enters the host and the electric matrix as a doping material, and these are salts of metals that are well dissolved in distilled water, that is, nitrates, acetates or salts of the metals. Chloride and the like, and preferably nitrate. As the mother, a water-soluble salt of barium (Ba), magnesium (magnesium, Mg), and aluminum (aluminum, Al) is used, and a water-soluble salt of europium (Europium, Eu) is used as an activator. When mixing them, the multi-component blue light emitting oxide phosphor (Ba _x Mg _y Al _z O _m : Eu ²⁺ (where 0.9 <x <1.3, 1 <y <2, 10 <z <22; and m) Is determined to be an arbitrary value depending on the subsequent reaction with the values of x, y, and z) to suit the stoichiometric ratio of barium, magnesium and aluminum to the water-soluble salts of barium 0.9 to 1.3; Water-soluble salts of magnesium 1 to 2; And dissolving the molar ratio of the water-soluble salt of aluminum 10-22 and the water-soluble salt of europium in distilled water in a composition such that the water-soluble salt is 1-100 mol% of the magnesium water-soluble salt to obtain a phosphor particle precursor solution. Since the size of the phosphor particles to be produced is determined according to the concentration of the precursor solution, the concentration of the precursor solution is selected to produce particles of a desired size. Preferably, the concentration is in the range of 0.02 to 2.0M. While changing from 0.02M to 2M it is possible to obtain the optimum light emission characteristics by controlling the size of the particles.

2nd process : spraying droplets using a spray pyrolysis apparatus

The precursor solution of the prepared phosphor particles was maintained at a high temperature of 200 to 1700 ° C., and the crystals were stabilized by crystallizing the phosphor in the gas phase by using a porous filter in the FEAG and a nebulizer in the ultrasonic spray pyrolysis apparatus. Droplets of about 10 μm, preferably about 10 μm are generated. At this time, by the FEAG, the flow rate of the air used as the carrier gas is 600L / min to enter into the tubular reactor that can raise the temperature to 1000 ℃ of 80cm in length, 100mm in inner diameter, by the ultrasonic spray pyrolysis device In this case, the flow rate of nitrogen and air used as the carrier gas is 0.1L / min to 15L / min, and enters into the tubular reactor capable of raising the temperature to 1700 ℃ of 1m length, 50mm inner diameter by a continuous process.

Third step : generation of phosphor particles through the reactor

Droplets entering the reactor are converted into phosphor particles through drying, decomposition, reaction and crystallization. At this time, drying is a process in which water contained in the droplets is evaporated and converted into solid particles, and decomposition is a process in which nitrogen or carbon components present in the phase-transformed particles are released as gases of NO ₂ or CO ₂ . The reaction is a process in which metal components, for example, Ba, Mg, Al, and the like are combined with oxygen and converted into oxides, and are converted into particles through crystallization in which the completed oxides are regularly rearranged. All these reactions are completed simultaneously in 0.01 seconds for FEAG and within several seconds for ultrasonic spray pyrolysis.

Fourth step : post-treatment for crystallization and activation of phosphor particles

When the residence time in the reactor is short or prepared at low temperature, for example, when BaMgAl ₁₀ O ₁₇ : Eu ²⁺ phosphor particles are produced at a residence time shorter than 1 second or at a temperature lower than 1200 ° C., crystallization and There is a need for a post treatment process for activation. At this time, the post-treatment process is carried out by heating the phosphor particles obtained in the third process at a temperature of 1000 to 1700 ℃ for 30 minutes to 12 hours, again 5 to 45% for the blue light emission of the activated particles Heated under hydrogen / nitrogen mixed gas and at a temperature of 1000-1700 ° C. for 30 minutes to 12 hours. In general, the luminous efficiency varies considerably according to the post-treatment temperature or the treatment time, and the phosphor prepared by spray pyrolysis shows sufficient light emission characteristics even at a lower temperature and a shorter post treatment time than the phosphor prepared by other methods. In addition, in order for the particles obtained through the heat treatment to emit blue light, Eu, an active agent, is converted from ³⁺ to ²⁺ when the heat treatment is performed in a hydrogen atmosphere.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention.

Example 1 Preparation of BaMgAl ₁₄ O ₂₂ : Eu ²⁺ Phosphors

The precursor solution dissolves nitrates of barium (Ba), magnesium (Mg) and aluminum (Aluminum, Al) in distilled water in a molar ratio of 1: 1: 14, and dope nitrates of europium (Eu). The concentration was made by adding fixed to the concentration that gives the best light emission, and the change in the size and shape of the particles was investigated while changing the total concentration of the precursor solution from 0.01 to 2M. FEAG or ultrasonic nebulizer was used as a droplet generator to spray the mixed solution into fine droplets, and the spray pyrolysis temperature was changed from the temperature at which the droplets were sufficiently dried to 1700 ° C. In order to observe the crystallinity, morphology, and optical properties of the particles produced by the tubular reactor for 30 minutes to 12 hours while changing the temperature of the particles from 1000 ° C to 1500 ° C, the heat-treated particles were again subjected to blue light emission. The heat treatment was repeated for 3 hours at a temperature of 1200 ° C. in a tubular reactor under a 25% nitrogen / hydrogen mixed gas atmosphere.

Next, the crystallinity and shape of the prepared particles were observed using an X-ray diffractometer (XRD) and a scanning electron microscopy (SEM), and centrifugal particle analyzers (CPSA) were used. The size and size distribution of the particles were measured using a size analyzer. The optical properties of the particles were measured by using a spectrophotometer (PL: photoluminescence) properties, and to excite the particles by using a Xenon lamp (Xenon lamp) was used to generate UV (see Fig. 3, 4, 5 and 6).

3 and 4 are heat treated for 3 hours at 1400 ℃ in the air prepared by the ultrasonic spray pyrolysis method when the reactor temperature is 900 ℃ (see Figure 3) or 1300 ℃ (see Figure 4), respectively 25 Electron micrographs of particles heat-treated for 2 hours under nitrogen / hydrogen atmosphere of%. As shown in FIGS. 3 and 4, the prepared particles remained perfectly spherical even after the heat treatment at high temperature irrespective of the preparation temperature, and no aggregation between the particles occurred. From the shape of the particles, it can be seen that crystals grow inside the micron-sized particles, that is, they have crystal growth characteristics in a plate-like structure, but are limited to the spherical particles to maintain a perfect spherical shape after crystallization. Confirmed. The particles prepared at a low temperature of 900 ° C. by spray pyrolysis do not show perfect spherical shape and agglomeration even after the heat treatment at a high temperature. As a result, spherical aluminate-based blue light-emitting phosphors can be produced even at low manufacturing temperatures above the temperature at which the droplets are completely dried. It can be seen that manufacturing is possible. The particles obtained by the above-described spray pyrolysis method maintained a spherical shape without agglomeration between the particles even at a heat treatment temperature of 1500 ° C. or higher. The reason why the agglomeration between the particles does not occur while maintaining the spherical shape after the high temperature heat treatment is because the individual components are well dispersed on the nanometer scale in the particles obtained by spray pyrolysis, and thus the final temperature is lower than the solid phase method. Because barium-aluminum-magnesium (BAM) crystals are obtained, the electrical BAM crystals are thermally stable, so once crystallized, they remain intact even after heat treatment at high temperatures.

FIG. 5 shows XRD results of particles prepared by spray pyrolysis at a temperature of 900 ° C. and subjected to heat treatment at 1400 ° C. for 3 hours, and the particles have crystals of pure BaMgAl ₁₄ O ₂₂ . The reason why the pure crystalline multicomponent particles are prepared at the heat treatment temperature lower than the solid phase method in the spray pyrolysis method is that the particles obtained by the spray pyrolysis method are well dispersed in the range of several to several tens of nanometers. In this example, BAM crystals began to appear at temperatures above 1200 ° C. and pure BAM crystals could be obtained above 1300 ° C.

6 is an electron micrograph of BaMgAl ₁₄ O ₂₂ : Eu ²⁺ particles prepared when FEAG is used as a spray pyrolysis apparatus. Particles were prepared at 900 ° C. by spray pyrolysis, and heat treated at 1400 ° C. for 3 hours, followed by heat treatment at 1100 ° C. in a hydrogen atmosphere. The oxide phosphor particles obtained by this process, like the particles obtained by ultrasonic spray pyrolysis, remained spherical without aggregation of the particles, and the prepared particles were pure BaMgAl ₁₄ O ₂₂ : It was confirmed that it had an Eu ²⁺ crystal.

Example 2 Preparation of BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ Phosphor

Except for varying the composition of the BAM material, BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ particles were prepared in the same manner as in Example 1, and the obtained oxide phosphor particles were X-ray diffractometer (XRD) and scanning electron microscope. (SEM) (see Figures 7, 8, 9 and 10).

7 and 8 are heat treated for 3 hours at 1400 ℃ in air, the particles prepared when the reactor temperature is 600 ℃ (see Figure 7) or 900 ℃ (see Figure 8) in the ultrasonic spray pyrolysis method, respectively, Electron micrographs of particles heat-treated again at 1100 ° C. for 2 hours under 20% nitrogen / hydrogen atmosphere. Like BaMgAl ₁₄ O ₂₂ : Eu ²⁺ obtained in Example 1, the particles remained perfectly spherical even after heat treatment at high temperatures regardless of the preparation temperature, no aggregation between the particles occurred, As in BaMgAl ₁₄ O ₂₂ : Eu ²⁺ , it was confirmed that plate crystals were grown in spherical particles.

FIG. 9 shows XRD results of BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ particles prepared by spray pyrolysis and subjected to heat treatment at 1400 ° C. for 3 hours. Again, the oxide phosphor particles obtained had a crystal structure similar to the particles obtained in Example 1.

FIG. 10 is an electron micrograph of BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ particles prepared when FEAG is used as a spray pyrolysis apparatus. Particles are prepared at 900 ° C. by spray pyrolysis to obtain electric particles. Heat treatment was performed at 1400 ° C. for 3 hours, and then heat treatment was performed at 1100 ° C. under hydrogen atmosphere. As shown in the figure, the obtained oxide phosphor particles, like the particles obtained by the ultrasonic spray pyrolysis apparatus, did not cause aggregation between particles and remained spherical, and the particles had pure BAM crystals as in the ultrasonic spray pyrolysis method. It was confirmed.

Example 3 Preparation of Ba _0.91 Al ₁₂ O ₁₂ : Eu ²⁺ Phosphors

An oxide phosphor was prepared in the same manner as in Example 1 except that the magnesium component was not included: In such an oxide phosphor, barium was more than quantitative (1 <x <1.8) or less (0.64 <x <1). In the case of blue light emission, it was found that x is 1.27 when the barium is more than quantitatively and x is 0.9 blue when the barium is less than the quantitative light. The preparation method and analysis method were the same as those of Examples 1 and 2, except that the composition of the substance was different. The obtained oxide phosphor particles were analyzed by X-ray diffractometer (XRD) and scanning electron microscope (SEM). 11, 12 and 13). 11 and 12 illustrate Ba _0.91 Al ₁₂ O ₁₂ : Eu ²⁺ particles prepared in the air by ultrasonic spray pyrolysis at 600 ° C. (see FIG. 11) and 900 ° C. (see FIG. 12), respectively. Electron micrographs of particles heat-treated at 1400 ° C. for 3 hours and heat-treated for 2 hours under 25% nitrogen / hydrogen atmosphere. As in Examples 1 and 2, the obtained particles remained perfectly spherical even after the heat treatment at high temperature, regardless of the preparation temperature, the aggregation of the particles did not occur at all, as well as the internal shape of the particles As in BaMgAl ₁₄ O ₂₂ : Eu ²⁺ obtained in Example 1, it was confirmed that plate-like crystals were grown inside spherical particles. 13 is XRD results of Ba _0.91 Al ₁₂ O ₁₂ : Eu ²⁺ particles prepared by spray pyrolysis at a temperature of 900 ° C. and subjected to a heat treatment at 1400 ° C. for 3 hours, wherein the particles were obtained in Example 1 It had a crystal structure similar to the oxide phosphor particles.

Example 4 Preparation of BaMgAl ₁₀ O ₁₇ : Eu ²⁺ Phosphors

BaMgAl ₁₀ O ₁₇ : Eu ²⁺ particles were prepared in the same manner as in Example 1 except for changing the composition of the BAM material, and the obtained oxide phosphor was analyzed by an electron microscope (see FIG. 14): FIG. In the ultrasonic spray pyrolysis method, the particles prepared at the reactor temperature of 900 ° C. were heat treated at 1400 ° C. for 3 hours in air, and subjected to heat treatment for 2 hours under a nitrogen / hydrogen atmosphere of 25%. As a result, a little different from the particles produced in Examples 1 to 3, agglomeration between particles occurred a lot, and spherical shapes disappeared and particles having irregular shapes were obtained. The reason for this is that in the case of BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , unlike the material obtained in Examples 1 to 3, a large amount of magnesium is contained, a magnesium component that is frequently used as a sintering aid of ceramic powder is It has been reconfirmed that it causes agglomeration between particles. In the case of BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ in the previous example, the ratio of magnesium / aluminum is higher than that of BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , but in the case of electrons, aggregation between particles does not occur and spherical It can be seen that maintaining the amount of aluminum rather than the relative ratio of magnesium / aluminum affects the shape of the particles. That is, in the case of BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ , the ratio of magnesium / aluminum is relatively higher than that of BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , but the high temperature sintering temperature is due to the large amount of aluminum. It was found to have a stable.

As described and demonstrated in detail above, the present invention provides a blue light emitting oxide phosphor by spray pyrolysis and a method of manufacturing the same. According to the present invention, a multi-component blue light emitting oxide having excellent crystallinity and luminescent properties with no agglomeration between particles while maintaining a perfect spherical shape even after long-term heat treatment at high temperature by spray pyrolysis using FEAG or ultrasonic spray pyrolysis. Phosphors can be prepared.

Claims (10)

(Iii) a water-soluble salt of barium, magnesium and aluminum as a host, and a water-soluble salt of barium 0.9 to 1.3; Water-soluble salts of magnesium 1 to 2; And 0.02 to 0.2 M of an oxide phosphor particle precursor by dissolving a water-soluble salt of aluminum 10-22 in a molar ratio of aluminum and an activator of europium as distilled water in a composition such that 1 to 100 mol% of the water-soluble salt of magnesium is dissolved. Obtaining a solution; (Ii) spraying the precursor solution of the oxide phosphor particles obtained in the foregoing into droplets having a diameter of 1 to 20 µm using a filter expansion aerosol generator (FEAG) or an ultrasonic spray pyrolysis apparatus; (Iii) converting the droplets into phosphor particles by dry-decomposition-reaction-crystallization reaction in a tubular reactor of FEAG or ultrasonic spray pyrolysis apparatus; And, (Iii) crystallization and activation by heating the phosphor particles for 30 minutes to 12 hours at a temperature of 1000 to 1700 ℃, again 30 minutes to 12 hours at a temperature of 1000 to 1700 ℃ under 5 to 45% hydrogen / nitrogen mixed gas Method of producing a multi-component blue light emitting oxide phosphor comprising the step of reheating during. delete delete The method of claim 1, Water-soluble salts are characterized in that the nitrate (acetate) or chloride (chloride) Method for producing a multi-component blue light emitting oxide phosphor. The method of claim 1, Spraying of the droplets is characterized in that it is carried out by crystallizing and stabilizing the phosphor in the gas phase by maintaining a high temperature of 200 to 1700 ℃ Method for producing a multi-component blue light emitting oxide phosphor. The method of claim 1, The sprayed droplets enter the tubular reactor capable of raising the temperature to 1000 ° C with a length of 80 cm and an inner diameter of 100 mm with a flow rate of 600 L / min for the air used as the carrier gas. Method for producing a multi-component blue light emitting oxide phosphor. The method of claim 1, The sprayed droplets have a flow rate of 0.1 L / min to 15 L / min for nitrogen and air used as a carrier gas in the case of the ultrasonic spray pyrolysis apparatus. Characterized by entering into a tubular reactor which can be elevated Method for producing a multi-component blue light emitting oxide phosphor. A multicomponent blue light emitting oxide phosphor prepared by the method of claim 1. The method of claim 8, The stoichiometric ratio is selected from the group consisting of water-soluble salts of barium, magnesium, and aluminum as water-soluble salts of barium 0.9 to 1.3; Water-soluble salts of magnesium 1 to 2; And a molar ratio of 10 to 22 water-soluble salts of aluminum and an activator of europium as a activator to be dissolved in distilled water in a composition such that 1 to 100 mol% of the water-soluble salts of magnesium are prepared. Multi-component blue light emitting oxide phosphor. The method of claim 8, Phosphor particles are BaMgAl ₁₄ O ₂₂ : Eu ²⁺ , BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ or BaMgAl ₁₀ O ₁₇ : Eu ²⁺ Multi-component blue light emitting oxide phosphor.