KR20120031355A

KR20120031355A - Preparing method of (y,gd)(p or v)o4:eu-type red phosphor powder and (y,gd)(p or v)o4:eu-type red phosphor powder by the same

Info

Publication number: KR20120031355A
Application number: KR1020100092837A
Authority: KR
Inventors: 박경순; 허미현
Original assignee: 세종대학교산학협력단
Priority date: 2010-09-24
Filing date: 2010-09-24
Publication date: 2012-04-03
Also published as: KR101207523B1

Abstract

PURPOSE: A manufacturing method of red phosphors powder is provided to manufacture (Y, Gd)(P or V)O4:Eu-based red phosphor powder with uniform powder shape, high brightness, high color purity and high luminance easily and quickly. CONSTITUTION: A manufacturing method of red phosphors powder comprises: a step of preparing the first solution in chemical formula: Y_xGd_(1-x))_(1-y)(P or V)O_4:Eu_y by dissolving a salt of Y, a salt of Gd and a salt of Eu into water(In chemical formula 0 <= x <=1, 0 < y < 1); a step of preparing a second solution comprising fuel, a salt of V or P, and a solvent; a step of forming the red phosphor powder of the chemical formula: (Y_xGd_(1-x))_(1-y)(P or V)O_4:Eu_y by heating a precursor solution, a mixture of the first solution and the second solution to 100-300 °C for combustion; and a step of annealing the resultant phosphor powder at 600-1300°C.

Description

(V, V) (P or V) Ok: Production method of Eu-based red phosphor powder and (V, Vd) (P or V) Ok: Eu-based red phosphor powder {PREPARING METHOD OF (Y, Gd (P or V) O4: Eu-TYPE RED PHOSPHOR POWDER AND (Y, Gd) (P or V) O4: Eu-TYPE RED PHOSPHOR POWDER BY THE SAME}

The present application provides a method for preparing (Y, Gd) (P or V) O ₄ : Eu-based red phosphor powder using solution combustion method and high temperature annealing and thereby (Y, Gd) (P or V) O ₄ : Eu-based red phosphor powder.

Recently, due to the development of digital video media such as full-scale digital terrestrial broadcasting and digitalization of cable TV, and the consumer's demand for large-area display, the market competition in the large flat-panel display field is accelerating. In addition, due to the global economic crisis, the necessity of quality and diversification of products is emerging as well as the shrinking of the consumer market and resulting manufacturing cost. According to the trend of the display industry up to now, the display market was mainly occupied by Cathode Ray Tube (CRT) until the 1990s, and from the late 1990s, the focus was on large area and light weight. The industry for Plasma Display Panel (LED) and Light Emitting Diode (LED) has been highly developed. Currently, LCD technology has been relatively highlighted by maximizing the advantages of mass production due to large investments, but PDP is receiving attention again as 3D-TV recently appeared in the display industry. First of all, the larger the screen, the more immersive the screen is, and the faster the response speed, the more the 3D stereoscopic effect can be made by reducing cross talk between screens. PDP has the best competitiveness as a 3D-TV among large flat panel display devices because it has the advantages of fast response speed, wide viewing angle, excellent color reproduction near nature, and low manufacturing cost. In order for PDP to have a competitive advantage in the field of large flat panel display devices, the development of Full-HD level 3D-PDP is on the rise. To realize Full-HD level 3D-PDP, high definition, high light emission, The condition of high efficiency must be satisfied. In particular, the role of phosphor, an important constituent material that directly affects the three conditions, is very important.

High resolution reduces the unit cell size to which the phosphor is applied in the PDP. In order to achieve such high resolution, a unit cell having a fine structure is required. Therefore, a phosphor having a fine and uniform size is required, and a condition of high efficiency and high emission is required in a small unit cell. However, commercially available phosphors are manufactured by the solid state method, and the average powder size is very large because of the high reaction temperature. In addition, the size of the powder that can be reduced by pulverization is limited, the shape of the powder is difficult to control, there is a high possibility of inflow of impurities in the milling process, damage to the surface of the phosphor and change in crystallinity has been raised as a problem.

Liquid phase methods such as coprecipitation, multi-stage precipitation, microemulsion, complex polymerization, sol-gel, hydrothermal synthesis, and solution combustion method enable uniform mixing of raw materials. It has the advantage of being manufactured. However, the liquid phase method has a disadvantage in that it is difficult to control the size and shape of the powder except for some phosphors.

Representative synthesis methods using the gas phase include gas phase condensation and spray pyrolysis. The powders produced by such a gas phase method have a fine size of 100 nm or less, and also have a good uniformity of powder size and can synthesize high purity powders, and also prevent agglomeration of powders, thereby producing phosphor powder for display. It is studied a lot. However, in the vapor phase process, since the vaporization characteristics and condensation characteristics of the respective raw material powders are different from each other, they are not suitable for the production of multicomponent powders and have problems in mass production.

The red (Y, Gd) BO ₃ : Eu phosphor has excellent emission intensity due to vacuum ultraviolet excitation, whereas it contains strong orange color and has a problem in color purity, and the green Zn ₂ SiO ₄ : Mn phosphor under vacuum ultraviolet ray It shows good light emission characteristics but has the disadvantage of long afterglow time and high discharge voltage. The blue BaMgAl ₁₀ O ₁₇ : Eu phosphor has a problem of shortening the life due to deterioration. In order to make up for the shortcomings of these phosphors, various researches have been conducted for several decades, and new phosphor compositions and manufacturing processes are being developed. The new compositions of YVO ₄ : Eu and Y ₂ O ₃ : Eu red phosphors achieve excellent color purity but have low luminescence intensity, so that Gd ³ ⁺ with good absorption characteristics at 147 nm is converted into YVO ₄ : Eu The (Y, Gd) VO ₄ : Eu phosphor was prepared by addition of, and the luminescence properties were studied. However, this phosphor also does not have a luminous intensity to replace a commercially available red phosphor. Therefore, in order to realize Full-HD 3D-PDP, it is necessary to simultaneously develop high phosphor and high color purity, and to have a phosphor having fine and uniform powder characteristics.

Accordingly, the present application provides a method for preparing (Y, Gd) (P or V) O ₄ : Eu-based red phosphor powder using solution combustion and high temperature annealing, in order to prepare red phosphor powder having fine and uniform powder characteristics. The (Y, Gd) (P or V) O ₄ : Eu-based red phosphor powder thereby.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the present application provides a method for preparing (Y, Gd) (P or V) O ₄ : Eu-based red phosphor powder using solution combustion and high temperature annealing. The red phosphor powder is prepared by dissolving salts of Y, salts of Gd and salts of Eu in water (Y _x Gd _1- _x ) _1-y (P or V) O ₄ : Eu _y (wherein Preparing a first solution having an atomic ratio of metals included in the formula represented by 0 ≦ x ≦ 1, 0 <y <1; Preparing a second solution comprising a fuel, a salt of V or a salt of P, and a solvent; The precursor solution in which the first solution and the second solution are mixed is heated to 100 ° C to 300 ° C to self-explode (Y _x Gd ₁ _-x ) _1-y (P or V) O ₄ : Eu _y (where Forming a red phosphor powder represented by 0 ≦ x ≦ 1 and 0 <y <1); And annealing the formed phosphor powder at 600 ° C to 1300 ° C.

In one embodiment, the red phosphor powder may be a nano powder, but is not limited thereto.

In another embodiment, the salts of Y, the salts of Gd and the salts of Eu each include those selected from the group consisting of nitrates, sulfates, chlorides, carbonates and combinations thereof of Y, Gd and Eu, respectively. May be, but is not limited thereto.

In another embodiment, the salts of Y, the salts of Gd and the salts of Eu may include, but are not limited to, nitrates of Y, nitrates of Gd and nitrates of Eu, respectively. For example, the nitrates of Y, the nitrates of Gd and the nitrates of Eu are each Y ₂ O ₃ , Gd ₂ O ₃ and Eu ₂ O _3. Each may be prepared by dissolving in nitric acid solution, but is not limited thereto. For example, the nitrates may act as oxidants, but are not limited thereto. For example, the ratio of the nitrates and the fuel may be 1: 1 in molar ratio, but is not limited thereto.

In another embodiment, the first solution may be an additional nitric acid, but is not limited thereto.

In another embodiment, each of the salts of V and the salts of P may include NH ₄ VO ₃ and (NH ₄ ) ₂ PO ₃ , but is not limited thereto.

In another embodiment, each of the salt of V and the salt of P may be to act as a reducing agent, but is not limited thereto.

In another embodiment, the fuel may include, but is not limited to, an organic compound containing at least one functional group of amine (-NH ₂ ) and carboxyl (-COOH).

In another embodiment, the fuel is aspartic acid, glutamic acid, carbohydrazide, citric acid, alanine, glycine, urea urea) and may include an organic compound selected from the group consisting of, but is not limited thereto.

In another embodiment, the solvent may include water, but is not limited thereto.

Another aspect of the present disclosure is prepared by the above production method, wherein (Y _x Gd _1- _x ) _1-y (P or V) O ₄ : Eu _y , wherein 0 ≦ x ≦ 1, 0 <y <1 Red phosphor powder, represented by) can be provided.

In one embodiment, the red phosphor powder may be in the form of a nano powder, but is not limited thereto.

In another embodiment, the red phosphor powder is a red phosphor represented by (Y _x Gd _1- _x ) _1- _y VO ₄ : Eu _y , wherein 0 ≦ x ≦ 1, 0 <y <1. Annealed at 600 ° C to 1200 ° C may include a tetragonal crystal structure, but is not limited thereto.

In another embodiment, the red phosphor powder is a red phosphor represented by (Y _x Gd _1- _x ) _1- _y PO ₄ : Eu _y (where 0 ≦ x ≦ 1, 0 <y <1). As annealed at 1100 ℃ to 1300 ℃ may include a tetragonal crystal structure, but is not limited thereto.

According to the present application, (Y, Gd) (P or V) O ₄ : Eu-based red phosphor powder having a uniform powder form can be easily prepared by preparing red phosphor powder by using solution combustion method and high temperature annealing. In particular, the solution combustion method (Y, Gd) (P or V) O ₄ having a uniform form in a short time by heating the precursor solution containing the metal salt and fuel for forming the red phosphor at a high temperature instantaneously self-explosion: Eu-based red phosphor powder is prepared. Since the nanopowder of the red phosphor can be obtained by the method of preparing the red phosphor powder of the present application, a milling process for pulverizing the obtained phosphor is not required additionally and thus has a uniform form at low cost in a short time through a simple process. (Y, Gd) (P or V) O ₄ : Eu-based red phosphor powder can be obtained. In addition, the (Y, Gd) (P or V) O ₄ : Eu-based red phosphor powder formed by annealing has high light emission, high color purity, and high brightness, thereby producing various displays such as PDPs manufactured using various phosphors. It can be suitably used as a red phosphor in the present invention.

1 is a schematic diagram showing a process of preparing an aqueous nitric acid solution according to an embodiment of the present application.
2 is a schematic diagram illustrating a process of synthesizing a (Y, Gd) VO ₄ : Eu or (Y, Gd) PO ₄ : Eu phosphor according to one embodiment of the present application.
Figure 3 is a (Y Gd ₀ _.5 ₀ _.5) synthesis according to one embodiment of the present _0.94 Eu ₀ _.06 VO ₄ It is a graph which shows the XRD pattern of (a) synthetic powder of fluorescent substance, and fluorescent substance annealed at (b) 600, (c) 800, (d) 1000, (e) 1100, and (f) 1200 degreeC, respectively.
Figure 4 is a (Y Gd ₀ _.5 ₀ _.5) synthesis according to one embodiment of the present _0.94 Eu ₀ _.06 VO ₄ FE- of phosphors annealed at (a) synthetic powder of phosphor and (b) 600, (c) 800, (d) 1000, (e) 1100, and (f) 1200 ° C (scale bar: 5 μm), respectively. SEM picture.
Figure 5 is a (Y Gd ₀ _.5 ₀ _.5) synthesis according to one embodiment of the present _0.94 Eu ₀ _.06 VO ₄ FE- of a phosphor annealed at (a) synthetic powder of phosphor and (b) 600, (c) 800, (d) 1000, (e) 1100, and (f) 1200 ° C (scale bar: 5 nm), respectively. SEM picture.
Figure 6 is a composite according to one embodiment of the present application _{(Y 0 .5 Gd 0 .5)} 0.94 Eu ₀ _.06 VO ₄ a phosphor (a) 600, (b) 800, (c) 1000, (d) 1100 And (e) emission spectra of the phosphors annealed at 1200 ° C. (λ _ex = 147 nm).
Figure 7 is a TGA / DSC curve of the _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO 4 powder synthesized in accordance with an embodiment of the present application.
8 is a (Y Gd ₀ _.5 ₀ _.5) synthesis according to one embodiment of the present _0.94 Eu ₀ _.06 PO ₄ (A) Synthetic powder of phosphor and (b) 600, (c) 800, (d) 1000, (e) 1100, (f) 1200, and (g) at 1300 ° C (●: monoclinic system, ▽: square Crystal structure) A graph showing an XRD pattern of an annealed phosphor.
9 is a (Y Gd ₀ _.5 ₀ _.5) synthesis according to one embodiment of the present _0.94 Eu ₀ _.06 PO ₄ (A) synthetic powder of phosphor and (b) 600, (c) 800, (d) 1000, (e), 1100 (f) 1200, and (g) 1300 ° C. (scale bar: 5 μm) FE-SEM photograph of the phosphor.
Figure 10 is a (Y Gd ₀ _.5 ₀ _.5) synthesis according to one embodiment of the present _0.94 Eu ₀ _.06 PO ₄ (A) synthetic powder of phosphor and (b) 600, (c) 800, (d) 1000, (e) 1100 (f) 1200, and (g) phosphor annealed at 1300 ° C. (scale bar: 500 nm) Is a FE-SEM picture
Figure 11 is annealed at 600, 800, 1000, 1100, 1200, and 1300 ℃ in accordance with one embodiment of the present application _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO 4 emission spectra (λ _ex of the phosphor = 147 nm) graph.
Figure 12 (a) 800 according to one embodiment of the present application - and 1000 (b) 1100 - annealing at _{1300 ℃ (Y 0 .5 Gd 0} .5) 0.94 Eu 0 .06 VUV emission spectra of the phosphor PO ₄ ( λ _ex = 147 nm).

DETAILED DESCRIPTION Hereinafter, embodiments and examples 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.

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, 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 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."

In one embodiment of the present application, the (Y, Gd) (P or V) O ₄ : Eu-based red phosphor powder is dissolved in a salt of Y, a salt of Gd and a salt of Eu in water (Y _x Gd ₁ _-x ) A first solution having an atomic ratio of the metals included in the formula represented by _1-y (P or V) O ₄ : Eu _y (where 0 ≦ x ≦ 1, 0 <y <1). Preparing; Preparing a second solution comprising a fuel, a salt of V or a salt of P, and a solvent; The precursor solution in which the first solution and the second solution are mixed is heated to 100 ° C to 300 ° C to self-explode (Y _x Gd ₁ _-x ) _1-y (P or V) O ₄ : Eu _y (where Forming a red phosphor powder represented by 0 ≦ x ≦ 1 and 0 <y <1); And annealing the formed phosphor powder at 600 ℃ to 1300 ℃ can be prepared by a method comprising a.

In preparing the red phosphor powder, a precursor solution obtained by mixing the first solution including the salt of Y, the salt of Gd and the salts of Eu, and the salt of V or the salt of P and a second solution containing a solvent When heated to 100 ° C to 300 ° C, the precursor solution instantaneously causes self-explosion, thereby synthesizing a uniform red phosphor powder, and the manufacturing method of the present application uses a kind of solution combustion method.

This solution combustion method is a process of the liquid phase method is a new process that can solve the disadvantages of the existing solid phase method. This method makes it possible to obtain the final phase easily and quickly from the mixture of precursor solutions without the formation of an intermediate phase, and to obtain very fine and homogeneous single or multicomponent oxide powders.

In an exemplary embodiment, in the preparation of the red phosphor powder by the solution combustion method, at least some of the components contained therein may act as an oxidizing agent or reducing agent. For example, when nitrate is used as the salt of each of Y, Gd and Eu, nitrate ions (NO ₃ ⁻ ) included in the nitrate may act as an oxidizing agent, and NH as the salt of V and the salt of P, respectively. ₄ VO ₃ and (NH ₄ ) ₂ PO ₃ Where each is used, the cations included in the salt may be each acting as a reducing agent, but is not limited thereto.

Thus, the oxidation-reduction relationship may be applied to the combustion synthesis reaction in preparing the red phosphor powder by the solution combustion method, thereby determining the valence ratio of the oxidizing agent and the reducing agent included in the precursor solution. By applying this method, an appropriate oxidation-reduction scheme can be made. The fuel may include, but is not limited to, an organic compound containing at least one functional group of amine (-NH ₂ ) and carboxyl (-COOH). For example, the fuel may be aspartic acid, glutamic acid, carbohydrazide, citric acid, alanine, glycine, urea and It may include an organic compound selected from the group consisting of a combination thereof, but is not limited thereto.

For example, when the nitrate of the metal is included in the precursor solution, that is, when nitrate is used as a salt of each of Y, Gd and Eu, the nitrate ions (NO ₃ ⁻ ) included in the nitrate may act as an oxidizing agent. In addition, when the nitrate of the metals, which can act as the fuel and the oxidant, is dissolved in distilled water and heated, the NO ₃ ⁻ in the solution undergoes a rapid exothermic reaction with the combustible gas decomposed from the fuel. The red phosphor powder synthesized after such a combustion reaction may be obtained in a single phase having excellent crystallinity or a powder having excellent properties through a simple heat treatment process. The valence number of the total oxidation-reduction of each of the salts of Y, salts of Gd and salts of Eu used above can be adjusted by methods reported in the art by stoichiometric calculations. In addition, when the red phosphor powder is synthesized, low pH of an additive or a solution in an oxide state, insufficient synthesis between ions, and the like may be a factor affecting combustion synthesis.

In one embodiment, the nitrate of Y, the nitrate of Gd and the nitrate of Eu are each Y ₂ O ₃ , Gd ₂ O ₃ and Eu ₂ O ₃ Each may be prepared by dissolving in nitric acid solution, but is not limited thereto.

In one embodiment, the ratio of the nitrates and the fuel may be 1: 1 in molar ratio, but is not limited thereto. This is because the stoichiometric ratio of nitrate ions acting as an oxidant and the fuel acting as a reducing agent controls the thermal energy during the combustion reaction, since the maximum energy is obtained under the condition that the ratio of reducing agent: oxidant is 1: 1. Under these conditions, the calorific value is large, so that the combustion reaction occurs well, and only the combustion process is known to be suitable for obtaining the crystal phase of the final purpose.

In this regard, in the exemplary _{embodiment, (Y 0 .5 Gd 0 .5} ) 0.94 Eu 0 .06 VO metal nitrate to synthesize the ₄ phosphor with a solution combustion process _{(Y (NO 3) 3?} 6H 2 O, Gd (NO ₃ ) ₃ ˜5H ₂ O, and Eu (NO ₃ ) ₃ ˜6H ₂ O) and nitric acid (HNO ₃ ) were used, and citric acid (C ₃ H ₄ (OH) (COOH) was used as the fuel. ) ₃ ) and NH ₄ VO ₃ (NH ₄ ⁺ ion in the salt Can act as a reducing agent), the ratio of the valence ratio of the oxidizing agent and the reducing agent in the above-described combustion synthesis reaction can be applied to make an appropriate redox reaction formula. In particular, the stoichiometric ratio of the reducing agent / oxidant may be calculated as 1 so that the combustion reaction occurs well.

In another exemplary _{embodiment, (Y 0 .5 Gd 0 .5} ) 0.94 Eu 0 .06 to synthesize the PO ₄ phosphor with a solution combustion method _{Y (NO 3) 3? 6H} 2 O, Gd (NO 3) _{3 to} 5H ₂ O, and Eu (NO ₃ ) _{3 to} 6H ₂ and nitric acid (HNO ₃ ), citric acid (C ₃ H ₄ (OH) (COOH) ₃ fuel and (NH ₄ ) ₂ HPO ₄ ) Can be.

The first solution may further include nitric acid, but is not limited thereto. The nitric acid to be added is weighed and added under the condition that the molar ratio of oxidizing agent: reducing agent in the precursor solution is 1: 1.

The precursor solution may be used by adding a solvent for more effective mixing, for example, may include acetone, alcohol and water, but is not limited thereto. It can be sufficiently mixed to stir using the selected solvent to have a uniform composition.

The (Y, Gd) (P or V) O ₄ : Eu-based red phosphor prepared by using the solution combustion method of the present application may be obtained in the form of a high luminescence, high purity color particulate powder replacing a commercially available red phosphor.

The red phosphor powder prepared by the above production method is (Y _x Gd _1- _x ) _1-y (P or V) O ₄ : Eu _y (where 0 ≦ x ≦ 1, 0 <y <1). It may be displayed, and may have a nano powder form.

In one embodiment, the red phosphor powder is a red phosphor represented by (Y _x Gd _1- _x ) _1- _y VO ₄ : Eu _y and annealed at 600 ° C. to 1200 ° C., or 600 ° C. to 1000 ° C. It may have a crystal structure, but is not limited thereto. When the red phosphor powder is annealed at 1000 ° C., the strongest emission intensity and the best color purity can be obtained. If the annealing temperature is less than 600 ° C it is not preferable because it has a monoclinic crystal structure, and if the annealing temperature exceeds 1200 ° C it is not preferable because the aggregation becomes severe.

In another embodiment, the red phosphor powder may be a red phosphor represented by (Y _x Gd _1- _x ) _1- _y PO ₄ : Eu _y and annealed at 1000 ° C. to 1300 ° C. to include a tetragonal crystal structure. However, it is not limited thereto. In the case of the red phosphor represented by (Y _x Gd _1- _x ) _1- _y PO ₄ : Eu _y , when the annealing temperature is less than 1000 ° C., it has a monoclinic crystal structure, which is not preferable. It is not preferable because the aggregation becomes severe.

For example, TGA-DSC (To analyze the thermal behavior of the (Y, Gd) VO ₄ : Eu-based phosphor and (Y, Gd) PO ₄ : Eu-based phosphor prepared by using the solution combustion method of the present application) Thermo Gravimetric Analysis-Differential Scanning Calorimeter can be used. In addition, in order to investigate the crystallinity and crystal structure of the synthesized phosphor, it can be analyzed using XRD (X-ray Diffraction), and to observe the size and shape of the phosphor powder, the sputter (sputter) After coating a thick platinum on the surface can be analyzed using a field emission scanning electron microscope (FE-SEM). In addition, the luminescence properties of the prepared phosphor powder can be analyzed using a Spectro-Fluorophotometer (PSI).

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

An embodiment of the preparation of the (Y, Gd) VO ₄ : Eu-based and (Y, Gd) PO ₄ : Eu-based red phosphors will be described as follows.

Yttrium oxide (III) (Y ₂ O ₃ , 99.99%, Kojundo Chemical Laboratory), gadolinium (III) oxide (Gd ₂ O ₃ , 99.99%, Kojundo Chemical Laboratory), uropium oxide (III) (Eu ₂ O ₃ , 99.99%, Kojundo Chemical Laboratory), vanadate nitride (NH ₄ VO ₃ , 99%, Kojundo Chemical Laboratory) and diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ , 99%, Junsei) were used.

One. Mixed Nitrate Aqueous Solution Preparation

A process of making a nitrate of a metal containing nitrate ions acting as an oxidant and an aqueous solution of nitrate using the same is shown in FIG. 1. Y ₂ O ₃ , Gd ₂ O ₃ , weighed according to the designed composition, And Eu ₂ O ₃ Each was slowly dissolved in a prepared beaker containing nitric acid (HNO ₃ , 60%, PFP Osaka Japan) and dried to prepare nitrate. The prepared nitrate solution was dissolved in distilled water to prepare an aqueous solution of Y nitrate, an aqueous solution of Gd nitrate, and an aqueous solution of Eu nitrate.

2. Using precursor preparation and solution combustion method (Y, Gd ) VO ₄ : Eu -System and (Y, Gd ) PO ₄ : Eu Synthesis of -based Phosphors

The synthesis process of the (Y, Gd) VO ₄ : Eu-based and (Y, Gd) PO ₄ : Eu-based phosphors using the solution combustion method is schematically shown in FIG. 2. Citric acid (C ₃ H ₄ (OH) (COOH) ₃ , 99.5%, Duksan) as a fuel and citric acid were weighed under the condition of 1: 1 with a molar ratio of nitrate (the nitrate ion acting as an oxidant) of the metals, and then distilled water To dissolve. The solution was prepared by adding NH ₄ VO ₃ (cationic as a reducing agent) or (NH ₄ ) ₂ HPO ₄ (cationic as a reducing agent), respectively, according to the designed composition. To prevent precipitation of aqueous solution of gadolinium phosphate (GdPO ₄ ~ H ₂ O) to the prepared mixture, NH ₄ VO ₃ Nitric acid (oxidant) was added to increase solubility. Silver nitrate was weighed under conditions such that the molar ratio of oxidizing agent: reducing agent is 1: 1. Finally, the precursor solution was prepared by mixing the prepared mixed solution and the mixed nitrate aqueous solution prepared above. The precursor solution was placed on a hot plate and heated to self-explosion at 100 ° C to 300 ° C. In order to increase the crystallinity of the powder synthesized by self-explosion and to improve the luminescence properties, annealing was performed at various temperatures (600-1300 ° C). After heating to an annealing temperature at a temperature increase rate of 10 ℃ / min and maintained at this temperature for 4 hours, and then cooled to room temperature to prepare a (Y, Gd) (P or V) O ₄ : Eu-based phosphor powder to be described later Characterization was performed as described.

3. (Y, Gd ) VO ₄ : Eu -System and (Y, Gd ) PO ₄ : Eu Characterization of -based Phosphor

(Y, Gd) VO ₄ : Eu-based and (Y, Gd) PO ₄ : Eu-based prepared according to this example 10 ° C./min heating rate using a thermal analysis device TGA-DSC (Thermo Gravimetric Analysis-Differential Scanning Calorimeter: Scinco STA S-1500) to analyze the thermal behavior of each phosphor powder and determine the optimum annealing temperature Thermal analysis was carried out in the temperature range of 40 ℃-1200 ℃.

Synthesized (Y, Gd) VO ₄ : Eu-based and (Y, Gd) PO ₄ : Eu-based In order to investigate the crystallinity and crystal structure of the phosphor, XRD (X-ray Diffraction: Rigaku RINT2000) was used. Voltage = 40 kV, current = 100 mA, target = Cu Kα ₁ , XRD experiments were performed under scanning range (2θ) = 10 °-60 °, scan speed = 4 ° / min, step size = 0.01 °, slit = 10 mm. The microcrystal size (D) was calculated using XRD results and Scherre's equation. Scherre's equation is

Where λ is Cu Ka ₁ The wavelength of the X-rays by the radiation (1.541 kHz, θ is the diffraction angle, B is the full width at the half-maximum (FWHM) at 2θ).

In order to observe the size and shape of the phosphor powder, the surface of the powder was coated with a thickness of sputter (E-1030, Hitachi) and then FE-SEM (Field Emission Scanning Electron Microscope: Hitachi S4700, JEOL JSM-6390) ). Acceleration voltage was 10-20 kV and working distance was 10-15 mm.

In order to analyze the emission characteristics of the prepared phosphor powder, an emission spectrum was obtained under a vacuum ultraviolet (VUV) using a Spectro-Fluorophotometer (PSI). A light source was used as a D ₂ lamp, and monochromatic at 147 nm using a monochromator. The monochromator and the specimen chamber were maintained at 4 × 10 ^-5 torr or higher vacuum using a turbo molecular pump (TMP), and the emission of phosphors was 380-780 nm using a grating of 1200 grooves / mm. The range was scanned at 0.5 nm intervals and then detected with a photomultiplier tube.

4. Annealing Depending on the temperature (Y, Gd ) VO ₄ : Eu -Characteristics of phosphor

In order to analyze the effect of the annealing temperature, (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 VO ₄ phosphor prepared as in the above example was heat-treated at various temperatures (600, 800, 1000, 1100, and 1200 ° C). The Eu ³ ⁺ ion added as an activator was 0.06 mol, 0.47 mol for Y ³ ⁺ and Gd ³ ⁺ ions, and 1 mol for V ⁵ ⁺ ions. The crystal structure, crystallinity, microcrystal size (microcrystal size), powder shape and size, luminescence intensity, and color purity of phosphors prepared at various annealing temperatures were studied. The annealing temperature showing the best luminescence properties was derived here.

( Y ₀ _.5 Gd ₀ _.5 ) _0.94 Eu ₀ _.06 VO ₄ Synthesis of Red Phosphor Powder

_{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 VO 4 to synthesize a red phosphor with a solution combustion _{process, Y (NO 3) 3?} 6H 2 O, Gd (NO 3) 3? 5H 2 O, and _{Eu (NO 3) 3? 6H} 2 O) ( was used HNO ₃₎ with an oxidizing agent, and citric acid (C ₃ H ₄ (OH) of metal nitrate and nitric acid (COOH) ₃₎ uses a fuel and NH ₄ VO ₃ as the reducing agent It was.

In the combustion synthesis reaction, the valence ratio of the oxidizing agent and the reducing agent can be applied to make an appropriate redox reaction formula. The stoichiometric ratio of the reducing agent / oxidizing agent was set to 1 as described above so that the combustion reaction occurred well. Silver nitrate was weighed under conditions such that the molar ratio of oxidizing agent: reducing agent is 1: 1. Finally, the precursor solution was prepared by mixing the prepared mixed solution and the mixed nitrate aqueous solution prepared above. The precursor solution was placed on a hot plate and heated to self-explosion at 100 ° C to 300 ° C. Annealing was performed at 600 ° C., 800 ° C., 1000 ° C., 1100 ° C., and 1200 ° C., respectively, to increase the crystallinity and the light emission characteristics of the powder synthesized by self-explosion. The heating to the annealing temperature at a heating rate of 10 ℃ / min, and the mixture was kept at this temperature for 4 hours, followed by ronaeng to room temperature _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 VO 4 red phosphor powder was prepared .

( Y ₀ _.5 Gd ₀ _.5 ) _0.94 Eu ₀ _.06 VO ₄ Crystal structure analysis of red phosphor

Figure 3 shows the _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 VO 4 phosphor composite powder and 600, respectively, XRD results of annealing the phosphor at 800, 1000, 1100, and 1200 ℃. All powders can be confirmed by JCPDS (no. 85-2317) as solid solutions of constituent oxides having tetragonal crystal structures. In addition, as the annealing temperature increases from 600 ° C. to 1200 ° C., the XRD peak intensity of the phosphor increases, and the XRD width becomes narrower. From this, we can assume that annealing temperature increases, crystallinity improves, and microcrystal size increases. (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 VO ₄ The main peaks of the phosphors (200), (112), and (312) and the Scherrer equation can be used to calculate the microcrystal size. As a result of calculation, the microcrystalline sizes of the powders annealed at 600, 800, 1000, 1100, and 1200 ° C. were 30.5, 59.4, 62.4, 62.6, and 63.7 nm, respectively. As the annealing temperature increased, it can be clearly seen that the _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 increase the fine grain size of the VO ₄ phosphors.

( Y ₀ _.5 Gd ₀ _.5 ) _0.94 Eu ₀ _.06 VO ₄ Fine structure of red phosphor

Figure 4 _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 is an FE-SEM photograph of a VO ₄ powder and annealing the phosphor in Synthesis, 600, 800, 1000, 1100, and 1200 ℃ of. The size of the synthetic powder and the phosphor powders annealed at 600 800, 1000, 1100, and 1200 ° C. were approximately 40-60 nm, 60-120 nm, 0.5-1.4 μm, 0.7-3.6 μm, 2.4-4.8 μm, and 3.3, respectively. 5.5 μm. As the annealing temperature increased _{(Y 0 .5 Gd 0 .5)} 0.94 a Eu ₀ _.06 VO size of the phosphor powder ₄ can be seen to increase significantly. Synthetic powder having a nano size and (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 VO ₄ phosphor powder annealed at 600 ° C. is difficult to identify the shape in FIG. Herein, nano-sized powders were synthesized using the solution combustion method. Most after annealing _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 VO 4 phosphor powders were maintained the spherical shape.

( Y ₀ _.5 Gd ₀ _.5 ) _0.94 Eu ₀ _.06 VO ₄ Luminescence Characteristics of Red Phosphors

6 is at 147 nm here was _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 VO 4 The emission spectrum according to the annealing temperature (600, 800, 1000, 1100, and 1200 ℃) of the phosphor is shown. Four emission peaks were observed at 594, 615-619, 653, and 698-704 nm in the emission spectrum of all (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 VO ₄ phosphors. The four light emitting peak is ⁵ D ₀ of Eu ³ ⁺ ion, respectively → ⁷ F ₁ , ⁵ D ₀ → ⁷ F ₂ , ⁵ D ₀ → ⁷ F ₃ , and ⁵ D ₀ ≧ the typical red emission pattern is due to a ⁷ F ₄ transition. ⁵ D ₀ → the strongest red emission intensity due to the ⁷ F ₂ transition was seen and observed at 619 nm. This means that a (Y Gd ₀ _.5 ₀ _.5) offered better color purity of _0.94 Eu ₀ _.06 VO ₄ phosphor produced in this study than commercial phosphor which emits light with the red and orange.

Annealing at different temperatures (Y Gd ₀ _.5 ₀ _.5) the light intensity of _0.94 Eu ₀ _.06 VO ₄ phosphor was observed for the 619 nm. Compared to phosphors annealed at 600 ° C., the red luminescence intensity of phosphors annealed at 800, 1000, 1100, and 1200 ° C. increased by 100, 244, 321, 290, and 248%, respectively. The specimen annealed at 1000 ° C. showed the strongest luminescence intensity, and the emission intensity increased about 3.2 times compared to the phosphor annealed at 600 ° C. This is because the crystallinity improved with annealing temperature. In addition, when the annealing temperature is more than 1100 ℃, it can be seen that the emission intensity decreases, which is more effective in reducing the emission intensity by increasing the size of the powder than the effect of improving the crystallinity to increase the emission intensity. do. In general, when the powder size decreases, the number of powders per unit area increases, thereby increasing luminous efficiency.

Eu ⁵ D ₀ of ³ ⁺ ≧ light is emitted by the ⁷ F ₁ transition (594 nm) and ⁵ D ₀ → it emits red color by the ⁷ F ₂ transition (619 nm). Therefore, the emission intensity ratio of the two peaks ( ⁵ D ₀ → ⁷ F ₂ ) / ( ⁵ D ₀ → ⁷ F ₁ ) correlates with the color purity of the red phosphor. ⁵ D ₀ by annealing temperature → ⁷ F ₁ transition and ⁵ D ₀ ≧ the luminous intensity due to the transition of ⁷ F ₂ , and ( ⁵ D ₀ → ⁷ F ₂ ) / ( ⁵ D ₀ → ⁷ F ₁ ) is shown in Table 1. Annealing Temperature ( ⁵ D ₀ → ⁷ F ₂ ) / ( ⁵ D ₀ → ⁷ F ₁ ) showed the same tendency as the emission intensity value at 619 nm shown in FIG. 6. As the annealing temperature increases to 1000 ° C ( ⁵ D ₀ → ⁷ F ₂ ) / ( ⁵ D ₀ → The value of ⁷ F ₁ ) increases and decreases above this temperature. Therefore we can expect the most excellent color purity of the _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 VO 4 phosphors annealed at 1000 ℃.

600-1 annealing at a temperature of _{1200 ℃ (Y 0 .5 Gd 0} .5) 0.94 Eu 0 .06 VO 4 phosphors all had a tetragonal crystal sphere. The phosphor annealed at 1000 ° C. showed the strongest luminous intensity and the best color purity. This phosphor was observed to have a greater maximum emission intensity by 321% than the phosphor annealed at 600 ° C.

In this embodiment, in order to study the effects of, one of the important processes in the synthesis annealing temperature _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO 4 phosphor to various temperatures (600, 800, 1000, 1100, 1200 And 1300 ° C.). The Eu ³ ⁺ ions added body activity of 0.06 mol, Y ⁺ ³ and Gd ³⁺ ion is 0.47 mol, ⁵ and P ⁺ ions 1 mol. The crystal structure, crystallinity, microcrystalline size, powder shape and size, luminescence intensity, and color purity of phosphors prepared at various annealing temperatures were studied.

( Y ₀ _.5 Gd ₀ _.5 ) _0.94 Eu ₀ _.06 PO ₄ Synthesis of Red Phosphor Powder

_{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 Y to synthesize the PO ₄ phosphor with a solution combustion process _{(NO 3) 3? 6H 2} O, Gd (NO 3) 3? 5H 2 O, and Eu ( NO _{3) 3?} (was used HNO _3), citric acid _{(C 3 H 4 (OH)} 6H 2 and nitric acid was used (COOH) ₃ fuel and (NH ₄₎ ₂ HPO _4.

The valences of C, H, and O are +4, +1, and -2, respectively, the valence of P is +5, and Y, Gd, and Eu are all +3. In the case of N, since it does not affect the oxidation-reduction reaction, it is not considered. The stoichiometric ratio of the reducing agent / oxidant was calculated to be 1 so that the oxidation valence of the reducing agent used and the reducing valency of the oxidizing agent were as described above.

Composite ( Y ₀ _.5 Gd ₀ _.5 ) _0.94 Eu ₀ _.06 PO ₄ Red phosphor Thermal analysis

The composite _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO was shown in FIG. 7, the results obtained with a differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) to determine the thermal behavior of _four. 40 - weight loss appears to 125 ℃ is due to the removal of the synthesized _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO 4 with water and the remaining water molecules adsorbed on the powder surface. The weight loss at 230-500 ° C. is due to the decomposition of citric acid remaining in the synthesized (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 PO ₄ powder, consistent with the large exothermic peak of DSC at 462 ° C. Small exothermic peak that appears in DSC at 742 ℃ is in the synthesized _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO 4 will by the crystallization of the powder, the amorphous powder, when heated above the temperature monoclinic crystal structure It is crystallized. The weak exothermic peak at 1030 ° C is thought to be phase transition from monoclinic crystal structure to tetragonal crystal structure.

( Y ₀ _.5 Gd ₀ _.5 ) _0.94 Eu ₀ _.06 PO ₄ Crystal structure of the red phosphor

By annealing temperature _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO to evaluate the crystallinity and the crystal structure of the phosphor _4, a composite powder and annealed at 600, 800, 1000, 1100, 1200, and 1300 ℃ XRD results of the phosphor are shown in FIG. 8. It can be seen that the (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 PO ₄ phosphor annealed at 600 ° C. with the synthetic powder is amorphous. _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO 4 phosphor has been crystallized in the annealing temperature of 800 ℃, which is consistent with the DSC results mentioned above. It was found that the phosphor annealed at 800-1000 ° C had a monoclinic structure by JCPDS (no. 32-0386). However, the (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 PO ₄ phosphor annealed at 1100 ° C has a tetragonal crystal structure in addition to the monoclinic crystal structure, which has a tetragonal crystal structure between 1000 ° C and 1100 ° C. It means that it started to change. (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 PO ₄ phosphors, annealed at 1300 ° C, had very little monoclinic crystal structure, mostly tetragonal It can be seen that it has a crystal structure. In addition, it can be seen that as the annealing temperature increases, the XRD peak intensity of the crystal phase increases and the peak becomes sharp, which shows that the crystallinity is improved and the microcrystal size is increased. Annealing in the Scherrer equation and the _{800, 1000 ℃ (Y 0 .5} Gd 0 .5) 0.94 Eu 0 .06 PO 4 phosphor main peaks of 200, 120, (012) using the peak size of the microcrystalline Was calculated. Annealing at 800 ℃ and _{1000 ℃ (Y 0 .5 Gd 0} .5) 0.94 Eu 0 .06 Microcrystalline amount of PO ₄ phosphor is 29.5 nm and 45.8 nm, respectively. Annealing at 1100, 1200, and _{1300 ℃ (Y 0 .5 Gd 0} .5) 0.94 Eu 0 .06 PO the main peaks of 200, 101 of the _fourth fluorescent material, and 312 calculated using the peak Microcrystalline sizes are 47.0, 47.8, and 52.9 nm, respectively.

( Y ₀ _.5 Gd ₀ _.5 ) _0.94 Eu ₀ _.06 PO ₄ Fine structure of red phosphor

9 shows synthetic powders (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 PO ₄ annealed at 600, 800, 1000, 1100, 1200, and 1300 ° C. FE-SEM photograph of the phosphor. Annealing in the synthetic powder and 600, 800, 1000, 1100, 1200, and 1300 ℃ temperature _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO ₄ size of the phosphor powder is about 3 each - 20 nm, 5 20 nm, 25-50 nm, 100-250 nm, 125-400 nm, 0.3-1 μm, and 0.75-1.5 μm. _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO ₄ size of the phosphor powder was increased as the annealing temperature increases. Annealing in the synthetic powder and 600 ℃ having a nano-scale (Y Gd ₀ _.5 ₀ _.5) to _0.94 Eu ₀ _.06 PO ₄ phosphor powder 10 to a FE-SEM photograph in a high magnification observation, because this shape is also difficult to make Indicated. FE-SEM results of these specimens showed discussed _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 VO 4 phosphor powders with different characteristics in the previous section. As the annealing temperature increased _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO 4 phosphor powders (Y _0.5 Gd _0.5) it can be seen that grow much less than _0.94 Eu _0.06 VO ₄ phosphors. Fine crystal grains (0.75-1.5 mu m) were observed in the phosphor annealed at a high temperature of 1300 ℃.

( Y ₀ _.5 Gd ₀ _.5 ) _0.94 Eu ₀ _.06 PO ₄ Luminescence Characteristics of Red Phosphors

11 is at 147 nm here was _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO 4 The emission spectrum for each annealing temperature of the phosphor is shown. Amorphous (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 PO ₄ annealed at 600 ° C Phosphor did not substantially emit light, the (Y _0.5 Gd _0.5) annealing at least 800 ℃ _0.94 Eu _0.06 PO ₄ phosphor is Eu ³ ⁺ ions of the transition ⁽⁵ D ₀ → ⁷ F ₁ , ⁵ D ₀ → ⁷ F ₂ , ⁵ D ₀ → ⁷ F ₃ , ⁵ D ₀ → ⁷ F ₄ ), four emission peaks were observed. In addition, four emission wavelengths of (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 PO ₄ phosphors according to annealing temperature were greatly influenced by the crystal structure. Phosphors annealed at 800 and 1000 ° C with monoclinic crystal structure showed four emission peaks at 588-594, 613-621, 653, and 667-700 nm, and partly tetragonal crystal structure in monoclinic crystal structure. annealing at 1100, 1200, and 1300 ℃ occurred in a phase change _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO 4 phosphor 592, 619, 651, and 696 - the four emission peak at 703 nm Was observed. It showed to such a light emitting annealing at 800 ℃ and 1000 ℃ to see easily know a change in the wavelength _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 12 PO ₄ the emission spectrum of the phosphor (a), 1100 The emission spectra of the phosphors annealed at, 1200, and 1300 ° C. are shown in FIG. 12 (b). 12 having a monoclinic crystal structure in _{(a) (Y 0.5 Gd 0.5} ) 0.94 Eu 0.06 PO 4 phosphor is Eu ³ ⁺ ⁵ D ₀ of the ion ¡Æ the emission intensity at 594 nm is the largest due to the ⁷ F ₁ transition, and these emission peaks show greater emission intensity than phosphors annealed at 1000 ° C than phosphors annealed at 800 ° C. This is due to the increased crystallinity as mentioned in the previous XRD. 12 (b), the (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 PO ₄ phosphor annealed at 1100 ° C. is ⁵ D _0. → ⁷ a light emission intensity of 592 nm by the F ₁ transition is the largest and, annealing at more than _{1200 ℃ (Y 0 .5 Gd 0} .5) 0.94 Eu 0 .06 PO 4 phosphor is ⁵ D ₀ ¡Æ the luminescence intensity of 619 nm by the ⁷ F ₂ transition is the largest. Results changing the main emission peak as described above, and considered that hayeotgi phase transition to monoclinic crystal structure is a tetragonal crystal structure by annealing at a temperature of at least 1100 ℃, a tetragonal crystal structure ⁵ D ₀ ¡Æ it is believed to increase the luminescence intensity due to the ⁷ F ₂ transition.

Eu ⁵ D ₀ of ³ ⁺ ≧ light is emitted at 594 nm by ⁷ F ₁ transition and ⁵ D ₀ → it emits red at 619 nm by the ⁷ F ₂ transition. Thus the ratio of luminous intensity by two transitions ( ⁵ D ₀ → ⁷ F ₂ ) / ( ⁵ D ₀ ¡Æ the value of ⁷ F ₁ ) is closely related to the color purity of the red phosphor. ⁵ D ₀ by annealing temperature → ⁷ F ₁ transition and ⁵ D ₀ ≧ the intensity of the luminescence peak by the ⁷ F ₂ transition, and ( ⁵ D ₀ → ⁷ F ₂ ) / ( ⁵ D ₀ → ⁷ F ₁ ) is shown in Table 2. (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 PO ₄ phosphor annealed at 1000 ° C. compared to phosphor annealed at 800 ° C. ( ⁵ D ₀ → ⁷ F ₂ ) / ( ⁵ D ₀ → ⁷ F ₁ ) was small. (Y _0.5 Gd _0.5 ) _0.94 Eu _0.06 PO ₄ phosphors annealed at 1100 ° C or above to form tetragonal crystal structure ( ⁵ D ₀₎ → ⁷ F ₂ ) / ( ⁵ D ₀ → ⁷ F ₁ ) was increased. Of phosphors annealed at 1300 ° C ( ⁵ D ₀ → ⁷ F ₂ ) / ( ⁵ D ₀ → ⁷ F ₁ ) is 1.037, the largest. ( ⁵ D ₀ → ⁷ F ₂ ) / ( ⁵ D ₀ ¡Æ the reason why the value of ⁷ F ₁ ) is increased is that the monoclinic crystal structure is changed to tetragonal crystal structure with increasing annealing temperature. Therefore, there is a _{(Y 0 .5 Gd 0 .5)} 0.94 Eu 0 .06 PO _4, the color purity of the phosphor annealing at 1300 ℃ can be seen that the most excellent.

_{600 - (Y 0 .5 Gd 0} .5) by annealing at a temperature of 1300 ℃ _0.94 Eu ₀ _.06 PO ₄ As a result of analyzing the crystal structure of the phosphor, the specimen annealed at 800 ° C. had a monoclinic crystal structure, and the specimen annealed at 1100 ° C. or higher coexisted with a phase having a monoclinic structure. When increasing the tetragonal phase Eu ³ ⁺ ⁵ D ₀ of the ion ¡Æ the red emission intensity by the ⁷ F ₂ transition is increased. Phosphors annealed at 1300 ° C had the most tetragonal phases, showing the strongest luminous intensity and the best color purity.

Hereinbefore, the present invention has been described in detail with reference to the embodiments and examples, but the present invention is not limited to the above embodiments and embodiments, and may be modified in various forms, and is commonly used in the art within the technical spirit of the present application. It is evident that many variations are possible by those of skill in the art.

Claims

Dissolve salts of Y, salts of Gd, and salts of Eu in water (Y _x Gd _1- _x ) _1-y (P or V) O ₄ : Eu _y (where 0 ≦ x ≦ 1, 0 <y Preparing a first solution having an atomic ratio of the metals included in the formula represented by <1);
Preparing a second solution comprising a fuel, a salt of V or a salt of P, and a solvent;
(Y _x Gd ₁ _-x ) _1-y (P or V) O ₄ : Eu _y (where Forming a red phosphor powder represented by 0 ≦ x ≦ 1 and 0 <y <1); And
Annealing the formed phosphor powder at 600 ° C to 1300 ° C: comprising, red phosphor powder manufacturing method.

The method of claim 1,
The red phosphor powder is a nano powder, the manufacturing method of red phosphor powder.

The method of claim 1,
Wherein each of the salts of Y, the salts of Gd and the salts of Eu are selected from the group consisting of nitrates, sulfates, chlorides, carbonates and combinations thereof of Y, Gd and Eu, respectively, Manufacturing method.

The method of claim 1,
The salt of Y, the salt of Gd and the salt of Eu each comprises a nitrate of each of Y, Gd and Eu, the method of producing a red phosphor powder.

The method of claim 4, wherein
Each of the nitrates is Y ₂ O ₃ , Gd ₂ O ₃ and Eu ₂ O ₃ It is prepared by dissolving each in a nitric acid solution, a method for producing a red phosphor powder.

The method of claim 1,
The first solution further comprises nitric acid, method of producing a red phosphor powder.

The method of claim 1,
The salt of V and the salt of P, respectively, will include NH ₄ VO ₃ and (NH ₄ ) ₂ PO ₃ , the method for producing a red phosphor powder.

The method of claim 1,
Wherein the fuel comprises an organic compound containing at least one functional group of amine (-NH ₂ ) and carboxyl (-COOH).

The method of claim 8,
The fuel is aspartic acid, glutamic acid, carbohydrazide, citric acid, alanine, glycine, urea, and combinations thereof. Method for producing a red phosphor powder comprising an organic compound selected from the group consisting of.

The method of claim 1,
The solvent is a method of producing a red phosphor powder, comprising water.

Prepared by the method according to any one of claims 1 to 10, wherein (Y _x Gd _1-x ) _1-y (P or V) O ₄ : Eu _y (where 0 ≦ x ≦ 1, 0 <y <1), a red phosphor powder.

The method of claim 11,
Red phosphor powder having a nano powder form.

The method of claim 11,
Red phosphor represented by (Y _x Gd _1- _x ) _y VO ₄ : Eu ₁ _- _y annealed at 600 ° C. to 1200 ° C. to comprise a tetragonal crystal structure.

The method of claim 11,
A red phosphor represented by (Y _x Gd _1- _x ) _1- _y PO ₄ : Eu _y , which is annealed at 1000 ° C. to 1300 ° C. to include a tetragonal crystal structure.