WO2012118310A2

WO2012118310A2 - Fluorescent substance, and method for preparing same

Info

Publication number: WO2012118310A2
Application number: PCT/KR2012/001459
Authority: WO
Inventors: 윤대호; 조덕수; 김봉성; 송영현; 타카키마사키; 정은준; 송석현; 강봉균; 김명오
Original assignee: 성균관대학교산학협력단
Priority date: 2011-02-28
Filing date: 2012-02-27
Publication date: 2012-09-07
Also published as: WO2012118310A3

Abstract

The present invention relates to a method for preparing an oxyhalide-based fluorescent substance, comprising the steps of: obtaining a solution containing a first metal halide, a second metal halide, and an oxide precursor of a period 3 element selected from the group consisting of Al, Si, P, and the combinations thereof; and performing heat treatment after adding a reducing agent to the solution.

Description

Phosphor, and method for producing same

The present application relates to an oxyhalide-based phosphor, a nitride-based or oxynitride-based phosphor, and a method for producing each thereof.

Conventional oxyhalide-based phosphors have been prepared by the solid precursor mixed with a solid state material being fired in a reducing atmosphere in which oxygen is blocked, i.e., "solid phase method". However, when a metal salt having dehumidification such as CaCl ₂ (s) is used in the solid phase method, there is a problem that uniform mixing is difficult due to the dehumidification of the metal salt. The problem can be partially solved by using a device using a glove box, but this problem of non-uniform mixing is not completely solved.

On the other hand, conventional nitride-based or oxynitride-based phosphors have been produced by firing metal or oxide-based phosphors under a nitrogen atmosphere, but the high cost of the metals and the stability of the oxide-based phosphors have been a problem. As a countermeasure, a method of nitriding carbonization by mixing carbon into an oxide-based phosphor by using a carbon thermal splitting method (CRN method; Cabothermal Reaction-Nitridation method) has been attempted, but the method is limited to materials having similar carbon and ion radius. It is pointed out that the problem can be applied and adversely affects the light emission of the phosphor, and improvement is needed.

On the other hand, the phosphor containing the rare earth metal has a feature that its emission and intensity vary depending on the valence of the rare earth metal. For example, Eu ³⁺ exhibits sharp light emission in a narrow region through the internal potential difference of ⁷ D ₀ → ⁷ F energy potential difference, while Eu ²⁺ exhibits light emission in a wide region due to the difference of 5d → 4f energy potential. The valence of the rare earth metal can be adjusted through oxidation or reduction. Conventionally, in order to reduce the electrons of the rare earth-based metal for controlling, the method of calcination in an atmosphere in which oxygen is excluded and hydrogen is used, but the method has a low degree of reduction and thus the emission intensity of the phosphor obtained as a result is high. There was a problem that it is not uniform.

When it becomes possible to manufacture phosphors with stable luminescence and uniform luminescence intensity in an easy and economical manner, the obtained phosphors may be light emitting diodes (LEDs), plasma display panels (PDPs), or electric fields. It can be used in various fields such as field emission display (FED), and cold cathode fluorescent lamp (CCFL). For example, Korean Patent No. 10-1053884 discloses that a phosphor may be usefully used in a PDP. A composition for forming a phosphor layer, a plasma display panel, and a method of manufacturing the plasma display panel are disclosed.

The present inventors have completed the present application by discovering that when the phosphor is produced according to the method of the present application, a phosphor having stable luminescence and a uniform luminescence intensity can be produced by an easy and economical method.

Accordingly, the present application is to provide an oxyhalide-based phosphor, a nitride or oxynitride-based phosphor, and their respective production methods.

However, the problem to be solved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present application provides a solution comprising a first metal halide, a second metal halide, and an oxide precursor of a tricycle element selected from the group consisting of Al, Si, P, and combinations thereof. It provides a method for producing an oxyhalide-based phosphor, comprising the step of, and heat treatment after the addition of a reducing agent to the solution.

A second aspect of the present application is an oxyhalide-based phosphor prepared by the method according to the first aspect of the present application, wherein the oxyhalide-based phosphor has a composition of M ¹ -M ² -OX: M ³ , wherein M ¹ is an alkali. A metal, an alkaline earth metal, or a transition metal, wherein M ² is a tricyclic element selected from the group consisting of Al, Si, P, and combinations thereof, X is a halogen element, and M ³ is a rare earth metal Provided are phosphorus and oxyhalide compounds.

A third aspect of the present application provides a solution comprising a first metal halide, a second metal halide, and an oxide precursor of a tricycle element selected from the group consisting of Al, Si, P, and combinations thereof. It provides a method of producing a nitride-based or oxynitride-based phosphor, including the step, and the step of adding a reducing agent to the solution and heat treatment in a nitrogen-containing atmosphere.

A fourth aspect of the present application is a nitride-based or oxynitride-based phosphor prepared by the method according to the third aspect of the present application, wherein the nitride-based or oxynitride-based phosphor is M ¹ -M ² -NX: M ³ or M ¹ -M ² -ONX: has a composition of M ³ , wherein M ¹ is an alkali metal, alkaline earth metal, or transition metal, and M ² is 3 cycles selected from the group consisting of Al, Si, P, and combinations thereof Is an element, X is a halogen element, and M ³ is a rare earth metal, and provides a nitride or oxynitride-based phosphor.

According to the present application, a phosphor having stable luminescence and uniform luminescence intensity can be produced by an easy and economical method.

Specifically, when the oxyhalide-based phosphor is manufactured by using a liquid phase method rather than the conventional solid-phase method according to the present application, the oxyhalide-based phosphor is obtained in the form of a single phosphor uniformly distributed evenly without aggregation, and excellent light emission efficiency By having a round shape, it can be used for a variety of purposes such as white LED or CCFL. In addition, when the oxyhalide-based fluorescent substance is manufactured according to the present application, since it can be manufactured in a short time, there is an advantage that the productivity and economy are also excellent.

On the other hand, when manufacturing a nitride or oxynitride-based fluorescent material according to the present application, by using a large ion size of the halogen atoms when firing the precursor in a nitrogen atmosphere, various metals such as alkali metal, alkaline earth metal, transition metal, rare earth metal Nitriding of ions can be easily implemented. In addition, by using a reducing gas to remove residual oxygen and nitriding relatively difficult to form chloride-based phosphors such as SiO ₂ (s), as a result, nitride-based or oxynitride-based phosphors can be easily and economically produced. .

On the other hand, the phosphor containing the rare earth metal is characterized in that the light emission and the intensity of the rare earth metal is different depending on the electron value, the treatment of the alkaline compound according to the present application by controlling the electron value of the rare earth metal, the light emission is It is possible to easily and economically produce a phosphor having stable and uniform luminous intensity.

1 is a schematic diagram showing a process of forming an oxyhalide-based, or nitride-based or oxynitride-based phosphor according to the present application.

2 is an SEM photograph of the phosphor powder prepared according to Example 1 of the present application.

3 is an XRD analysis result of the phosphor powder prepared according to Example 1 of the present application.

4 is an SEM photograph of the phosphor powder prepared according to Example 1 of the present application.

5 is a SEM-EDS analysis result of the phosphor powder prepared according to Example 1 of the present application.

6A and 6B are PL analysis results of the phosphor powder prepared according to Example 1 of the present application.

7 is a PL analysis result of the phosphor powder prepared according to Example 2 of the present application.

8 is an X-ray pattern analysis result of the phosphor powder prepared according to Example 2 of the present application.

9 is a PL analysis result of the phosphor powder prepared according to Example 3 of the present application.

10 is an X-ray pattern analysis result of the phosphor powder prepared according to Example 3 of the present application.

11 is an X-ray pattern analysis of the phosphor powder prepared according to Example 4 of the present application.

12 is a PL analysis result of the phosphor powder prepared according to Example 4 of the present application.

13A to 13D are FE-SEM photographs of phosphor powders prepared according to Example 4 of the present application.

14 is an XRD analysis result of the phosphor powder prepared according to Example 5 of the present application.

15 is a PL analysis result of the phosphor powder prepared according to Example 5 of the present application.

16 is a schematic diagram of a nitriding process of the phosphor powder according to Example 6 of the present application.

17 is a PL analysis result of the phosphor powder prepared according to Example 6 of the present application.

18 is a PL analysis result of the phosphor powder prepared according to Example 7 of the present application.

19 is a PL analysis result of the phosphor powder prepared according to Example 8 of the present application.

20 is an XRD analysis result of the phosphor powder prepared according to Example 8 of the present application.

21A and 22B are SEM photographs of the phosphor powder prepared according to Example 9 of the present application.

22 is a PL analysis result of the phosphor powder prepared according to Example 9 of the present application.

23 is an XRD analysis result of the phosphor powder prepared according to Example 10 of the present application.

24 is a PL analysis result of the phosphor powder prepared according to Example 10 of the present application.

25 is an XRD analysis result of the phosphor powder prepared according to Example 11 of the present application.

26 is a PL analysis result of the phosphor powder prepared according to Example 11 of the present application.

27 is an XRD analysis result of the phosphor powder prepared according to Example 12 of the present application.

28 is a PL analysis result of the phosphor powder prepared according to Example 12 of the present application.

29 is an XRD analysis result of the phosphor powder prepared according to Example 13 of the present application.

30 is a PL analysis result of the phosphor powder prepared according to Example 13 of the present application.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a portion is "connected" to another portion, this includes not only "directly connected" but also "electrically connected" with another element in between. do.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise. As used throughout this specification, the terms "about", "substantially" and the like are used at, or in the sense of, numerical values when a manufacturing and material tolerance inherent in the stated meanings is indicated, Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term "step to" or "step of" does not mean "step for."

Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

Hereinafter, with reference to the accompanying drawings will be described embodiments and embodiments of the present application;

For example, the oxyhalide-based phosphor is prepared by dissolving a first metal halide and a second metal halide in a solvent to form an aqueous solution, and adding a liquid silica precursor thereto to form a uniform mixed solution through liquid stirring. Obtained by impregnating the mixed solution into a polymeric material which is a reducing agent, to obtain an impregnated material, and heat treating the impregnated material to obtain an impurity-free phosphor powder, and pulverizing the phosphor powder to finally increase the surface area and uniformity. It may be prepared in the form of a phosphor having a composition, but is not limited thereto.

In addition, for example, the oxyhalide-based fluorescent substance, after adding SiO ₂ sol as a liquid precursor to a solution containing a rare earth metal and metal chlorides to obtain a uniform mixed solution through liquid stirring, the mixed solution Impregnated to obtain an impregnated material by impregnating a polymer material such as cellulose, which is a reducing agent, and drying the impregnated product to obtain a form of xerogel or xerosol, and finally heat treating the xerogel or xerosol. It may be prepared in the form of a phosphor, but is not limited thereto.

According to an embodiment of the present disclosure, the first metal halide includes a halide selected from the group consisting of alkali metal halides, alkaline earth metal halides, transition metal halides, and combinations thereof. The second metal halide may include, but is not limited to, a rare earth metal halide. For example, in synthesizing an oxyhalide-based fluorescent substance advantageously with high efficiency by using a liquid phase method according to the first aspect of the present application, by varying the metal contained in each of the first metal halide and the second metal halide The new composition of the prepared oxyhalide-based phosphor may be easily searched for, but is not limited thereto.

For example, a metal chloride having an ion radius of about 0.92 GPa to about 1.4 GPa may be used as the first metal halide to facilitate replacement with a rare earth metal material, but is not limited thereto. For example, the first metal halide has an ion radius of from about 0.92 kPa to about 1.0 kPa, from about 0.92 kPa to about 1.2 kPa, from about 0.92 kPa to about 1.4 kPa, from about 1.0 kPa to about 1.2 kPa, about 1.0 kPa About 1.4 kPa, or about 1.2 kPa to about 1.4 kPa, but is not limited thereto.

According to one embodiment of the present application, the alkali metal halide includes a chloride selected from the group consisting of LiCl, NaCl, KCl, and combinations thereof, and the alkaline earth metal halide is BeCl ₂ , MgCl ₂ , CaCl ₂ , SrCl ₂ , BaCl ₂ , and combinations thereof, may include chloride, but is not limited thereto.

For example, the transition metal halide is ScCl ₂ , 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 chlorides selected from the group consisting of combinations thereof, but is not limited thereto.

For example, the rare earth metal halide is a chloride selected from the group consisting of LaCl ₃ , CeCl ₃ , NdCl ₃ , EuCl ₃ , GdCl ₃ , TbCl ₃ , DyCl ₃ , ErCl ₃ , YbCl ₃ , and combinations thereof It may be to include, but is not limited thereto.

According to the exemplary embodiment of the present application, the oxide precursor of the tricycle element may include SiO ₂ , Si (OH) ₄ , SiH ₄ , Si (OC ₂ H ₅ ) ₄ , or a water-soluble silane, but is not limited thereto. It doesn't happen. For example, the oxide precursor of the tricycle element may include, but is not limited to, water soluble silicate (WSS) or SiO ₂ sol having a particle size of about 5 nm to about 3000 nm. . For example, it may be preferable to use SiO ₂ , Si (OH) ₄ , or water-soluble silane as the oxide precursor of the tricycle element, but is not limited thereto.

According to one embodiment of the present application, the reducing agent 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 It may be to include a high molecular material, but is not limited thereto. For example, it may be desirable to use a high purity pulp having a purity of about 99.8% or more and having a fine matrix form, but is not limited thereto.

According to one embodiment of the present disclosure, the heat treatment includes: a first heat treatment performed at about 150 ° C. to about 400 ° C., a second heat treatment performed at about 500 ° C. to about 1000 ° C., and about 700 ° C. to about 1400 ° C. Tertiary heat treatment performed in may be to include that is performed sequentially, but is not limited thereto.

For example, the step of heat treatment may include, but is not limited to, primary heat treatment at about 150 ° C to about 400 ° C. For example, the first heat treatment may be about 150 ° C. to about 200 ° C., about 150 ° C. to about 250 ° C., about 150 ° C. to about 300 ° C., about 150 ° C. to about 350 ° C., about 150 ° C. to about 400 ° C., about 200 ° C to about 250 ° C, about 200 ° C to about 300 ° C, about 200 ° C to about 350 ° C, about 200 ° C to about 400 ° C, about 250 ° C to about 300 ° C, about 250 ° C to about 350 ° C, about 250 ° C To about 400 ° C, about 300 ° C to about 350 ° C, about 300 ° C to about 400 ° C, or about 350 ° C to about 400 ° C, but is not limited thereto.

The first heat treatment may decompose the polymer material used as a reducing agent such as cellulose, but is not limited thereto. For example, decomposition of the polymer material formed through the first heat treatment may include decomposition of a polymer ring, -OH group or -CH ₂ O group in the polymer, and in addition to NO ₃ of a metal halide. The first heat treatment may be performed to decompose and remove the impurity ligand of, but is not limited thereto. When the primary heat treatment temperature is less than about 150 ° C., it may be difficult to decompose a polymer material used as a reducing agent such as cellulose, but is not limited thereto. On the other hand, when the primary heat treatment temperature is greater than about 400 ° C, the precursor of the phosphor is decomposed and oxidized to form an oxide such as an oxide silicate, which may affect the final resulting phosphor, but is not limited thereto. The primary heat treatment may be performed without a separate grinding process, and when the grinding process is performed in parallel, it may be easy to obtain a uniform oxyhalide-based phosphor at a lower temperature, but is not limited thereto.

For example, the heat treatment may include, but is not limited to, secondary heat treatment at about 500 ° C. to about 1000 ° C. after the first heat treatment. For example, the secondary heat treatment may be about 500 ° C. to about 600 ° C., about 500 ° C. to about 700 ° C., about 500 ° C. to about 800 ° C., about 500 ° C. to about 900 ° C., about 500 ° C. to about 1000 ° C., about 600 ° C to about 700 ° C, about 600 ° C to about 800 ° C, about 600 ° C to about 900 ° C, about 600 ° C to about 1000 ° C, about 700 ° C to about 800 ° C, about 700 ° C to about 900 ° C, about 700 ° C To about 1000 ° C, about 800 ° C to about 900 ° C, about 800 ° C to about 1000 ° C, or about 900 ° C to about 1000 ° C, but is not limited thereto. The secondary heat treatment may be performed under an oxygen atmosphere to remove residual organic materials from the phosphor precursor powder in the solid state obtained through the first heat treatment and to crystallize the phosphor precursor powder, but is not limited thereto. . At this time, by appropriately adjusting the temperature at which the second heat treatment is performed, it is possible to easily remove the residual organic material and crystallize the phosphor precursor powder, but is not limited thereto. For example, when the secondary heat treatment is performed at a temperature of less than about 500 ° C., it is difficult to crystallize the amorphous precursor precursor powder and a long time heat treatment may be required, but is not limited thereto. Meanwhile, when the secondary heat treatment is performed at a temperature of more than about 1000 ° C., some of the oxides may be oxidized according to the crystal stability of the phosphor precursor to form an oxide such as an oxidized silicate phosphor, but the present invention is not limited thereto.

For example, in preparing an oxyhalide-based phosphor according to the first aspect of the present application, LiCl, MgCl ₂ , ScCl ₃ , TiCl ₄ , VCl ₄ , CrCl ₃ , MnCl ₃ , FeCl ₃ , CoCl as the first metal halide _{When using 2} , NiCl ₂ , CuCl ₂ , or ZnCl ₂ and using a SiO ₂ or SiO ₂ + Al salt as the oxide precursor of the bicycle element, a large ion between the metal ion and Cl ion of the first metal halide Due to the difference in radius ratio, it may be preferable to perform the secondary heat treatment for a long time of about 10 hours or more at a low temperature of about 500 ° C., but is not limited thereto. On the other hand, when the ion radius where the metal ions hold Cl ions is sufficiently secured according to the type of the first metal halide, the secondary heat treatment may be performed at a temperature of about 600 ° C. to about 800 ° C. for about 5 hours. It may be preferred, but is not limited thereto.

For example, the heat treatment may include, but is not limited to, a third heat treatment at about 700 ° C. to about 1400 ° C. after the second heat treatment. For example, the third heat treatment may be about 700 ° C. to about 800 ° C., about 700 ° C. to about 900 ° C., about 700 ° C. to about 1000 ° C., about 700 ° C. to about 1100 ° C., about 700 ° C. to about 1200 ° C., about 700 ° C to about 1300 ° C, about 700 ° C to about 1400 ° C, about 800 ° C to about 900 ° C, about 800 ° C to about 1000 ° C, about 800 ° C to about 1100 ° C, about 800 ° C to about 1200 ° C, about 800 ° C To about 1300 ° C, about 800 ° C to about 1400 ° C, about 900 ° C to about 1000 ° C, about 900 ° C to about 1100 ° C, about 900 ° C to about 1200 ° C, about 900 ° C to about 1300 ° C, about 900 ° C to about 1400 ° C, about 1000 ° C to about 1100 ° C, about 1000 ° C to about 1200 ° C, about 1000 ° C to about 1300 ° C, about 1000 ° C to about 1400 ° C, about 1100 ° C to about 1200 ° C, about 1100 ° C to about 1300 ° C , About 1100 ° C. to about 1400 ° C., about 1200 ° C. to about 1300 ° C., about 1200 ° C. to about 1400 ° C., or about 1300 ° C. to about 1400 ° C., but is not limited thereto. By performing the third heat treatment in a reducing atmosphere, crystals of the phosphor precursor formed through the second heat treatment may be grown while reducing an activator such as a rare earth metal, but the present invention is not limited thereto. For example, when the tertiary heat treatment is performed at a temperature of less than about 700 ° C., it is difficult to form a sufficient reducing atmosphere, and as a result, a decrease in luminance and emission intensity of the phosphor may be caused, but is not limited thereto. On the other hand, if the third heat treatment is performed at a temperature of more than about 1400 ℃, as the phosphor powder becomes a sintered body may lose the properties of the powder, but is not limited thereto.

For example, the reducing atmosphere may be N ₂ / H ₂ = (about 90 to about 95) / (about 10 to about 5) or Ar / H ₂ = (about 90 to about 95) / (about 10 to about 5) It may be to be formed by, but is not limited thereto.

For example, in the preparation of the oxyhalide-based fluorescent substance according to the first aspect of the present application, in the case of using a matrix in which SiO ₂ is used as a matrix of phosphors, a light substance that is easy to dissolve and evaporates, such as B, is used. The organic material is removed by performing a long time at a low temperature of about 500 ° C. for about 10 hours or more, and the crystallization of SiO ₂ is induced by performing the tertiary heat treatment for about 2 hours or more at about 700 ° C. in a reducing atmosphere without oxygen, Thereafter, a method of inducing growth of the phosphor crystal at about 900 ° C. may be selected, but is not limited thereto.

For example, in the preparation of the oxyhalide-based fluorescent substance according to the first aspect of the present application, in the case of using a matrix of SiO ₂ and P as the parent of the phosphor, P having a high ion binding property and high magnetism is different from Si. Since the possibility of forming MPO-Cl forms before forming the metal salt and the matrix is high, once the amorphous phase is obtained through the first heat treatment, the second heat treatment is performed at a temperature of about 700 ° C. or more through a rapid temperature increase rate to crystallize SiO ₂ . It is possible to take a method of obtaining a parent while inducing, but is not limited thereto.

For example, an additional salt may be used in the method for preparing an oxyhalide-based phosphor according to the first aspect of the present application to easily control the amount of halogen in the phosphor, but is not limited thereto. For example, when calcium chloride is used as the first metal halide to produce the oxyhalide-based phosphor according to the first aspect of the present application, different salts containing the same metal as the calcium chloride and containing oxygen, for example For example, the addition of calcium nitrate salt can easily control the amount of chlorine in the phosphor produced, but is not limited thereto. Representing this example as a reaction scheme is as follows:

[반응식 1] Scheme 1

2CaCl ₂ + Ca (NO ₃ ) ₂ + SiO ₂ → Ca ₃ SiO ₄ Cl ₂

The reactants used in the reaction scheme 1 are all present in the liquid phase in the solvent, and a brief amount of the lubricant is omitted in order to simplify the reaction. In the reaction scheme 1, the calcium nitrate salt contains oxygen and thus can be easily oxidized, whereas the calcium chloride does not contain oxygen, so that the oxyhalide-based phosphor can be easily controlled through the reaction scheme, and the halogen in the phosphor The amount can be easily controlled, but is not limited thereto.

According to the exemplary embodiment of the present disclosure, the method for preparing the oxyhalide-based phosphor may further include treating an alkaline compound to the oxyhalide-based phosphor prepared after the heat treatment, but is not limited thereto. .

For example, the method of manufacturing the oxyhalide-based phosphor may further include treating an alkaline compound to the oxyhalide-based phosphor prepared for improving luminance of the phosphor after the heat treatment, but is not limited thereto. It is not.

For example, the alkaline compound may include, but is not limited to, a compound including an -OH group or a -NH ₂ group.

According to one embodiment of the present application, the alkaline compound is a compound selected from the group consisting of LiOH, NaOH, KOH, RbOH, CsOH, NH ₄ OH, H ₂ O ₂ , and combinations thereof, or propylamine (propylamine) ) -Based compound, butylamine-based compound, pentylamine-based compound, hexylamine-based compound, heptylamine-based compound, aminobenzene-based compound, metal amide compound, organic-based compound It may include, but is not limited to, a compound selected from the group consisting of alkaline compounds, and combinations thereof. For example, the metal amide compound may be a lithium amide compound, a sodium amide compound, a potassium amide compound, a cesium amide compound, and combinations thereof. It may be to include a compound selected from the group consisting of, but is not limited thereto. In addition, for example, the organic-based alkaline compound may include NH ₄ OH, NH ₂ NH ₂ , C ₆ H ₅ NH ₂ , or C ₃ H ₆ NH ₂ , but is not limited thereto.

For example, the alkaline compound may include a compound selected from the group consisting of LiOH, NaOH, KOH, RbOH, CsOH, and combinations thereof, and a compound selected from the group consisting of combinations thereof. However, the present invention is not limited thereto. When the alkaline compound is used, chlorine contained in the phosphor may be removed using a difference in reactivity through the ionic radius ratio between the chlorine contained in the phosphor and the alkaline compound, and the -OH group may be substituted in place of the place. As a result, the electron value of the rare earth metal contained in the phosphor is increased, so that the function as an activator of the rare earth metal can be improved. Of the alkaline compounds containing Li, Na, K, Rb, or Cs, an alkaline compound containing Cs may be particularly preferable, because Cs is a soft metal and the chlorine and the ion radius ratio are similar, so that the reactivity with chlorine is good. The reaction scheme of the oxidation reaction involving the alkaline compound is as follows:

[반응식 2] Scheme 2

Ca ₂ SiO ₃ Cl ₂ : Eu ³⁺ + 2CsOH → Ca ₂ SiO ₃ (OH) ₂ : Eu ³⁺ + 2CsCl + H ₂ O → Ca ₂ SiO ₄ : Eu ³⁺ + H ₂ O

For example, the alkaline compound may be a propylamine compound, a butylamine compound, a pentylamine compound, a hexylamine compound, or a heptylamine compound. , Aminobenzene-based compound, lithium amide-based compound, sodium amide-based compound, potassium amide-based compound, cesium amide-based compound, and combinations thereof It may be to include a compound selected from the group consisting of, but is not limited thereto. The alkaline compound may be used in a strong reduction reaction to remove chlorine by reacting with a phosphor. As the carbon ring of the alkaline compound is more stable, the substitution reaction may occur more rapidly. Among the alkaline compounds, an aminobenzene-based compound or a hydrazine-based compound may be preferable, but is not limited thereto. Of the alkaline compounds containing Li, Na, K, Rb, or Cs, alkaline compounds containing Cs may be particularly preferred, since Cs is a soft metal and its chlorine and ion radius ratio are similar, which makes it highly reactive with chlorine. . For example, the reaction schemes of the reduction reaction involving the alkaline compound are as follows:

[반응식 3] Scheme 3

Ca ₃ SiO ₄ Cl ₂ + [2KOH (aq), 2NaOH (aq), or NH ₄ OH (aq)] → Ca ₃ SiO ₄ (OH) ₂ + [2KCl (aq), 2NaCl (aq), or NH ₄ Cl (aq); Generated and then removed] + [2NaNH ₂ , 2NH ₃ (gas or aq), or 2NH ₂ NH ₂ (aq)] (reacts under NH ₂ NH ₂ solution or aniline) → Ca ₃ SiO ₄ (NH ₂ ) ₂ + [ 2NaOH (aq), 2H ₂ O (aq), or NH ₄ OH (aq)] (temperature above 50 ° C., and reaction under N ₂ gas, inert gas, H ₂ gas, or vacuum) → Ca ₃ SiO ₄ + [ NH ₂ ↑, or NH ₃ ↑]

[반응식 4] Scheme 4

Ca ₃ SiO ₄ Cl ₂ + 2NaNH ₂ (reacted under NH ₂ NH ₂ solution or aniline) → Ca ₃ SiO ₄ (NH ₂ ) ₂ + [2NaCl (aq); Generated and then removed] (reaction under temperature above 50 ° C. and under N ₂ gas, inert gas, H ₂ gas or vacuum) → Ca ₃ SiO ₄ + [NH ₂ ↑, or NH ₃ ↑]

[반응식 5]Scheme 5

Ca₃SiO₄Cl₂ + 2 NH₂NH₂ (aq) (50 ° C. temperature, and H₂ Gas or NH₃ Reaction under gas) → Ca₃SiO₄(NH₂)₂ + 2 NH₄Cl → Ca₃SiO₄(NH₂)₂+2NH₃↑+ 2HCl ↑ → Ca₃SiO₄ + [NH₂↑ or NH₃↑]

[반응식 6]Scheme 6

Ca₃SiO₄Cl₂ + 2 NH₃ (aq) (temperature below -30 ° C, and H₂ Gas, NH₃ Gas, N₂ Gas or reaction under inert gas) Ca₃SiO₄(NH₂)₂ + 2 NH₄Cl → Ca₃SiO₄(NH₂)₂2NH₃↑+ 2HCl ↑ → Ca₃SiO₄ + [NH₂↑ or NH₃↑]

[반응식 7]Scheme 7

Ca₃SiO₄(OH)₂ + 2 NH₃ (aq) or NH₂NH₂ (aq) (temperature below -30 ° C or above 50 ° C, and H₂ Gas, NH₃ Gas, N₂ Gas or reaction under inert gas) Ca₃SiO₄(NH₂)₂ + 2 NH₄OH → Ca₃SiO₄(NH₂)₂2NH₃↑+ 2H₂O ↑ → Ca₃SiO₄ + [NH₂↑ or NH₃↑]

On the other hand, for example, the step of treating the alkaline compound may be performed at about -100 ℃ to about 1500 ℃, but is not limited thereto. In order to increase the efficiency of the reaction involving the alkaline compound, the alkaline compound may be dissolved and reacted in a solvent, and the reaction may be performed at a melting point or higher of the alkaline compound itself, but is not limited thereto. For example, the treating of the alkaline compound may be performed at about -100 ° C to about 1500 ° C, but is not limited thereto. For example, treating the alkaline compound may comprise about -100 ° C to about 0 ° C, about -100 ° C to about 500 ° C, about -100 ° C to about 1000 ° C, about -100 ° C to about 1500 ° C, about 0 Is performed at from about 500 ° C. to about 500 ° C., from about 0 ° C. to about 1000 ° C., from about 0 ° C. to about 1500 ° C., from about 500 ° C. to about 1000 ° C., from about 500 ° C. to about 1500 ° C., or from about 1000 ° C. to about 1500 ° C. May be, but is not limited thereto. When the alkaline compound is present at a temperature below about -100 ° C., the reaction may be difficult to perform due to its low reactivity, and at temperatures above about 1500 ° C., the alkaline compound may react with the matrix of the phosphor itself even after reacting with the chlorine of the phosphor. The reaction may occur to synthesize a second phase, but is not limited thereto.

On the other hand, for example, the phosphor obtained by treating the alkaline compound is washed with distilled water, alcohols, or nonpolar solvent to remove residual alkali metal chlorides, and then dried in a manner of drying at about 200 ° C. or lower. It may be, but is not limited thereto. For example, it may be preferable to remove the residual alkali metal chloride because it may react with the phosphor to affect the emission decrease, but is not limited thereto. Further, for example, the drying may be performed at a temperature of about 200 ° C. or less, about 180 ° C. or less, about 160 ° C. or less, about 140 ° C. or less, about 120 ° C. or less, or about 100 ° C. or less, but is not limited thereto. It is not. When the drying is performed at a temperature exceeding about 200 ° C., the remaining alkali metal may react with the phosphor, causing a decrease in emission of the phosphor, but is not limited thereto. For example, when the alkaline compound is used as a reducing agent, for drying the obtained phosphor, it may be preferable to use a vacuum oven or to dry using nitrogen or an inert gas, but is not limited thereto. In addition, the amount of alkali metal chloride remaining may be adjusted or removed by adjusting the amount of the phosphor containing alkali metal and chloride, but is not limited thereto.

Meanwhile, for example, the phosphor as a precursor in the reduction schemes may be a material including an activator, but is not limited thereto. In addition, all reactions in the reduction schemes may be performed under ultraviolet light, thereby improving reaction rate and reactivity, but are not limited thereto. The reaction may be carried out in a very small amount on the surface of the phosphor particles, but may have a condition that can be reduced from Eu ³⁺ to Eu ²⁺ on the surface with respect to the amount of lubricant of the phosphor. In addition, an alkaline solution material such as hydrazine may be synthesized by reducing the firing of the phosphor or reducing the phosphor, but the present invention is not limited thereto. In addition, the side reaction product generated during the reaction may be removed or separated through centrifugation or gasification, but is not limited thereto. In addition, the hydroxy group synthesis reaction may contribute to the improvement of the reaction, but is not limited thereto.

For example, by adding the step of pulverizing the oxyhalide-based phosphor during the manufacturing process of the oxyhalide-based phosphor according to the first aspect of the present application, the time required for oxidation and reduction by further atomizing the phosphor powder and increasing the surface area It is possible to shorten or lower the synthesis temperature, but is not limited thereto. For example, in the grinding step, a ball mill, a roller mill, a vibrating ball mill, an atorita mill, a planetary ball mill, a sand mill, a cutter mill Drying dispersers such as cutter mills, hammer mills, jet mills, ultrasonic dispersers, or grinding apparatuses such as high pressure homogenizers may be used, but are not limited thereto.

For example, the composition of the oxyhalide-based phosphor according to the second aspect of the present application may also be represented by M ⁴ _v− u Si _w A _x O _y Cl _z : M ⁵ _u , wherein M ⁴ is an alkali metal or Chlorides of alkaline earth metals (eg, LiCl, NaCl, KCl, BeCl ₂ , MgCl ₂ , CaCl ₂ , SrCl ₂ , BaCl _2, etc.), or chlorides of transition metals (eg, 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 is B, Al, or P; M ⁵ is a chloride of a rare earth metal (eg, LaCl ₃ , CeCl ₃ , NdCl ₃ , EuCl ₃ , GdCl ₃ , TbCl ₃ , DyCl ₃ , ErCl ₃ , YbCl _3, etc.); V is any one of about 1 to about 8, w is any one of about 1 to about 7, x is any one of about 1 to about 5, and y is about 3 To any one of about 40 to about 40, and z is any value of about 0.5 to about 40, and u may be within about 0.5 mol% to about 20 mol% of v, but is not limited thereto. .

For example, the basic composition of the oxyhalide-based phosphor according to the second aspect of the present application may also be represented as M-Si-AO-Cl (A: B, Al, or P), for example, M-Si-O -Cl, M-Si-BO-Cl, M-Si-Al-O-Cl, or M-Si-PO-Cl, wherein M may be a combination of at least two metals, but It is not limited. For example, M may be a combination of at least two metals selected from alkali metals, alkaline earth metals, transition metals, or rare earth metals, but is not limited thereto.

For example, the oxyhalide-based phosphor may have ultra long afterglow phosphor characteristics, and may have a round particle shape and a particle size of about 50 nm to about 10 μm, but is not limited thereto. For example, the oxyhalide-based phosphor may be about 50 nm to about 100 nm, about 50 nm to about 500 nm, about 50 nm to about 1 μm, about 50 nm to about 10 μm, about 100 nm to about 500 nm , About 100 nm to about 1 μm, about 100 nm to about 10 μm, or about 1 μm to about 10 μm, but is not limited thereto.

The present application may include, for example, a display including the oxyhalide-based phosphor, but is not limited thereto.

For example, the display may include a cathode ray tube, a light emitting diode (LED), a plasma display panel (PDP), or a field emission display (FED), but is not limited thereto. It doesn't happen.

The present application may include, for example, a lamp including the oxyhalide-based phosphor, but is not limited thereto.

For example, the method for producing a nitride-based or oxynitride-based phosphor according to the third aspect of the present invention, the step of heat treatment under a nitrogen-containing atmosphere in the middle of the method for producing an oxyhalide-based phosphor according to the first aspect of the present application, That is, by including the step of nitriding, by inducing a thermochemical reaction to replace the halogen element and nitrogen of the oxyhalide-based phosphor, the nitride-based or oxynitride-based phosphor may be easily and economically obtained, but is not limited thereto. no.

For example, the nitride-based or oxynitride-based phosphor may be prepared by dissolving the first metal halide and the second metal halide in a solvent to form an aqueous solution, adding liquid silica precursor thereto, and then uniformly stirring the liquid. A mixed solution is obtained, and the mixed solution is impregnated into a polymeric material which is a reducing agent to obtain an impregnation, and the impregnated phosphor powder is obtained by heat treatment of the impregnation, and finally the surface area increased by pulverizing the phosphor powder. It may be prepared in the form of a phosphor having a uniform composition with, but is not limited thereto.

In addition, for example, the nitride-based or oxynitride-based fluorescent material, after adding SiO ₂ sol as a liquid precursor to a solution containing a rare earth metal and metal chlorides to obtain a uniform mixed solution through liquid stirring, The mixed solution is impregnated with a polymer material such as cellulose, which is a reducing agent, to obtain an impregnation. The impregnation is dried to obtain a form of xerogel or xerosol, and finally, the heat treatment of the xerogel or xerosol is carried out. It can be prepared in the form of a spherical phosphor, but is not limited thereto.

According to an embodiment of the present disclosure, the first metal halide includes a halide selected from the group consisting of alkali metal halides, alkaline earth metal halides, transition metal halides, and combinations thereof. The second metal halide may include, but is not limited to, a rare earth metal halide. For example, in synthesizing nitride-based or oxynitride-based phosphors with high efficiency by using the liquid phase method according to the third aspect of the present application, the metals contained in the first metal halide and the second metal halide are diversified. It is possible to facilitate the search for a new composition of the nitride-based or oxynitride-based fluorescent material prepared by, but is not limited thereto.

For example, it may be desirable to completely remove moisture by performing a drying process before performing the primary heat treatment, but is not limited thereto. The drying process may be performed at a temperature of about 50 ° C. to about 80 ° C. in a general drying oven or at a temperature of about 50 ° C. to about 150 ° C. in a vacuum oven, but is not limited thereto.

For example, in the heat treatment step, the secondary heat treatment may be omitted, and only the first heat treatment and the third heat treatment may be continuously performed, but the present invention is not limited thereto. For example, each of the primary, secondary, and tertiary heat treatments may be performed under a nitrogen atmosphere in which oxygen is excluded or under an inert gas atmosphere, but is not limited thereto.

The first heat treatment may decompose the polymer material used as a reducing agent such as cellulose, but is not limited thereto. For example, the decomposition of the polymer material formed through the first heat treatment may include decomposition of the ring of the polymer, -OH group or -CH ₂ O group in the polymer, in addition to NO ₃ and the like of the metal halide The first heat treatment may be performed to decompose and remove the impurity ligand of, but is not limited thereto. When the primary heat treatment temperature is less than about 150 ° C., it may be difficult to decompose a polymer material used as a reducing agent such as cellulose, but is not limited thereto. On the other hand, when the primary heat treatment temperature is greater than about 400 ° C, the precursor of the phosphor is decomposed and oxidized to form an oxide such as an oxide silicate, which may affect the final resulting phosphor, but is not limited thereto. The primary heat treatment may be performed without a separate grinding process, and when the grinding process is performed in parallel, the surface area may be increased, so that it may be easy to obtain a uniform phosphor at a lower temperature, but is not limited thereto.

For example, in preparing a nitride-based or oxynitride-based phosphor according to the third aspect of the present application, as the first metal halide, LiCl, MgCl ₂ , ScCl ₃ , TiCl ₄ , VCl ₄ , CrCl ₃ , MnCl ₃ , FeCl _{When using 3} , CoCl ₂ , NiCl ₂ , CuCl ₂ , or ZnCl ₂ and using the SiO ₂ or SiO ₂ + Al salt as the oxide precursor of the bicycle element, between the metal and Cl ions of the first metal halide Due to the large difference in the ion radius ratio of, it may be preferable to perform the secondary heat treatment at a low temperature of about 500 ° C. for a long time of about 10 hours or more, but is not limited thereto. On the other hand, when the ion radius where the metal ions hold Cl ions is sufficiently secured according to the type of the first metal halide, the secondary heat treatment may be performed at a temperature of about 600 ° C. to about 800 ° C. for about 5 hours. It may be preferred, but is not limited thereto.

According to one embodiment of the present application, the tertiary heat treatment may be performed in an atmosphere in which a nitrogen-containing gas flows at a speed of about 0.1 cm / s to about 10 cm / s, but is not limited thereto. For example, the tertiary heat treatment may comprise a nitrogen-containing gas from about 0.1 cm / s to about 1 cm / s, from about 0.1 cm / s to about 3 cm / s, from about 0.1 cm / s to about 5 cm / s, About 0.1 cm / s to about 7 cm / s, about 0.1 cm / s to about 10 cm / s, about 1 cm / s to about 3 cm / s, about 1 cm / s to about 5 cm / s, about 1 cm / s to about 7 cm / s, about 1 cm / s to about 10 cm / s, about 3 cm / s to about 5 cm / s, about 3 cm / s to about 7 cm / s, about 3 cm / s performed in an atmosphere flowing at s to about 10 cm / s, about 5 cm / s to about 7 cm / s, about 5 cm / s to about 10 cm / s, or about 7 cm / s to about 10 cm / s flux It may be, but is not limited thereto.

According to one embodiment of the present application, the nitrogen-containing atmosphere may be formed by N ₂ , NH ₃ , or a combination thereof, but is not limited thereto.

For example, the nitrogen-containing atmosphere may include one formed by N ₂ , NH ₃ , or a combination thereof, and may further include H ₂ , or CH ₃ , but is not limited thereto.

For example, in the manufacture of a nitride-based or oxynitride-based fluorescent material according to the third aspect of the present application, in the case of using a matrix in which SiO ₂ is used as a matrix of phosphors, a light substance that is easy to dissolve and evaporates, such as B, is used. The secondary heat treatment is performed at a low temperature of about 500 ° C. for at least about 10 hours to remove organics, and the third heat treatment is performed at about 700 ° C. for at least about 2 hours at a reduced atmosphere in which oxygen is excluded to crystallize SiO ₂ . Induction, and may be selected to induce the growth of the phosphor crystal at about 900 ℃, but is not limited thereto.

For example, in the manufacture of a nitride-based or oxynitride-based phosphor according to the third aspect of the present application, in the case of using a matrix of SiO ₂ in combination with P as a parent of the phosphor, P having a high ionic bondability and high magnetism is Since Si is more likely to form MPO-Cl before forming a matrix with other metal salts, once the amorphous phase is obtained through primary heat treatment, the secondary heat treatment is carried out at a temperature of about 700 ° C. or higher through a rapid temperature increase rate to form SiO. _A method of obtaining a matrix while inducing crystallization of ₂ may be selected, but is not limited thereto.

In preparing the nitride-based or oxynitride-based fluorescent material according to the third aspect of the present application, the part which is different from the manufacturing of the oxyhalide-based fluorescent material according to the first aspect of the present application may be referred to as a part for nitriding metal ions. For example, when chloride is used as the first metal halide and SiO ₂ is used as the oxide precursor of the tricycle element, the difference in the ion radius ratio between Cl (~ 1.81 kV) and N (1.46 kV) The nitriding can be achieved by inducing covalent bonds by substituting N for Cl instead of Cl, but the present invention is not limited thereto. In terms of ion radius ratio, it may be preferable to use chloride as the first metal halide, but is not limited thereto. For example, when the chloride is used as the first metal halide, nitriding may be induced by a relatively low temperature reaction, but is not limited thereto.

In order for the nitride-based or oxynitride-based fluorescent material to be manufactured according to the third aspect of the present application, since the rare earth-based metal needs to be effectively substituted with the metal ions of the phosphor matrix, the ion radius size of the rare earth-based metal is about 0.92 kPa to It is preferable that the metal ion of the phosphor matrix also has a similar ion radius in that it is about 1.4 GHz, but is not limited thereto.

On the other hand, the method for producing a nitride or oxynitride-based phosphor according to the third aspect of the present application, the general carbon thermal decomposition method (CRN method; Cabothermal Reaction-Nitridation method) or gas reduction method (GRN method; Gas-Reduction-Nitridation ) In parallel with, but is not limited to. Conventionally, high purity nitride-based phosphors are formed by mixing carbon with oxide-based phosphors and nitriding them through carbonization using the CRN method. However, such a conventional method is applicable only to materials having similar carbon and ionic radii, such as SiO _2. There was a limitation, and the present invention was intended to solve the above limitation.

For example, when preparing a nitride-based or oxynitride-based phosphor according to the third aspect of the present application, when the Al-O or Si-O-based nonmetallic materials are nitrided by replacing metal chlorides, the difference in ion radius is large. Nitrile is advantageous in that it is easy to nitride due to the strong ionic bonding of chlorine, but on the other hand, oxidation may proceed before nitriding due to instability, and it is difficult to maintain chloride state due to the strong hydroxyl action during solution formation. There may be. In addition, there may also be a problem that the uniformity of the composition is lowered by being lost to the gas at a low or medium temperature of about 400 ℃ or less. In this regard, in the case of nitriding the non-metallic materials, the CRN method or the GRN method is preferably combined with the method of the present application, and by inducing self oxidation using a nitrate-based material as a liquid material of the Al compound. It may be desirable to induce the solution of the problem, but is not limited thereto.

On the other hand, when combining the method of the present application and the CRN method or the GRN method, it is preferable to consider a high molecular material which is used as a reducing agent and is also a carbon source. Representative schemes of the CRN method and the GRN method may be represented as follows, but are not limited thereto.

<CRN법의 경우><CRN Act>

[Reaction Scheme _{_{8] 2CaCl 2 + 5SiO 2 +}} 4N 2 + 10C → Ca 2 Si 5 N 8 + 10CO

[ Chemical Scheme 9] CaCl ₂ + SiO ₂ + 1 / 2Al ₂ O ₃ + 3 / 2N ₂ + 3.5C → CaSiN ₃ + 3.5CO

<GRN법의 경우><In case of GRN method>

[Reaction Scheme _{_{10] 2CaCl 2 + 5SiO 2 +}} 8NH 3 → Ca 2 Si 5 N 8

[ Chemical Scheme 11] CaCl ₂ + SiO ₂ + 1 / 2Al ₂ O ₃ + 3NH ₃ → CaAlSiN ₃

In the above schemes, the rare earth metal, which is a substance added in a small amount, is not shown for convenience of description. In the reaction scheme of the GRN method, when a gas containing carbon, such as methane gas, is added as a gas to react with the precursor, the efficiency of the reaction may be improved, but is not limited thereto.

For example, using the Si ₃ N ₄ , Si ₂ ON ₂ , Si ₃ O ₃ N ₂ , Si ₆ O ₉ N ₂ , or CRN method to induce the nitriding reaction of the chloride-based phosphor to the acid of the third aspect of the present application Nitride-based or nitride-based phosphors may be prepared, and reaction schemes related thereto may be represented, for example, as follows, but are not limited thereto.

< Preparation of MSi ₂ O ₂ N ₂ : Eu ²⁺ Phosphor Using Chloride-based Phosphor >

[Reaction Scheme _{_{_{12] 2M 2 SiO 3 Cl 2}}} + 3Si 2 ON 2 + 2H 2 → 4MSi 2 O 2 N 2 + H 2 O + 2HCl

[Reaction Scheme _{_{13] M 2 SiO 4- (1x}} / 2) Cl x + Si 3 N 4 + x / 2H 2 → 2MSi 2 O 2- (1x / 2) N 2 + xHCl (x = 0.001 ~ 2)

< Preparation of M ₂ Si ₅ N ₈ Eu ²⁺ Phosphor Using MCl ₂ : Eu ²⁺ Chloride-Based Phosphor >

[Reaction Scheme 14] MCl ₂ + 5/3 Si ₃ N ₄ + 2 / 3NH ₃ → M ₂ Si ₅ N ₈ + 2HCl

[Reaction Scheme _{_{_{15] 2M 3 SiO 4 Cl 2}}} + 13 / 3Si 3 N 4 + 10H 2 → 3M 2 Si 5 N 8 + 4HCl + 8H 2 O

< Preparation of CaAl ₂ Si ₄ O ₁₂ N ₂ : Eu ²⁺ Phosphor Using CaAl ₂ Si ₄ O ₁₂ (Cl ₂ ): Eu ²⁺ Chloride-Based Phosphor >

[Reaction Scheme _{_{_{16] MAl 2 Si 4 O 12}}} (Cl 2) 3 + (2x + y) NH 3 → MAl 2 Si 4 O (12-3y / 2) N (x2 / 3 + y2 / 3) + xNH 4 Cl + (x + y / 2) H ₂ + (3y / 2) H ₂ O + yN ₂

When the present method is combined with the CRN method or the GRN method, there is a problem that the reaction rate is lowered if the precursor materials are already crystallized before reacting with a gas containing a nitrogen atom, and thus the temperature at which crystallization becomes active is about 700 ° C. or less. It may be preferable to perform the second heat treatment at a temperature of, but is not limited thereto. In addition, since it is preferable to reach the third heat treatment temperature, which is a temperature at which the precursor crystallizes to the gas containing the nitrogen atom in a state where the crystallization is minimal, it may be advantageous to rapidly increase the temperature to the third heat treatment temperature. It is not. For example, when using the method of the present invention and the CRN method in parallel, it is preferable to raise the temperature by about 30 minutes to about 1 hour 30 minutes, and when using the method of the present invention and the GRN method in parallel, about 2 hours to about 3 It may be desirable to increase the temperature for a time, but is not limited thereto. Meanwhile, the third heat treatment temperature is preferably about 1400 ° C. to about 1700 ° C. when the method of the present invention is combined with the CRN method, and about 1200 ° C. to about 1400 when the method of the present invention is combined with the GRN method. ℃ may be preferred, but is not limited thereto.

On the other hand, the flux of the gas containing a nitrogen atom in the above methods is a factor that must be considered for an efficient and safe nitriding reaction, when the method of the present invention and the CRN method in parallel, about 1 cm / s to about 2 cm / It is preferable to inject a gas containing the nitrogen atom at a flux of s, and when the method of the present application and the GRN method are used in combination, the nitrogen atom is removed at a flux of about 0.3 cm / s or less in consideration of the safety of NH ₃ . It may be desirable to inject a gas containing, but is not limited thereto.

According to the exemplary embodiment of the present disclosure, the method of manufacturing the nitride-based or oxynitride-based phosphor may further include treating an alkaline compound to the nitride-based or oxynitride-based phosphor prepared after the heat treatment. However, the present invention is not limited thereto.

For example, the method of manufacturing the nitride-based or oxynitride-based phosphor may further include treating an alkaline compound to the nitride-based or oxynitride-based phosphor prepared for improving the brightness of the phosphor after the heat treatment step. However, it is not limited thereto.

For example, the alkaline compound may include a compound selected from the group consisting of LiOH, NaOH, KOH, RbOH, CsOH, and combinations thereof, and a compound selected from the group consisting of combinations thereof. However, the present invention is not limited thereto. When the alkaline compound is used, chlorine contained in the phosphor may be removed using a difference in reactivity through the ionic radius ratio between the chlorine contained in the phosphor and the alkaline compound, and the -OH group may be substituted in place of the place. As a result, the electron value of the rare earth metal contained in the phosphor is increased, so that the function as an activator of the rare earth metal can be improved. Of the alkaline compounds containing Li, Na, K, Rb, or Cs, an alkaline compound containing Cs may be particularly preferable, because Cs is a soft metal and the chlorine and the ion radius ratio are similar, so that the reactivity with chlorine is good.

For example, the alkaline compound may be a propylamine compound, a butylamine compound, a pentylamine compound, a hexylamine compound, or a heptylamine compound. , Aminobenzene-based compound, lithium amide-based compound, sodium amide-based compound, potassium amide-based compound, cesium amide-based compound, and combinations thereof It may be to include a compound selected from the group consisting of, but is not limited thereto. The alkaline compound may be used in a strong reduction reaction to remove chlorine by reacting with a phosphor. As the carbon ring of the alkaline compound is more stable, the substitution reaction may occur more rapidly. Among the alkaline compounds, an aminobenzene-based compound or a hydrazine-based compound may be preferable, but is not limited thereto. Of the alkaline compounds containing Li, Na, K, Rb, or Cs, alkaline compounds containing Cs may be particularly preferred, since Cs is a soft metal and its chlorine and ion radius ratio are similar, which makes it highly reactive with chlorine. .

For example, by pulverizing the nitride-based or oxynitride-based phosphor during the manufacturing process of the nitride-based or oxynitride-based phosphor according to the third aspect of the present application, the phosphor powder is further atomized and the surface area is increased to oxidize It may shorten the time required for reduction or lower the synthesis temperature, but is not limited thereto. For example, in the grinding step, a ball mill, a roller mill, a vibrating ball mill, an atorita mill, a planetary ball mill, a sand mill, a cutter mill Drying dispersers such as cutter mills, hammer mills, jet mills, ultrasonic dispersers, or grinding apparatuses such as high pressure homogenizers may be used, but are not limited thereto.

For example, the nitride-based or oxynitride-based phosphor may have ultra long afterglow phosphor characteristics, and may have a round particle shape and a particle size of about 50 nm to about 10 μm, but is not limited thereto. For example, the nitride-based or oxynitride-based phosphor may be about 50 nm to about 100 nm, about 50 nm to about 500 nm, about 50 nm to about 1 μm, about 50 nm to about 10 μm, about 100 nm to It may have a size of about 500 nm, about 100 nm to about 1 μm, about 100 nm to about 10 μm, or about 1 μm to about 10 μm, but is not limited thereto.

The present application may include, for example, a display including the nitride-based or oxynitride-based phosphor, but is not limited thereto.

The present application may include, for example, a lamp including the nitride-based or oxynitride-based phosphor, but is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present application is not limited thereto.

[실시예]EXAMPLE

1. 옥시할로겐화물계 형광체의 제조 및 분석 (알칼리성 화합물 미 처리)1. Preparation and analysis of oxyhalide-based phosphor (untreated alkaline compound)

Example 1 Preparation of Ca ₃ SiO ₄ Cl ₂ : Eu ²⁺ Phosphor Using SiO ₂

In Example 1, according to the method of the first aspect of the present application, 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 , respectively, in deionized water After dissolution for about 10 to 20 minutes, a 20 wt% mixed solution was made through stirring. Ca ₃ SiO ₄ Cl ₂ : Eu ²⁺ phosphor powder was weighed out to 5 g in the mixed solution. Thereafter, the cellulose powder was impregnated into the mixed solution with a ratio of 2: 1 of the mixed solution and cellulose powder. At this time, the mixture was stirred for 10 minutes using an ultrasonic apparatus for uniform stirring and impregnation. Thereafter, the impregnated precursor was placed in an 80 ° C. dryer, dried for 10 hours, and then calcined at 225 ° C. for 6 hours.

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

Example 2 Preparation of Ca ₃ SiO ₄ Cl ₂ : Eu ²⁺ Phosphor Using Water-Soluble Silicon Compound (WSS)

In Example 2, according to the method of the first aspect of the present application, 1.97 mol of CaCl ₂ , 1 mol of Ca (NO ₃ ) ₂ , 1 mol of WSS (Sol), and 0.03 mol of EuCl ₃ , respectively, were dissolved in deionized water. After dissolving for 10 to 20 minutes, a 20 wt% mixed solution was made through stirring. Ca ₃ SiO ₄ Cl ₂ : Eu ²⁺ phosphor powder was weighed out to 5 g in the mixed solution. Thereafter, the mixed solution was stirred at a ratio of 1: 3 with Starch (potato powder), and then stirred and impregnated for 10 minutes using an ultrasonic apparatus for uniform stirring. Thereafter, the impregnated precursor was placed in an 80 ° C. drier and then dried for 10 hours and calcined at 225 ° C. for 6 hours.

The impregnated precursor became bulky as it became xerogel during drying and primary calcination. After the first calcination, the powder obtained by heat treatment at 500 ° C. for 2 hours was increased to be easily oxidized through grinding, and further calcined in air at 700 ° C. for 1 hour. Thereafter, firing was performed at 700 ° C., 900 ° C., and 1000 ° C. for 3 hours for phosphor powder reduction.

Thereafter, PL characteristics analysis and X-ray powder pattern analysis were performed on the manufactured phosphor powder, and the results are shown in FIGS. 7 and 8, respectively. As a result, it was confirmed that the center of luminescence moved in the order of green, green, yellow, and yellow at low temperature, and the pattern similar to 70-2447 and Ca ₃ SiO ₄ Cl ₂ at 700 ° C through X-ray powder pattern analysis. It was confirmed. In addition, it was confirmed that Ca ₃ SiO ₄ Cl ₂ changes to a high temperature phase as the synthesis temperature increases.

Example 3 Preparation of Ca ₃ (Si, Al) O ₄ Cl: Eu ²⁺ Phosphor and (Ca, Mg) ₃ (Si, Al) O ₄ Cl: Eu ²⁺ Phosphor

0.77 mol of CaCl ₂ , 0.2 mol of Mg (NO ₃ ) ₂ to prepare (Ca _2.77 Mg _0.2 ) (Si _0.8 , Al _0.27 ) O ₄ Cl: 0.03Eu ²⁺ phosphor in the same manner as in Example ₂ , 20 mol of Ca (NO ₃ ) ₂ , 0.27 mol of Al (NO ₃ ) ₃ , 0.8 mol of WSS (Sol), and 0.03 mol of EuCl ₃ were dissolved in deionized water for about 10 to 20 minutes respectively. A% mixed solution was prepared. In addition, to prepare Ca _2.97 (Si _0.8 , Al _0.27 ) O ₄ Cl: 0.03Eu ²⁺ phosphor, 0.77 mol CaCl ₂ , 2.2 mol Ca (NO ₃ ) ₂ , 0.27 mol Al (NO ₃ ) ₃ 20 wt% of a mixed solution was prepared by dissolving 0.8 mol of WSS (sol) and 0.03 mol of EuCl ₃ in deionized water for about 10 to 20 minutes, respectively. Thereafter, the mixed solution was mixed with Starch (potato starch), dried at 100 ° C., calcined at 225 ° C., and then obtained green phosphor through oxidation at 700 ° C. and reduction at 700 ° C. PL analysis and X-ray powder pattern analysis of the obtained phosphor were performed and shown in FIGS. 9 and 10, respectively.

Example 4 Preparation of (Na _1.49-x Na _x ) Si _0.45 , Al _1.55 O _{4-1 / 2x} Cl _x : 0.06Eu ²⁺ Phosphor

To prepare (Na _1.55-x Na _x ) Si _0.45 , Al _1.55 O _{4-1 / 2x} Cl _x : Eu ²⁺ (x = 0.0, 0.2, 0.4, 0.6 mol%) phosphors in the same manner as in the above examples 1.49 to 1.43 mol of NaNO ₃ (containing 1.49 to 1.43 Na), 0.0 to 0.06 mol of NaCl (containing Cl of 0.0 to 0.06), 1.55 mol of Al (NO ₃ ) ₃ , 0.45 mol of WSS (Sol) , And 0.06 mol of EuCl ₃ were dissolved in deionized water for about 10 to 20 minutes, respectively, to prepare a 20 wt% mixed solution. Thereafter, the mixed solution was mixed with Starch (potato starch), dried at 100 ° C., calcined at 225 ° C., and then phosphors were obtained through oxidation at 700 ° C. and reduction at 700 ° C. X-ray powder pattern analysis, PL analysis, and FE-SEM analysis results according to the Cl content of the obtained phosphor are shown in Figs. 11 to 13, respectively.

2. 옥시할로겐화물계 형광체의 제조 및 분석 (알칼리성 화합물 처리)2. Preparation and Analysis of Oxyhalide-Based Phosphors (Alkaline Compound Treatment)

<실시예 5> Example 5

Example 5 was carried out in the same manner as in Scheme 3 in the present specification. Specifically, Ca ₃ SiO ₄ Cl ₂ : 0.03Eu ²⁺ phosphor and a 10 wt% NaOH solution were mixed at a molar ratio of 1: 2 (Na: Cl = 1: 1 molar ratio) and reacted at room temperature for 24 hours. Thereafter, the solution layer and the powder layer of the material obtained through the reaction were separated and placed in a weight ratio of 70 wt% of the powder initially added with H ₂ O in the powder layer, followed by washing in the same manner twice. Thereafter, the powder layer was dried at 80 ° C. for 6 hours to obtain a phosphor powder treated with an alkaline compound. Subsequently, 1 g of the phosphor powder treated with the alkaline compound was reacted at room temperature with stirring under ultraviolet light with 10 mL of NH ₂ NH ₂ solution to reduce the phosphor powder. The powder obtained in this way was dried under N ₂ / H ₂ (95/5) atmosphere under 200 ° C., and safely removed by reacting NH ₂ NH ₂ with NH ₃ . XRD and PL analysis results of the obtained phosphor powder are shown in FIGS. 14 and 15.

<실시예 6><Example 6>

Example 6 was carried out in the same manner as in Scheme 5 in the present specification. Specifically, Ca ₃ SiO ₄ Cl ₂ : 0.03Eu ²⁺ phosphor and NH ₂ NH ₂ solution was mixed in a molar ratio of 1: 4 and put in an aluminum crucible with a lid to achieve the same effect as FIG. 16. Thereafter, under a N ₂ / H ₂ (95/5) reducing atmosphere, reduction reaction was performed at 700 ° C. for 3 hours to obtain a phosphor powder, and the PL characteristics of the phosphor powder were analyzed and shown in FIG. 17.

<실시예 7> <Example 7>

Example 7 was carried out in the same manner as in Scheme 4 in the present specification. Specifically, NaNH ₂ powder was added at a molar ratio of 1: 2 to Ca ₃ SiO ₄ Cl ₂ : 0.03Eu ³⁺ phosphor and NH ₂ NH ₂ solution at high temperature, and then mixed evenly through a stirrer for 2 hours, followed by N ₂ / H ₂ (95/5) was reacted at a temperature of 400 ° C. under a reducing atmosphere. Thereafter, the obtained phosphor and the side reaction product were washed with H ₂ O and dried. The result of PL analysis of the phosphor powder obtained by the above method is shown in FIG. 18.

<실시예 8> <Example 8>

Example 8 was carried out in the same manner as in Scheme 5 of the present specification. Specifically, the Ca ₃ SiO ₄ Cl ₂ : 0.03Eu ³⁺ phosphor and the NH ₂ NH ₂ solution at high temperature were mixed in a molar ratio of 1: 4, and then placed in a glass vial and maintained for 5 hours while stirring the magnetic bar under ultraviolet light at 254 nm. I was. Subsequently, the phosphor powder was reduced into a vacuum oven at 100 ° C., and the PL characteristics and the XRD change of the phosphor powder were shown in FIGS. 19 and 20, respectively.

<실시예 9> Example 9

Example 9 was carried out in the same manner as in Scheme 5 in the present specification. Specifically, a nano-sized Na _1.49 Al _1.55 Si _0.45 O ₄ : 0.06Eu ³⁺ phosphor containing 0.06 mol% and NH ₂ NH ₂ solution were mixed at a molar ratio of 1: 4, and then placed in an alumina crucible at a high temperature of 700 ° C. It was kept for 5 hours while heating to. SEM photographs and PL characterization results of the obtained phosphor powders are shown in FIGS. 21 and 22, respectively.

3. 산질화물계 또는 질화물계 형광체의 제조 및 분석3. Preparation and analysis of oxynitride- or nitride-based phosphors

<Example 10> Preparation of Ca ₂ Si ₅ N ₈ : Eu ²⁺ phosphor using Ca ₃ SiO ₄ Cl ₂ : Eu ²⁺ precursor phosphor

Example 10 was carried out in the same manner as in Scheme 15 of the present specification. Specifically, a mixed solution was obtained by dissolving 2.94 mol of CaCl ₂ and 0.06 mol of EuCl ₃ in deionized water, respectively, and stirring with 1 mol of SiO ₂ (sol, 20 nm). Thereafter, the mixed solution was impregnated with 1 μm cellulose (C ₆ H ₁₀ O ₅ ) in a ratio of 2: 1 and dried. The impregnated material was then heat treated at 225 ° C. and hand milled to increase the surface area. Thereafter, the obtained material was calcined in an oxidizing atmosphere at 700 ° C. to remove carbon, to obtain an intermediate of Ca ₃ SiO ₄ Cl ₂ Eu ³⁺ , and a Ca ₃ SiO ₄ Cl ₂ : Eu ³⁺ phosphor and Si ₃ N _4. Was mixed at a ratio of 2: 13/3 mol. Subsequently, the mixed material was placed in an electric furnace in the form of a tube flowing with N ₂ / H ₂ (95/5) gas at a rate of 0.5 cm / s, and thermally treated at 1300 ° C. for 5 hours to provide Ca ₂ Si ₅ N ₈ : Eu ^{2 +} Phosphor was obtained. XRD analysis results and PL analysis results of the nitride-based phosphors obtained by the above method are shown in FIGS. 23 and 24.

Example 11 Preparation of CaSi ₂ O ₂ N ₂ : Eu ²⁺ Phosphor Using Ca ₃ SiO ₄ Cl ₂ : Eu ²⁺ Precursor

Example 11 was carried out in the same manner as in Scheme 14 in the present specification. Specifically, a mixed solution was obtained by dissolving 3 mol CaCl ₂ and 0.06 mol EuCl ₃ in deionized water, respectively, and stirring with 1 mol SiO ₂ (sol, 20 nm). Thereafter, the mixed solution was impregnated with 1 μm cellulose (C ₆ H ₁₀ O ₅ ) in a ratio of 2: 1 and dried. The impregnated material was then heat treated at 225 ° C. and hand milled to increase the surface area. Thereafter, the obtained material was calcined in an oxidizing atmosphere at 700 ° C. to remove carbon, to obtain an intermediate of Ca ₃ SiO ₄ Cl ₂ Eu ³⁺ , and a Ca ₃ SiO ₄ Cl ₂ : Eu ³⁺ phosphor and Si ₂ ON _2. Was mixed at a ratio of 1: 1 mol. Then, the mixed materials into the NH ₃ in the form of a tube diameter of 50 mm in the flowing speed of 300 ccm electric furnace and heat treated at 1200 ℃ temperature for 10 hours, CaSi _{_₂} O ₂ N _2: Eu ²⁺ phosphor was obtained. XRD analysis results and PL analysis results of the nitride-based phosphors obtained by the above method are shown in FIGS. 25 and 26.

Example 12 Preparation of SrSi ₂ O ₂ N ₂ : Eu ²⁺ Phosphor Using Sr ₂ SiO ₃ Cl ₂ : Eu ²⁺ Precursor

Example 12 was carried out in the same manner as in Scheme 14 in the present specification. Specifically, a mixed solution was obtained by dissolving 2 mol of SrCl ₂ and 0.06 mol of EuCl ₃ in deionized water, respectively, and stirring with 1 mol of SiO ₂ (sol, 20 nm). Thereafter, the mixed solution was impregnated with 1 μm cellulose (C ₆ H ₁₀ O ₅ ) in a ratio of 2: 1 and dried. The impregnated material was then heat treated at 225 ° C. and hand milled to increase the surface area. Thereafter, the obtained material was calcined in an oxidizing atmosphere at 700 ° C. to remove carbon, to obtain an intermediate of Sr ₂ SiO ₃ Cl ₂ Eu ³⁺ , and an Sr ₂ SiO ₃ Cl ₂ : Eu ³⁺ phosphor and Si ₂ ON _2. Was mixed at a ratio of 1: 1.5 mol. Thereafter, the mixed material was placed in a tube-type electric furnace having a diameter of 50 mm flowing with NH ₃ at a rate of 300 ccm, and heat-treated at 1200 ° C. for 5 hours to obtain a SrSi ₂ O ₂ N ₂ : Eu ²⁺ phosphor. XRD analysis results and PL analysis results of the nitride-based phosphors obtained by the above method are shown in FIGS. 27 and 28.

Example 13 Preparation of Ca-alpha SiAlON: Eu ²⁺ Phosphor Using CRN Method

Example 13 was carried out in the same manner as in Scheme 15 of the present specification. In particular, Example 13 was performed by preparing five kinds of mixed solutions having different compositions as follows: ① 0.92 mol CaCl ₂ , 0.08 mol Eu (NO ₃ ) ₃ , and 1 mol Al (NO ₃ ) ₃ , respectively, in deionized water. Was dissolved in to prepare a 50 wt% mixed solution and stirred with 1 mol SiO ₂ (sol, 20 nm); ② 0.92 mol CaCl ₂ , 0.08 mol EuCl ₃ , and 1 mol Al (NO ₃ ) ₃ were dissolved in deionized water, respectively, to prepare a 50 wt% mixed solution, and stirred with 1 mol SiO ₂ (sol, 20 nm); ③ 0.92 mol CaCl ₂ , 0.08 mol EuCl ₃ , and 1 mol AlCl ₃ were dissolved in deionized water, respectively, to prepare a 50 wt% mixed solution, and stirred with 1 mol SiO ₂ (sol, 20 nm); ④ 0.92 mol Ca (NO ₃ ) ₂ , 0.08 mol EuCl ₃ , and 1 mol AlCl ₃ were each dissolved in deionized water to prepare a 50 wt% mixed solution, and stirred with 1 mol SiO ₂ (sol, 20 nm); ⑤ 50 wt% mixed solution was prepared by dissolving 0.92 mol Ca (NO ₃ ) ₂ , 0.08 mol EuCl ₃ , and 1 mol Al (NO ₃ ) ₃ in deionized water, respectively, and using 1 mol SiO ₂ (sol, 20nm) and Stirring. The mixed solutions of five different compositions were reacted with 3.58, 3.5, 2, 2.92, and 4.42 mol of cellulose (C ₆ H ₁₀ O ₅ ) having a size of 1 μm, respectively, and impregnated and dried. Thereafter, each of the mixed materials was placed in a tube-type electric furnace having a diameter of 50 mm flowing N ₂ at a rate of 1 cm / min, and heat-treated at 1600 ° C. for 5 hours to obtain a Ca-alpha SiAlON: Eu ²⁺ phosphor. XRD analysis results and PL analysis results of the nitride-based fluorescent material obtained by the above method are shown in FIGS. 29 and 30.

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present application. .

Claims

Obtaining a solution comprising an oxide precursor of a tricycle element selected from the group consisting of a first metal halide, a second metal halide, and Al, Si, P, and combinations thereof; And,

Heat treatment after addition of a reducing agent to the solution

Including,

Method for producing an oxyhalide-based phosphor.
The method of claim 1,

The first metal halide includes a halide selected from the group consisting of alkali metal halides, alkaline earth metal halides, transition metal halides, and combinations thereof, and the second metal halide is rare earth-based. A method for producing an oxyhalide-based fluorescent substance containing a metal halide.
The method of claim 2,

The alkali metal halide includes a chloride selected from the group consisting of LiCl, NaCl, KCl, and combinations thereof, and the alkaline earth metal halide includes BeCl 2 , MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , And chlorides selected from the group consisting of combinations thereof.
The method of claim 1,

The oxide precursor of the tricycle element is SiO 2 , Si (OH) 4 , SiH 4 , Si (OC 2 H 5 ) 4 , or a method for producing an oxyhalide-based fluorescent substance containing water-soluble silane.
The method of claim 1,

The reducing agent comprises a polymeric material 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. And oxyhalide-based phosphor production method.
The method of claim 1,

The heat treatment may include a first heat treatment performed at 150 ° C. to 400 ° C., a second heat treatment performed at 500 ° C. to 1000 ° C., and a third heat treatment performed at 700 ° C. to 1400 ° C. sequentially. It is, a method for producing an oxyhalide-based phosphor.
The method of claim 1,

After the heat treatment step, further comprising the step of treating the alkaline compound to the prepared oxyhalide-based phosphor, a method for producing an oxyhalide-based phosphor.
The method of claim 7, wherein

The alkaline compound is a compound selected from the group consisting of LiOH, NaOH, KOH, RbOH, CsOH, NH 4 OH, H 2 O 2 , and combinations thereof, or a propylamine compound, butylamine (butylamine ) -Based compound, pentylamine-based compound, hexylamine-based compound, heptylamine-based compound, aminobenzene-based compound, lithium amide-based compound, sodium amide Oxyhalide-based fluorescent substance comprising a compound selected from the group consisting of) -based compounds, potassium amide-based compounds, cesium amide-based compounds, hydrazine-based compounds, and combinations thereof Method of preparation.
An oxyhalide-based phosphor prepared by the method according to claim 1, wherein the oxyhalide-based phosphor has a composition of M 1 -M 2 -OX: M 3 , wherein M 1 is an alkali metal, an alkaline earth metal, or a transition metal. , M 2 is a tricyclic element selected from the group consisting of Al, Si, P, and combinations thereof, X is a halogen element, and M 3 is a rare earth metal, oxyhalide-based phosphor.
Obtaining a solution comprising an oxide precursor of a tricycle element selected from the group consisting of a first metal halide, a second metal halide, and Al, Si, P, and combinations thereof; And,

Adding a reducing agent to the solution and then heat-treating it under a nitrogen-containing atmosphere

Including,

Method for producing a nitride or oxynitride-based phosphor.
The method of claim 10,

The first metal halide includes a halide selected from the group consisting of alkali metal halides, alkaline earth metal halides, transition metal halides, and combinations thereof, and the second metal halide is rare earth-based. A method for producing a nitride-based or oxynitride-based phosphor containing a metal halide.
The method of claim 11,

The alkali metal halide includes a chloride selected from the group consisting of LiCl, NaCl, KCl, and combinations thereof, and the alkaline earth metal halide includes BeCl 2 , MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , And chlorides selected from the group consisting of combinations thereof.
The method of claim 10,

The oxide precursor of the tricycle element is SiO 2 , Si (OH) 4 , SiH 4 , Si (OC 2 H 5 ) 4 , or a method for producing a nitride-based or oxynitride-based phosphor containing water-soluble silane.
The method of claim 10,

The reducing agent comprises a polymeric material 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. And a method for producing a nitride or oxynitride-based phosphor.
The method of claim 10,

The heat treatment may include a first heat treatment performed at 150 ° C. to 400 ° C., a second heat treatment performed at 500 ° C. to 1000 ° C., and a third heat treatment performed at 700 ° C. to 1400 ° C. sequentially. The method for producing a nitride or oxynitride-based phosphor.
The method of claim 15,

The tertiary heat treatment is a method of producing a nitride-based or oxynitride-based phosphor that is carried out in an atmosphere in which a nitrogen-containing gas flows at 0.1 cm / s to 10 cm / s flux.
The method of claim 10,

The nitrogen-containing atmosphere may be formed by N 2 , NH 3 , or a combination thereof, a method for producing a nitride or oxynitride-based phosphor.
The method of claim 10,

After the heat treatment step, further comprising the step of treating the alkaline compound to the nitride-based or oxynitride-based phosphor prepared, a method for producing a nitride or oxynitride-based phosphor.
The method of claim 18,

The alkaline compound is a compound selected from the group consisting of LiOH, NaOH, KOH, RbOH, CsOH, NH 4 OH, H 2 O 2 , and combinations thereof, or a propylamine compound, butylamine (butylamine ) -Based compound, pentylamine-based compound, hexylamine-based compound, heptylamine-based compound, aminobenzene-based compound, lithium amide-based compound, sodium amide ) -Based compound, potassium amide-based compound, cesium amide-based compound, hydrazine-based compound, and a compound selected from the group consisting of a combination thereof, nitride-based or acid Method for producing nitride phosphor.
A nitride-based or oxynitride-based fluorescent material prepared by the method according to claim 10, wherein the nitride-based or oxynitride-based fluorescent material is M 1 -M 2 -NX: M 3 or M 1 -M 2 -ONX: M 3 Has a composition, wherein M 1 is an alkali metal, an alkaline earth metal, or a transition metal, and M 2 is a tricyclic element selected from the group consisting of Al, Si, P, and combinations thereof, wherein X is a halogen element , M 3 is a rare earth metal, nitride or oxynitride-based phosphor.