KR101388189B1 - Chlorosilicate phosphor and preparing method of the same - Google Patents

Abstract

The present invention relates to a chlorinated silicate-based phosphor added with a rare earth metal and a method for producing the same, and a chlorinated silicate-based phosphor added with a rare earth metal having an effect of emitting light at a long wavelength using a large ionic radius of chlorine atom .

Description

TECHNICAL FIELD [0001] The present invention relates to a chlorosilicate-based phosphor and a method for producing the same. BACKGROUND ART [0002]

The present invention relates to a chlorinated silicate-based phosphor added with a rare earth metal and a method for producing the same, and a chlorinated silicate-based phosphor added with a rare earth metal having an effect of emitting light at a long wavelength using a large ionic radius of chlorine atom .

In the conventional art of producing a phosphorus silicate-based phosphor, solid precursors mixed with a solid state material are usually obtained through firing in a reducing atmosphere in which oxygen is intercepted. However, in such a phosphor preparation method, solid CaCl ₂ and When the same metal salt is used and solid phase mixing is carried out using such a sample, uniform mixing is difficult due to the dehumidification property of the metal salt, and it has a great influence on the resultant (Korean Patent Laid-Open No. 10-2010-0070731). This problem can be minimized through the use of a glove box device, but still heterogeneous mixing by the solid state method is a problem. Accordingly, there is a demand for development of a method for producing a phosphorus silicate-based phosphor having high dispersibility and high brightness by solving such problems.

The inventors of the present invention have studied a method for producing a phosphorus silicate-based phosphor powder in which uniform phosphor and single particles of single crystal are uniformly distributed without agglomeration. As a result, The present invention also relates to a process for producing a novel chlorosilicate-based phosphor capable of synthesizing a chlorosilicate-based phosphor powder having a particle shape and also a round shape and which can be used for a white LED or any lamp, and a novel chlorosilicate- Thus completing the present invention.

Accordingly, the present invention relates to a chlorosilicate-based phosphor added with a rare earth metal and a method for producing the same, and a chlorosilicate-based phosphor added with a rare earth metal having an effect of emitting light at a long wavelength using a large ion radius of chlorine atom .

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

According to an aspect of the present invention, a metal salt mixed solution containing a metal chloride for synthesizing a chlorosilicate-based phosphor to which a rare earth metal is added is mixed with a SiO ₂ sol in a liquid phase to obtain a metal salt -SiO ₂ sol mixed solution; The method comprising impregnating and drying the metal salt -SiO ₂ sol mixed solution into a polymer material, followed by low-temperature calcination, pre-acidification and post-reduction calcination to obtain a chlorosilicate-based phosphor .

Another aspect of the present invention relates to a chlorosilicate-based phosphor prepared by the method of the present invention and a use thereof.

The present invention provides a chlorinated silicate-based phosphor added with a rare earth metal and a method for producing the same, and a chlorinated silicate-based phosphor added with a rare earth metal having an effect of emitting light at a long wavelength using a large ion radius of chlorine atom . Specifically, a novel synthesis method of synthesizing a high-efficiency chlorosilicate-based phosphor after impregnating a polymer material with a solution of a metal salt mixed solution containing a chloride-based metal and a SiO ₂ sol and heat-treating the polymer material in an atmosphere in which the polymer material is decomposed . According to one of some embodiments of the present application, a liquid precursor is impregnated with cellulose and dried, followed by a low-temperature calcining step and pulverization to obtain a uniform precursor. The preform is subjected to a pre- It is possible not only to have a luminous efficiency but also to produce a halogenated chlorosilicate-based phosphor excellent in productivity and economy because it can be produced in a short time. The phosphor may be a display including any one of a cathode ray tube, a light emitting diode (LED), a plasma display panel (PDP), and a field emission display (FED) and a cold cathode fluorescent lamp (CCFL).

Figure 1 is a flow chart of a method of making a chlorosilicate according to one embodiment of the present invention.
FIG. 2 is a SEM image of a precursor of Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +} phosphor powder showing the shape and size of the powder obtained through low-temperature calcination in the process according to Example 1 of the present application.
FIG. 3 shows a pattern obtained by X-ray diffraction of a Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +} phosphor powder obtained according to an embodiment of the present invention, in comparison with JCPDS card number: 70-2447.
4 is an SEM image of the Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +} phosphor powder obtained according to one embodiment of the present invention.
FIG. 5 shows the results of SEM-EDS analysis of Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +} phosphor powder obtained according to one embodiment of the present invention.
FIG. 6 is a result obtained by PL analysis of the Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +} phosphor powder obtained according to one embodiment of the present invention.
FIG. 7 shows the result of PL analysis of Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +} phosphor powder obtained according to one embodiment of the present invention.
8 is a result obtained by analyzing an X-ray powder pattern of a Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +} phosphor powder obtained according to an embodiment of the present invention.
FIG. 9 is a graph showing the relationship between the PL of Ca ₃ (Si, Al) O ₄ Cl ₂ : Eu ^{2 +} and (Ca, Mg) ₃ (Si, Al) O ₄ Cl ₂ : Eu ²⁺ phosphor powder obtained according to an embodiment of the present invention This is the result obtained through analysis.
10 is obtained in accordance with one embodiment of the present _{Ca 3 (Si, Al) O} 4 Cl 2: Eu 2 + , and _{(Ca, Mg) 3 (Si} , Al) O 4 Cl 2: Eu 2+ X of the phosphor powder - The results obtained by analyzing the line powder pattern.
11 is obtained _{(Na 1 .49- x Na x)} Si 0 .45, Al 1 .55 O 4 -1 / 2x Cl x , in accordance with an embodiment of the present application: X- ray powder of 0.06Eu ²⁺ phosphor powder This is the result obtained by pattern analysis.
12 is obtained _{(Na 1 .49- x Na x)} Si 0 .45, Al 1 .55 O 4 -1 / 2x Cl x , in accordance with an embodiment of the present application: PL through the analysis of 0.06Eu ²⁺ phosphor powder The results obtained.
13 is obtained _{(Na 1 .49- x Na x)} Si 0 .45, Al 1 .55 O 4 -1 / 2x Cl x , in accordance with an embodiment of the present application: FE-SEM image of 0.06Eu ²⁺ phosphor powder to be.

Hereinafter, embodiments and examples of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention with reference to the accompanying drawings.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

As used herein, the terms "about,"" substantially, "and the like are used herein to refer to or approximate the numerical value of manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to prevent unauthorized exploitation by unauthorized intruders of the mentioned disclosure. Also, throughout the present specification, the phrase " step "or" step "does not mean" step for.

According to an aspect of the present invention, a metal salt mixed solution containing a metal chloride for synthesizing a chlorosilicate-based phosphor to which a rare earth metal is added is mixed with a SiO ₂ sol in a liquid phase to obtain a metal salt -SiO ₂ sol mixed solution; The method comprising impregnating and drying the metal salt -SiO ₂ sol mixed solution into a polymer material, followed by low-temperature calcination, pre-acidification and post-reduction calcination to obtain a chlorosilicate-based phosphor .

In one embodiment of the present invention, the chlorosilicate-based phosphor may have high dispersibility and high brightness, but is not limited thereto.

In one embodiment of the present invention, the chlorosilicate-based phosphor may have high dispersibility and high brightness, but is not limited thereto.

In one embodiment of the invention, the polymeric material is selected from the group consisting of corn starch, potato starch, cellulose powder, cellulose sheet, spherical cellulose, water soluble cellulose, pulp, crystallized cellulose, amorphous cellulose, rayon and combinations thereof But are not limited thereto.

In one embodiment of the present invention, the metal salt may be selected from the group consisting of a chloride-based metal salt, a nitride-based metal salt, a sulfide-based metal salt, an acetate-based metal salt, and combinations thereof.

 In one embodiment of the present invention, the metal salt including the metal chloride may be selected from the group consisting of a salt of an alkali metal or an alkaline earth metal, a salt of a transition metal, a salt of a rare earth metal, and combinations thereof. It is not.

In one embodiment of the source, the alkali metal or alkaline earth metal chloride is a chloride selected from the group consisting of LiCl, NaCl, KCl, BeCl _2, MgCl _2, CaCl _2, SrCl _2, BaCl _2, and combinations thereof But is not limited thereto.

In one embodiment of the invention, the chloride of the transition metal is selected from the group consisting of ScCl ₃ , TiCl ₄ , VCl ₄ , CrCl ₃ , MnCl ₃ , FeCl ₃ , CoCl ₂ , NiCl ₂ , CuCl ₂ , ZnCl ₂ , YCl ₃ , ZrCl ₄ , NbCl ₅ , MoCl ₅ And a chloride selected from the group consisting of combinations thereof. However, the present invention is not limited thereto.

In one embodiment of the invention, the chloride of the rare earth metal is selected from the group consisting of LaCl ₃ , CeCl ₃ , NdCl ₃ , EuCl ₃ , GdCl ₃ , TbCl ₃ , DyCl ₃ , ErCl ₃ , YbCl ₃ , But are not limited to, the chloride to be selected.

In one embodiment of the invention, the SiO ₂ precursor may be one selected from the group consisting of SiO ₂ , Si (OH) ₄ , SiH ₄ , Si (OC ₂ H ₅ ) ₄ and water soluble silane But is not limited to.

In one embodiment of the present invention, the chlorinated silicate-based phosphor obtained is at least one selected from the group consisting of M-Si-O-Cl, M-Si-BO-Cl, M-Si- And M is selected from the group consisting of an alkali metal, an alkaline earth metal, a transition metal, a rare earth metal, and a combination thereof, but the present invention is not limited thereto.

In one embodiment of the present invention, the metal chloride mixed solution containing the metal chloride may include at least one chloride-based metal salt, but is not limited thereto.

In one embodiment of the invention, the SiO ₂ sol comprising a water-soluble SiO ₂ or a water-soluble _{Si (OC 2 H 2 OH)} 4, the particle size of the SiO _2, for example about 5 nm to about 3000 nm,, From about 100 nm to about 3000 nm, from about 100 nm to about 3000 nm, from about 100 nm to about 3000 nm, from about 200 nm to about 3000 nm, from about 300 nm to about 3000 nm, from about 400 nm to about 3000 nm, from about 700 nm to about 3000 nm, from about 800 nm to about 3000 nm, from about 900 nm to about 3000 nm, from about 1000 nm to about 3000 nm, from about 5 nm to about 3000 nm, From about 5 nm to about 2000 nm, from about 5 nm to about 1500 nm, from about 5 nm to about 1000 nm, or from about 5 nm to about 500 nm, and may be an acidic or basic solution, It is not.

In one embodiment of the present invention, in the above manufacturing method, the metal salt mixed solution containing the metal chloride is impregnated into the polymer material and dried to remove the solvent to form a xerogel or a cresol. But is not limited thereto.

In one embodiment herein, the cold calcination is conducted at a temperature of from about 150 to about 400 DEG C, such as from about 180 to about 400 DEG C, from about 200 to about 400 DEG C, from about 250 to about 400 DEG C, from about 300 to about 400 DEG C , About 150 to about 350 캜, about 150 to about 300 캜, or about 150 to about 250 캜.

In one embodiment herein, the line-of-sight pixelability is about 500 to about 1000 캜, such as about 600 to about 1000 캜, about 700 to about 1000 캜, about 800 to about 1000 캜, about 900 to about 1000 캜 , About 500 to about 900 캜, about 500 to about 800 캜, about 500 to about 700 캜, or about 500 to about 600 캜.

In one embodiment herein, the post-calcination is performed at a temperature of from about 700 to about 1400 DEG C, such as from about 800 to about 1400 DEG C, from about 900 to about 1400 DEG C, from about 1000 to about 1400 DEG C, from about 1100 to about 1400 DEG C ℃, within from about 1200 to about 1400 ℃, about 700 to about 1300 ℃, about 700 to about 1200 ℃, about 700 to about 1100 ℃, about 700 to about 1000 ℃, or from about 700 to about 900 ℃ H ₂ - Containing reducing gas in the presence of a reducing gas.

 In one embodiment of the present invention, the manufacturing method may include, but is not limited to, a crushing process after calcination and firing.

 In one embodiment of the present invention, the chlorosilicate-based phosphor obtained may have a round particle shape and a particle size of from about 50 nm to about 10 탆, but the present invention is not limited thereto. For example, the particle size may range from about 50 nm to about 10 microns, from about 80 nm to about 10 microns, from about 100 nm to about 10 microns, from about 200 nm to about 10 microns, from about 300 nm to about 10 microns, from about 400 from about 500 nm to about 10 탆, from about 600 nm to about 10 탆, from about 700 nm to about 10 탆, from about 800 nm to about 10 탆, from about 900 nm to about 10 탆, from about 1000 nm to about 10 nm, About 10 microns, about 50 nanometers to about 5 microns, or about 50 nanometers to about 1 micron, but is not limited thereto.

In one embodiment, a solution comprising a rare earth metal and a chloride is mixed with a SiO ₂ sol as a liquid precursor, the cell is impregnated with a polymer material such as rosewise, dried, , And then a spherical phosphor is obtained through line oxidation and post-reduction firing.

In one embodiment, during the course of the linearisation, the first polymer is decomposed by calcination to a temperature of about 150 to about 400 DEG C and the preferred temperature is between about 200 and about 300 DEG C The solid precursor powder obtained by decomposing a high-molecular substance such as rosewose is roasted to increase the surface area by pulverization, thereby inducing uniform decomposition and oxidation. In addition, the chlorination is oxidized during the second firing without pulverization And the oxide-based silicate is obtained before the carbon material is oxidized. Polymeric materials such as celluloses are difficult to decompose at temperatures below 150 ° C and degradation and oxidation at temperatures above 400 ° C may affect the resulting product because the secondary firing process without grinding at the intermediate stage As the process proceeds, chlorides mixed with the oxide can be obtained. Through the pulverization, a uniform chlorosilicate-based phosphor can be obtained at a lower temperature, but is not limited thereto.

In one embodiment, as a secondary calcination of the obtained solid precursor powder, the residual organic matter is removed at a temperature of about 500 to about 1000 DEG C and calcined in an oxygen-containing atmosphere to achieve crystallinity. The temperature of the secondary baking may be, for example, from about 500 to about 1000 캜, from about 600 to about 1000 캜, from about 700 to about 1000 캜, from about 800 to about 1000 캜, from about 900 to about 1000 캜, About 900 ° C, about 500 ° C to about 800 ° C, about 500 ° C to about 700 ° C, or about 500 ° C to about 600 ° C. This process is characterized by providing a temperature at which the SiO ₂ sol crystallizes and removing residual organic matter. A temperature of 400 ° C or less is difficult to crystallize amorphous SiO ₂ and requires a long baking time. On the other hand, at a temperature of 1000 ° C or higher, the chlorosilicate system is not preferable because the chloride compound is oxidized according to the crystal stability to obtain the silicate phosphor, and a temperature of about 600 to about 800 ° C is preferable, but not limited thereto.

The phosphor powder obtained is then subjected to heat treatment at a temperature of about 700 to about 1400 ° C, for example, about 800 to about 1400 ° C, about 900 to about 1400 ° C, about 1000 to about 1400 ° C, about 1100 to about 1400 ° C, Crystal growth and resurrection through firing at about 1200 to about 1400 ° C, about 700 to about 1300 ° C, about 700 to about 1200 ° C, about 700 to about 1100 ° C, about 700 to about 1000 ° C, or about 700 to about 900 ° C Based phosphor and a method for producing the same. At a temperature of 700 ° C or less, it may lead to an unfavorable environment for a good reducing atmosphere and may cause a decrease in luminance and luminescence intensity. Also, at a temperature of 1400 ° C or higher, the powder becomes a sintered body and the powder is lost in its properties. Temperatures between about 800 and about 1100 < 0 > C are preferred, but are not limited thereto.

In one embodiment of the present invention, since the synthesis of the high-efficiency chlorosilicate-based phosphor is advantageous by using the liquid precursor, in the production of the precursor for synthesizing the phosphor, the metal M is an alkali metal or an alkaline earth metal chloride (for example, LiCl _{, NaCl, KCl, BeCl 2,} MgCl 2, CaCl 2, SrCl 2, BaCl 2 , and the like); The transition metal metal chlorides (for example, ScCl ₃ , TiCl ₄ , VCl ₄ , CrCl ₃ , MnCl ₃ , FeCl ₃ , CoCl ₂ , NiCl ₂ , CuCl ₂ , ZnCl ₂ , YCl ₃ , ZrCl ₄ , NbCl ₅ , MoCl ₅ Etc); A novel composition of a chlorosilicate-based phosphor is obtained by using a lanthanide (rare earth) chloride (for example, LaCl ₃ , CeCl ₃ , NdCl ₃ , EuCl ₃ , GdCl ₃ , TbCl ₃ , DyCl ₃ , ErCl ₃ or YbCl ₃ ) But it is not limited thereto.

In one embodiment, chlorides are used in the case of LiCl, MgCl ₂ , ScCl ₃ , TiCl ₄ , VCl ₄ , CrCl ₃ , MnCl ₃ , FeCl ₃ , CoCl ₂ , NiCl ₂ , CuCl ₂ , ZnCl ₂ , In the production process using SiO ₂ or SiO ₂ + Al salt due to the large difference in ionic radius between each metal ion and Cl ion in the synthesis process, it is baked at a temperature of about 500 ° C. for about 10 hours as a heat treatment temperature for the second firing And the other chlorinated materials described above are preferably subjected to heat treatment at a temperature of about 600 to about 800 ° C for less than about 5 hours because the ionic radius holding the chlorine is sufficiently secured, but the present invention is not limited thereto.

In one embodiment, the chlorinated silicate-based phosphor has a composition based on M-Si-O-Cl, M-Si-BO-Cl, M-Si-Al- The M may be a combination of at least two or more metals, but the present invention is not limited thereto, although the novel chloride silicate-based phosphor may be easily synthesized based on such a composition.

In one embodiment, in order to form a matrix in which SiO ₂ is easily soluble and easily evaporable, such as B, the substrate is fired at a low temperature of about 400 ° C. for about 10 hours or more during the second firing, The chloride-based fluorescent material can be obtained by inducing crystallization of SiO ₂ at about 700 ° C for about 2 hours in a reducing atmosphere in which oxygen of firing is excluded, and then inducing crystal growth at about 900 ° C.

In one embodiment, when a matrix is formed by mixing P ₂ with SiO ₂ , P having strong ionic and high electron mobility is likely to form an MPO-Cl form before forming a matrix with Si and other metal salts After obtaining the amorphous phase of the first calcination, the mother of M-Si-PO-Cl should be obtained by inducing crystallization of SiO _{2 at} a temperature of about 700 ° C or higher through a rapid heating rate.

In one embodiment, the composition of the silicate-based phosphor may be represented by M1 _{v -u} Si _w A _x O _y Cl _z : M2 _u , wherein M1 is an alkali metal or alkaline earth metal chloride (eg , LiCl, NaCl, KCl, BeCl ₂ , MgCl ₂ , CaCl ₂ , SrCl ₂ , BaCl _2, etc.); The transition metal metal chlorides (for example, ScCl ₃ , TiCl ₄ , VCl ₄ , CrCl ₃ , MnCl ₃ , FeCl ₃ , CoCl ₂ , NiCl ₂ , CuCl ₂ , ZnCl ₂ , YCl ₃ , ZrCl ₄ , NbCl ₅ , MoCl ₅ Etc); (E.g., LaCl ₃ , CeCl ₃ , NdCl ₃ , EuCl ₃ , GdCl ₃ , TbCl ₃ , DyCl ₃ , ErCl ₃ , YbCl _3, etc.) ; A may comprise B, Al, or P; M2 represents a rare-earth-based material of M1; v represents a number from about 1 to about 8, w represents a number from about 1 to about 7, x represents a number from about 1 to about 5, y represents a number from about 3 to about 40 , z represents a number from about 0.5 to about 40, and u may be within about 0.5 to about 20 mol% of v, but is not limited thereto.

In one embodiment, a novel chlorosilicate-based phosphor having a basic composition such as M-Si-A-O-Cl (A: B, Al, P)

In one embodiment, the amount of chlorine in a single crystal can be controlled by using another kind of salt containing oxygen using the same kind of metal material. As a simple example, it can be expressed by equation 1:

<Reaction Scheme 1>

₂ CaCl ₂ (metal chloride) + Ca (NO ₃ ) ₂ (metal nitride) + SiO ₂ (sol) → Ca ₃ SiO ₄ Cl ₂

The metal chloride salt, metal nitrate salt, and sol used in Scheme 1 exist in a liquid form in a solvent. Also, to illustrate the simple reaction, the lubricant was ignored because it was a minor additive. In addition, the metal nitrate has the condition that oxygen is easily contained in the material and can be easily oxidized. On the other hand, since the metal chloride salt does not contain oxygen in the material, the chlorinated silicate-based phosphor can be easily obtained by the above reaction scheme, and chlorine in the single crystal can be controlled, but the present invention is not limited thereto.

In one embodiment, the pulverization of the phosphor powder may be performed in any of the processes described above. Examples of the pulverizing process include a ball mill, a roll mill, a vibrating ball mill a dry type disperser such as a ball mill, an attritor mill, a planetary ball mill, a sand mill, a cutter mill, a hammer mill, a jet mill or the like, Or a high-pressure homogenizer. By using the pulverization process through this apparatus, the phosphor powder can be further atomized and the surface area can be widened to shorten the time of oxidation or reduction and lower the synthesis temperature. , But is not limited thereto.

In one embodiment, the silicon-containing compound as the SiO ₂ precursor may be a silicon precursor compound commonly used in the art, for example, water soluble silicate (WSS), SiO ₂ sol (Sol) Size 5 to 3000 nm or less), and the like, but the present invention is not limited thereto.

In one embodiment, the polymeric material may be selected from the group consisting of cellulose, amorphous cellulose, pulp, rayon, and combinations thereof, but is not limited thereto. For example, the polymeric material may be crystalline cellulose (purity 99.99%), spherical cellulose (purity 99.9%), high purity pulp (99.8%) or rayon. For example, it is preferable, but not limited, to select a high purity pulp having a finer matrix shape.

In one embodiment, the calcination in the reducing atmosphere is performed in a reducing atmosphere of N ₂ / H ₂ = (90 to 95) / (10 to 5) or Ar / H ₂ = (90 to 95) / (10 to 5) But is not limited thereto.

In one embodiment, the phosphorus silicate-based phosphor powder may have a particle size of from about 50 nm to about 10 m, but is not limited thereto.

Another aspect of the present invention provides a chlorosilicate-based phosphor which is produced by the manufacturing method according to the present invention.

In one embodiment of the present invention, the chlorosilicate-based phosphor may be one used for a display or a lamp, but is not limited thereto.

In one embodiment of the present invention, the display may be any one of a cathode ray tube, a light emitting diode (LED), a plasma display panel (PDP), and a field emission display (FED) , But is not limited thereto.

In one embodiment of the present invention, the chlorosilicate-based phosphor may have a characteristic of a super long afterglow phosphor, but is not limited thereto.

Another aspect of the present invention relates to a lamp comprising a chlorosilicate-based phosphor produced by the process according to the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited by these Examples.

[ Example ]

< Example  1> SiO ₂  in  Synthesized Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +}  Phosphor experiment

1.97 mol of CaCl ₂ , 1 mol of Ca (NO ₃ ) ₂ , 1 mol of SiO ₂ (Sol) and 0.03 mol of EuCl ₃ were dissolved in deionized water (DI water) according to the procedure described in FIG. Each was dissolved for about 10 to 20 minutes, followed by stirring to form a 20 wt% solution. The mixed solution was weighed so that the Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +} phosphor powder was 5 g. The mixed solution was impregnated with cellulose powder at a ratio of 2: 1, uniformly stirred and impregnated for 10 minutes through an acetone, an ultrasonic device and stirring. The impregnated precursor was placed in a dryer at 80 ° C., dried for 10 hours, and then calcined at 225 ° C. for 6 hours.

The calcined powder was pulverized into fine particles (FIG. 2) through a hand mill to increase the surface area, and the powder thus obtained was calcined at 700 DEG C for 2 hours in an atmosphere containing oxygen. Finally, the thus-obtained white powder was fired at 700 ° C. for 2 hours in a reducing atmosphere of N ₂ / H ₂ (95/5) through a tube furnace to obtain a Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +} phosphor powder . The obtained phosphor powders were analyzed by XRD (FIG. 3), SEM (FIG. 4), SEM-EDS (FIG. 5) and PL (FIG. 6).

< Example  2> water soluble silicone compound ( Water soluble 실리콘 compound ; WSS Synthesized with Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +}  Phosphor experiment

1.97 mol CaCl ₂ , 1 mol Ca (NO ₃ ) ₂ , 1 mol WSS (Sol) and 0.03 mol EuCl ₃ were dissolved in deionized water (DI water) for about 10 to 20 minutes, To make a 20 wt% solution. The mixed solution was weighed so that the Ca ₃ SiO ₄ Cl ₂ : Eu ^{2 +} phosphor powder was 5 g. This mixed solution was mixed with Starch (potato powder) at a ratio of 1: 3. And homogeneously stirred and impregnated for 10 minutes through an ultrasonic device and stirring. The impregnated precursor was placed in a dryer at 80 ° C., dried for 10 hours, and then calcined at 225 ° C. for 6 hours. As the impregnated precursor was dried and first calcined, it became a xerogel and its volume increased greatly. After the first calcination, the powder obtained after the heat treatment at 500 ° C for 2 hours was pulverized to increase the surface area so that it could be easily oxidized, and further calcined in air at 700 ° C for 1 hour. Further, PL characteristic (FIG. 7) and X-ray powder pattern analysis (FIG. 8) were performed by firing at 700 ° C., 900 ° C. and 1000 ° C. for 3 hours to reduce the phosphor powder. As a result, the center of luminescence was shifted in the order of green, green, yellow and yellow at low temperature. The X-ray powder pattern analysis showed a pattern similar to Ca ₃ SiO ₄ Cl ₂ at 700 ° C and 70-2447. As the synthesis temperature increased, it became a high temperature phase of Ca ₃ SiO ₄ Cl ₂ .

< Example  3> Ca ₃ ( Si , Al ) O ₄ Cl: Eu ^{2 +}  And ( Ca , Mg ) ₃ ( Si , Al ) O ₄ Cl : Eu ^{2 +}  Synthesis experiment of phosphor

The same manner as in Example 2 by _{(Ca 2 .77 Mg 0 .2)} (Si 0 .8, Al 0 .27) O 4 Cl: 0.03Eu 2 + CaCl of 0.77 mol to prepare the phosphor _2, 0.2 mol Mg (NO ₃ ) ₂ , 2 mol Ca (NO ₃ ) ₂ , 0.27 mol Al (NO ₃ ) ₃ , 0.8 mol WSS (Sol) and 0.03 mol EuCl ₃ in deionized water, DI water ) Was dissolved in about 10 to 20 minutes each to make a 20 wt% solution. _{Ca 2.97 (Si 0.8, Al 0.27} ) O 4 Cl: 0.03Eu 2+ phosphor similarly 0.77 mol of CaCl _2, 2.2 mol of _{Ca (NO 3) 2, 0.27} mol of Al (NO _{3) 3,} 0.8 mol of the WSS and a 20 wt% solution containing 0.03 mol of EuCl ₃ were mixed with starch and dried at 100 ° C. and calcined at 225 ° C., followed by oxidation treatment at 700 ° C. and reduction treatment at 700 ° C., And x-ray powder pattern analysis (Fig. 10).

< Example  4> Na _{One .49- x} Na _x ) Si _{0 .45} , Al _{One .55} O _{4 -1/2 x} Cl _x : 0.06 Eu ^{2 +}  Synthesis experiment of phosphor

In the same manner as in Example _{2 (Na 1 .55- x Na x} ) Si 0 .45, Al 1 .55 O 4 -1/2 x Cl x: Eu 2 + (x = 0.0, 0.2, 0.4, 0.6 mol%) 1.49 to 1.43 mol (Na of 1.49 to 1.43) NaNO ₃ , 0.0 to 0.06 mol (Cl of x = 0.0 to 0.06), 1.55 mol of Al (NO ₃ ) ₃ , 0.45 to prepare the phosphor mol of WSS (Sol) and 0.06 mol of EuCl ₃ were dissolved in deionized water (Deionized water, DI water) for about 10 to 20 minutes, respectively, to make a 20 wt% solution. The precursor solution was mixed with starch and dried at 100 캜 and calcined at 225 캜, and then phosphor was synthesized through oxidation treatment at 700 캜 and reduction treatment at 700 캜. (Fig. 11), PL (Fig. 12) and FE-SEM (Fig. 13) were performed according to the content of chlorine (Cl).

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the present invention is not limited to the disclosed exemplary embodiments and the exemplary embodiments, and various changes and modifications may be made without departing from the scope of the present invention. It is evident that many variations are possible by the possessors.

Claims (22)

Rare earth metal is a metal salt mixture solution including a metal chloride to synthesize a silicate-based phosphor chloride was added by mixing in the liquid phase with a SiO ₂ sol salt - to give a SiO ₂ sol and a mixed solution;
Impregnating and drying the metal salt-SiO ₂ sol mixed solution into a polymer material and then performing low-temperature calcination, preoxidative oxidation and postreduction to obtain a silicate-based phosphor.
/ RTI &gt;
Wherein the polymeric material is selected from the group consisting of corn starch, potato starch, cellulose powder, cellulose sheet, spherical cellulose, water soluble cellulose, pulp, crystallized cellulose, amorphous cellulose, rayon and combinations thereof,
Lt; RTI ID = 0.0 &gt; 400 C, &lt; / RTI &gt;
A method for producing a chlorosilicate-based phosphor.
delete delete delete delete delete delete delete delete The method according to claim 1,
The phosphorus silicate-based phosphor obtained has a composition of M-Si-O-Cl, M-Si-BO-Cl, M-Si-Al- , An alkaline earth metal, a transition metal, a rare earth metal, and combinations thereof.
delete delete delete delete delete delete delete The method according to claim 1,
Wherein the chlorosilicate-based phosphor obtained has a round particle shape and a particle size of 50 nm to 10 mu m.
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