KR20020040500A - Gas-phase Combinatorial chemistry apparatus for searching on the composition of phosphors and preparing powders - Google Patents

Abstract

PURPOSE: Provided is a gas phase combinatorial chemistry synthetic device which synthesizes the powder of phosphors according to the composition ratio simply and continuously, controlled by a computer. The ratio of the composition is controlled by the changing quantity of the spraying solution. The device makes the synthesis fast and enables the low cost detection, in reduced time, of the composition ratio of dielectric materials, magnetic substances, material for electrodes and catalysts. CONSTITUTION: The device comprises: several solution storage tanks(1) which keep a certain quantity of various metal ion solution such as metal nitrate, metal acetate and metal chelate; a delivery pipe, a revolving speed induction motor which is computer controlled, and a solution introducing equipment which is composed of a pump head with the delivery pipe introducing a certain amount of different metal ion solution at the same time with a certain speed and time to suit each composition ratio; a high temperature tube reactor(4) or a spray equipment of air nozzle or micro wave nozzle which sprays solution as liquid into a flame reactor; a high temperature tube vapor reaction reactor with 1-2 meter length or flame reactor equipped with quarts tube or ceramic tube; a detector(5) which detects the existence or non-existence of powder and controls the operation of powder recovery equipment; a filter connected to a vacuum pump(7) and a continuous powder collecting equipment(6) composed of revolving belt with the filter which is controlled by a computer; a recovery equipment(8) for waste solution and waste powder which are not collected; and a computer(9) controlling the whole device.

Description

Gas-phase Combinatorial chemistry apparatus for searching on the composition of phosphors and preparing powders}

The present invention relates to a gas phase combination chemical synthesis apparatus for the exploration of the composition ratio of the fluorescent substance and powder production, and more particularly at a low cost in the exploration of the composition ratio of the fluorescent substance composed of a combination of the parent, the active agent and the sensitizer. In addition, the present invention relates to a gas-combination chemical synthesis apparatus for exploring the composition ratio and powder production of a new fluorescent substance which enables the exploration of the composition ratio more quickly.

The types of displays that make up the display industry can be roughly classified into three types: cathode ray tube (CRT), flat panel, and projection. Since these displays implement a natural color in each method, fluorescent materials required for this display are different, and accordingly, development of fluorescent materials suitable for each characteristic is essential.

The fluorescent material is composed of a combination of a mother, an active agent, a sensitizer, and the like, which is a material that emits light in the visible region after receiving energy from the outside and effectively absorbing it. The display quality of the information display device is closely related to the fluorescent material, and the development of highly efficient fluorescent material is a technology that must be solved in the field of the information display device.

In order to develop such a fluorescent material systematically and efficiently, technology for designing and searching materials, synthesizing and manufacturing materials, and evaluating and analyzing characteristics are basically required.

The new fluorescence and composition ratio search methods have been reported so far using chemical vapor deposition and inkjet printers, and these have been synthesized to have a composition of phosphor on a substrate and evaluated for fluorescence characteristics.

However, the chemical vapor deposition method is inexpensive because it requires expensive equipment to perform experiments under vacuum, and it is applicable to a system that can be applied as a thin film, but the actual plasma display panel (PDP) or field emission display (FED) In the case of using the powder form has a lot of problems in the application.

Even if the optimum composition is explored, there is a disadvantage in that the process of preparing the fluorescent material in powder form is performed.

In addition, the method using the inkjet printer is more economical than chemical vapor deposition, but it is easy to manufacture the fluorescent material because it is not uniformly mixed because it requires a process of repeatedly spraying the composition ratio without controlling the composition ratio at one time by spraying on a substrate and forming a thin film. Instead, it is subjected to heat treatment by coating on the substrate, and thus greatly affected by the substrate.

In addition, since the characteristics of the substrate are evaluated, there is a limit to properly assessing the characteristics of the powder, and even if the composition is searched, the fluorescent substance must be manufactured in the form of powder like chemical vapor deposition.

Accordingly, the present invention provides a new combination chemical powder combination chemical synthesis apparatus for exploring the composition ratio of a fluorescent substance composed of a combination of a parent, an active agent, a sensitizer, etc. more easily and quickly at a lower cost. In addition, since metal oxides of fluorescent materials having different composition ratios are continuously obtained in the form of spherical powders, fluorescent materials having good dispersibility can be produced even after post-heating treatment, and various solutions can be used simultaneously. It is an object of the present invention to provide a gas-combination chemical synthesis apparatus for the exploration of the composition ratio of fluorescent materials and for the preparation of powder effective for the exploration of materials.

Figure 1 shows the overall configuration of the gas phase combined chemical synthesis apparatus for the composition ratio search and powder production of the fluorescent material of the present invention.

Figure 2 is an electron micrograph of the powder synthesized in Example 1 by the gas phase combination chemical synthesis apparatus for the composition ratio search and powder production of the fluorescent material of the present invention,

3 shows the luminance of the powder synthesized in Example 1,

4 is an electron micrograph of the synthesized powder of Example 2,

Figure 5 shows the brightness of the powder synthesized in Example 2.

[Description of Symbols for Main Parts of Drawing]

1: solution storage device 2: solution injection device

3: injector 4: high temperature tube reactor (flame reactor)

41: thermostat 5: detector

6: continuous powder collecting device 7: vacuum pump

8: Waste liquid and waste powder recovery device 9: Control computer

The present invention provides a plurality of solution storage device capable of storing a certain amount of various metal ion solutions,

A solution injection device capable of injecting a metal ion solution of a certain concentration consisting of a transfer tube, a computer controlled rotational speed motor, and a pump head containing the transfer tube at a constant speed for a predetermined time;

An injector capable of injecting droplets of the solution injected into the hot tube reactor or flame reactor,

A high temperature tube reactor or flame reactor in which a gas phase reaction in which a quartz tube or a ceramic tube is mounted is performed,

A detector for determining the operation of the powder recovery apparatus by determining the presence or absence of powder;

A continuous powder collection device consisting of a rotary belt loaded with a filter connected to a vacuum pump and a computer controlled filter;

A waste and waste powder recovery device adapted to collect uncollected powder and filtrate,

In addition, the present invention is characterized by a gas phase combined chemical synthesis apparatus for exploring the composition ratio of the fluorescent substance and the powder production, which is composed of a computer controlling the whole.

Hereinafter, with reference to the accompanying drawings of the present invention in more detail as follows.

In order to achieve the above object, the present invention enables the manufacture of a metal oxide of a fluorescent material according to the composition ratio by injecting a solution using a precise motor controlled by a computer controlled rotation speed control, and a high temperature tube reactor or a flame reactor. The sprayed droplets can be made into a phosphor having direct crystallinity, and at the same time, it is characterized in that it is prepared in the form of a spherical powder having a dispersibility. In addition, the present invention in order to recover the fluorescent powder with a different composition ratio continuously to install a detector in the portion where the powder comes out and to install a collecting device that is moved by a computer to recover dozens to hundreds of different fluorescent powder each composition The present invention relates to a combinatorial chemical synthesizing apparatus.

Such a device according to the present invention, as shown in Figure 1, a high temperature tube reactor (or flame reactor) is installed, the solution storage device 1, the solution injection device 2, the injection device 3, the temperature controller 41 (4), detector 5, continuous powder collection device 6, vacuum pump 7, waste liquid and waste powder recovery device 8, and control computer 9.

The solution storage device (1) is composed of a plurality of, it is used to store a variety of metal ion solution of a constant concentration constituting the fluorescent material. The metal ion solution is preferably one selected from a metal nitrate solution, a metal acetate solution and a metal complex solution.

The solution injection device 2 according to the present invention is used to transfer a solution of a constant concentration to the injection device for a certain time at a constant speed. The device consists of a feed tube, a computer-controlled speed-sensitive motor, and a pump head with a feed tube. The metal ion solutions having a certain concentration are mixed and injected into the spray apparatus while being quantitatively injected simultaneously by the rotational speed motor. At this time, different metal ion solutions are injected at the same time by varying the rotational speed so as to match the composition ratio, and when the injection motors of the metal ion solutions are turned off at the same time, a certain amount of powder is synthesized and a different metal ion solution is added again. If the rotational speed is changed to match the composition ratio and injected at the same time, it is possible to synthesize a certain amount of powder of different composition. That is, by repeating the above experiment with the apparatus of the present invention, powders having different composition ratios can be continuously obtained. Such a solution injection device may adjust the injection speed of the reaction solution by applying a linear force by a computer controlled motor using a syringe-type injection device.

The injector 3 is used to inject droplets of solution injected into the hot tube reactor (or flame reactor) 4. This uses high pressure gas (nitrogen, argon, air, oxygen, etc.) to make a mixed solution into droplets and spray it into a hot tube reactor. At this time, the injection device uses a selected one of the air nozzle and the ultrasonic nozzle.

The high temperature tube reaction apparatus 4 is composed of a quartz tube or a ceramic tube and a temperature control controller, and the fluorescent substance having a uniform composition is produced by the gas phase reaction from the metal ion solution constituting the fluorescent substance by the apparatus. According to the present invention, the mixed metal ion droplets introduced into the high temperature tube reactor at a constant rate are reacted while passing through the tube at a set temperature (900 to 1500 ° C.), and at the same time, crystallization occurs during the reaction holding time to synthesize phosphor powder. At this time, the temperature reactor 41 is installed in the tube reactor in which the reaction takes place, the reaction holding time can be adjusted by the inner diameter and the length of the tube, the length of the tube is used 1 to 2 meters. The material of the reactor is mainly selected from a quartz tube, mullite or alumina tube.

In particular, the present invention may optionally use a flame reactor for the same purpose as the high temperature tube reactor, which forms a flame by injection of fuel and oxygen and uses it for the reaction. In the case of the flame reactor, the temperature is controlled according to the consumption of combustion gas, that is, propane gas or ethylene gas and oxygen gas, and the reaction occurs while passing through the flame. Therefore, in the present invention, by directly spraying the droplets injected from the injector into a high-temperature flame to react the fluorescent material, it is possible to obtain a fluorescent material having a crystalline and powder composition having a different composition ratio.

The detector 5 of the present invention is used to determine the operation of the powder recovery apparatus by determining the presence or absence of the powder obtained through the above steps.

In addition, the powder recovery device 6 is composed of a rotary belt loaded with a filter, a computer-controlled filter. This allows the powders to be collected by different filters after the detector 5 determines the presence or absence of powder from the reaction tube. The filter is connected to a vacuum apparatus, and the powder is immediately collected when the vacuum is maintained by the vacuum pump.

At this time, the uncollected powder and the filtrate are collected through the waste liquid and the waste powder recovery apparatus 8.

And all the above devices are controlled by the computer 9.

When the metal oxide of the fluorescent material is manufactured using the gas phase combined chemical synthesis apparatus described above, tens to hundreds of powders having different compositions from tens of mg to several g can be obtained continuously. In addition, for the purpose of improving the crystallinity of the metal oxide prepared from the gas phase combination chemical apparatus, after the post-heat treatment, a spherical fluorescent substance with uniform particles and a controlled shape can be obtained. have. The apparatus can be used to search for composition ratios of multicomponent oxides selected from dielectrics, magnetic materials, superconductors, electrode materials and catalysts.

Example 1

The proposed device was used to search for Yttrium oxide phosphors doped with europium. The concentration of the solution was 1 M and Europium had a doping concentration of 6 mol%. In order to manufacture phosphor powders having optimal luminescence properties, the present inventors of FIG. 1 tried to search for the optimum amount of flux and flux. In this embodiment, it was intended to compare the luminescence properties of the powders obtained by the change of the amount of boric acid used as a flux at the reactor temperature of 1300 ℃. The amount of boric acid added was continuously produced in 0% up to 40% in 1% increments. At this time, the optimum manufacturing conditions were searched through the form, crystallinity and luminescence properties of the powders obtained.

2 shows electron micrographs of Y ₂ O ₃ : Eu phosphor powders prepared when the amount of boric acid, typically flux, is 0, 5, 10%. The addition of flux did not significantly change the morphological properties of the powder. 3 shows the light emission characteristics of the powders obtained. When the addition amount of the flux was 10%, the maximum was reached, and the emission luminance decreased as the addition amount was increased.

Example 2

The kind and production conditions of the phosphor powder were the same as in Example 1 except that Na ₂ CO ₃ was used as the kind of flux. FIG. 4 shows electron micrographs of Y ₂ O ₃ : Eu phosphor powders prepared when the flux of Na ₂ CO ₃ is 0, 10, and 20%, respectively. In some cases, the addition of fluxes greatly influenced the shape of the powder. That is, when no flux was added, the spherical shape was maintained, whereas when the flux was added, the powder partially dissolved at high temperature, and the spherical shape was distorted.

5 shows the light emission characteristics of the powders. As shown in FIG. 5, it can be seen that the optimum amount of flux added varies depending on the production temperature, the heat treatment temperature, and the like in the spray pyrolysis method. Although the present apparatus has been seen in the present embodiment, since the dozens of sample powders can be manufactured continuously in a short time, it can be used in various ways such as searching for new fluorescent materials or optimizing existing fluorescent materials.

As described above, using the gas phase combined chemical synthesis apparatus provided in the present invention has the following advantages.

1. Since the metal oxide of the fluorescent material is produced by the gas phase reaction from the solution, it is possible to produce the fluorescent material with a uniform composition.

2. It can be made into powder with high crystallinity and good dispersion because of using high temperature tube reactor or flame reactor.

3. By using computer-controlled injection device and collection device, it is possible to continuously manufacture metal oxides with different composition ratios at regular intervals.

4. It is effective to search multi-component fluorescent materials because several solutions can be used at the same time.

5. Since the synthesized metal oxide is obtained in the form of powder even though there is little crystallinity, it is possible to prepare a fluorescent material having good dispersibility even after the post heat treatment.

6. Since the optimal fluorescent substance can be obtained in the form of powder by post-heat treatment, the result of evaluating the fluorescence characteristics can be applied to the application of the display device as it is.

Claims (10)

A plurality of solution storage device for storing a certain amount of various metal ion solution, A solution injection device capable of injecting a metal ion solution of a certain concentration consisting of a transfer tube, a computer controlled rotational speed motor, and a pump head containing the transfer tube at a constant speed for a predetermined time; An injector capable of injecting droplets of the solution injected into the hot tube reactor or flame reactor, A high temperature tube reactor or flame reactor in which a gas phase reaction in which a quartz tube or a ceramic tube is mounted is performed, A detector for determining the operation of the powder recovery apparatus by determining the presence or absence of powder; A continuous powder collection device consisting of a rotary belt loaded with a filter connected to a vacuum pump and a computer controlled filter; A waste and waste powder recovery device adapted to collect uncollected powder and filtrate, And a chemical composition control device for exploring the composition ratio of the fluorescent substance and for producing a powder. The apparatus of claim 1, wherein the metal ion solution stored in the solution storage device is selected from metal nitrate, metal acetate, and metal complex solution. . The method of claim 1, wherein the solution injection device is to control the injection speed of the different metal ion solution by a computer-controlled rotational speed-sensing motor to simultaneously inject different metal ion solutions to match each composition ratio Gas phase combined chemical synthesis apparatus for the composition ratio search and powder production of the fluorescent material. According to claim 1 or 3, wherein the solution injection device is in the form of a syringe, the composition ratio search and powder of the fluorescent material, characterized in that for controlling the injection rate of the reaction solution by applying a linear force by a motor controlled by a computer Vapor combination chemical synthesis apparatus for manufacturing. The apparatus of claim 1, wherein the injector is selected from an air nozzle and an ultrasonic nozzle. According to claim 1, wherein the tube length of the high-temperature tube reaction apparatus is a gas phase combined chemical synthesis apparatus for the composition ratio search and powder production of the fluorescent material, characterized in that 1 to 2 meters. The apparatus of claim 1 or 6, wherein the material of the high temperature tube reaction apparatus is selected from a quartz tube, a mullite, or an alumina tube. The method of claim 1, wherein in the flame reactor, the droplets formed from the injector are directly injected into the flame formed by the injection of fuel and oxygen, and the reaction is performed. Synthesis device. The method of claim 1, wherein the continuous powder collecting device is a computer-controlled composition ratio of the fluorescent material characterized in that the computer is controlled so as to continuously synthesize the oxide having a different composition ratio, and then to collect the powder by the detector and recover each with a filter. Vapor combination chemical synthesis apparatus for manufacturing. The apparatus of claim 1, wherein the apparatus is used to search for a composition ratio of a multi-component oxide selected from a dielectric, a magnetic material, a superconductor, an electrode material, and a catalyst.