KR102326279B1 - Selective Fabrication Method of Metal Fluoride-based Phosphors - Google Patents

Abstract

The present invention relates to a method for manufacturing a metal fluoride-based phosphor, wherein the manufacturing method according to the present invention has the formula MOx (M is a host element selected from the group of metalloids, post-transition metals and transition metals, and x is the oxidation number of the host element M) A metal fluoride-based phosphor is produced by heating a reaction solution containing a raw material and an organic solvent containing a first precursor that satisfies charge neutralization) and a second precursor that satisfies the formula AHF _{2 (A is an alkali metal).} It relates to a manufacturing method.

Description

Selective Fabrication Method of Metal Fluoride-based Phosphors

The present invention relates to a method for selectively manufacturing a metal fluoride-based phosphor, and more particularly, to a method for selectively producing metal fluoride-based phosphors having different compositions from each other using the same raw material, free from hydrofluoric acid.

Metal fluoride-based phosphors are widely applied to light emitting devices such as light emitting diodes, laser diodes, surface light emitting diodes, inorganic-electroluminescent devices, and organic-electroluminescent devices.

As a general method for manufacturing a metal fluoride-based phosphor, a solid-phase method and a liquid-phase method may be used. The solid-state method is a method of manufacturing a phosphor by weighing and mixing each precursor of a metal fluoride-based phosphor in a desired ratio, and then performing a solid-phase reaction in a high-temperature electric furnace. The use of the solid-phase method has the advantage of being able to mass-produce phosphors more simply than other manufacturing methods, but there is a high risk of fluoride having an undesired composition by reacting with other elements during the solid-phase reaction. Accordingly, the solid-phase method is convenient in terms of method, but has a disadvantage in that it is not easy to synthesize a fluoride-based phosphor having a desired composition.

On the other hand, the liquid phase method has the advantage that it is possible to prepare a phosphor having a desired composition compared to the solid phase method because the fluoride is converted into a solution state and reacted. In the liquid phase method, the so-called precipitation method, in which precursors are dissolved in a solvent, and then precipitated using the solubility of each solution to synthesize a fluoride phosphor, is the most widely used. However, there are a number of problems to be overcome in order to commercially synthesize a fluoride-based phosphor using a precipitation method. As a typical problem, hydrofluoric acid (HF) is used as a solvent for precipitation when manufacturing a metal fluoride-based phosphor using the precipitation method. and very dangerous In addition, in the case of a phosphor having superior luminescence characteristics such as _{K 3} SiF ₇ :Mn ⁴⁺ , a two-step method in which _{K 2} SiF ₆ :Mn ⁴⁺ is first prepared _{using hydrofluoric acid and then reacted with KF or KHF 2} It is usually produced by However, for mass production, a metal fluoride-based phosphor of a desired composition is manufactured in a single process (one-step, one-pot) using not only HF-free, but also cheap, easy-to-supply and easy-to-handle raw materials. Process development that can do this should be done.

Republic of Korea Patent No. 10-1854114

An object of the present invention is to provide a method for selectively producing metal fluoride-based phosphors having different compositions from the same raw material, in which the entire process is free from hydrofluoric acid, from raw materials to the stage of obtaining a desired fluoride-based fluorescent agent.

Another object of the present invention is to provide a method capable of mass-producing a metal fluoride-based phosphor in a single process using a cheap, easy-to-supply and easy-to-handle raw material.

In the manufacturing method according to the present invention, a metal fluoride-based phosphor is prepared by heating a reaction solution containing a raw material and an organic solvent including a first precursor satisfying the following Chemical Formula 1 and a second precursor satisfying the following Chemical Formula 2.

(Formula 1)

MOx

In Formula 1, M is a host element selected from the group of metalloids, post-transition metals and transition metals, and x is a real number satisfying charge neutralization according to the oxidation number of the host element M.

(Formula 2)

AHF ₂

In Formula 2, A is an alkali metal.

In the manufacturing method according to an embodiment of the present invention, the metal fluoride-based phosphor may satisfy Formula 3 below.

(Formula 3)

A _m MF _n :Mn ⁴⁺

In Formula 3, A is the same as A in Formula 2, M is the same as M in Formula 1, m is a real number of 2-3, and n is a real number of 6-7.

In the manufacturing method according to an embodiment of the present invention, the composition of the manufactured metal fluoride-based phosphor may be controlled by controlling the type of the organic solvent.

In the manufacturing method according to an embodiment of the present invention, the organic solvent is a C4 to C30 aliphatic amine, and the metal fluoride-based phosphor may satisfy the following Chemical Formula 3-1.

(Formula 3-1)

A ₃ MF ₇ :Mn ⁴⁺

In Formula 3-1, A is the same as A in Formula 2, and M is the same as M in Formula 1.

In the preparation method according to an embodiment of the present invention, the organic solvent may be a C10 to C30 aliphatic amine.

In the manufacturing method according to an embodiment of the present invention, the aliphatic amine may have a boiling point (1 atm) of 250° C. or higher.

In the preparation method according to an embodiment of the present invention, the aliphatic amine may be trioctylamine, dioctylamine, oleylamine, diethanolamine, triethanolamine, dodecylamine, or a mixture thereof.

In the manufacturing method according to an embodiment of the present invention, the organic solvent is a C4 to C30 fatty acid, and the metal fluoride-based phosphor may satisfy the following Chemical Formula 3-2.

(Formula 3-2)

A ₂ MF ₆ :Mn ⁴⁺

In Formula 3-2, A is the same as A in Formula 2, and M is the same as M in Formula 1.

In the manufacturing method according to an embodiment of the present invention, the fatty acid may have a boiling point (boiling point, 1 atm) of 250° C. or higher.

In the manufacturing method according to an embodiment of the present invention, the fatty acid is pelargonic acid, capric acid, undecylic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, paulinic acid, oleic acid, elaidic acid, erucic acid, or mixtures thereof.

In the manufacturing method according to an embodiment of the present invention, the raw material may further include a third precursor, which is a manganese precursor.

The manufacturing method according to an embodiment of the present invention may be a hydrofluoric acid-free (HF-free) method that does not use hydrofluoric acid.

In the manufacturing method according to an embodiment of the present invention, the heating temperature may be 250 to 500 ℃.

In the manufacturing method according to an embodiment of the present invention, the molar ratio of the first precursor to the second precursor contained in the raw material may be 1: 2 to 10.

The manufacturing method according to an embodiment of the present invention may further include; washing and drying the metal fluoride-based phosphor prepared from the reaction solution.

In the manufacturing method according to an embodiment of the present invention, the molar ratio of the first precursor contained in the reaction solution to the organic solvent may be 1:1 to 100.

The present invention includes a metal fluoride-based phosphor manufactured by the above-described manufacturing method.

The method for manufacturing a metal fluoride-based phosphor according to the present invention has the advantage of being able to manufacture a fluoride-based phosphor without using a strong acid including hydrofluoric acid. Accordingly, the working environment is greatly improved, the corrosion phenomenon of the equipment is significantly lowered, the workability and safety are greatly improved, and there is an advantage of easy construction and management of the process.

In addition, the method for manufacturing a metal fluoride-based phosphor according to the present invention has an advantage in that metal fluoride-based phosphors having different compositions can be selectively manufactured using the same raw material, but only through simple control of controlling an organic solvent.

In addition, in the method for manufacturing a metal fluoride-based phosphor according to the present invention, it is easy to supply and supply raw materials and lower the manufacturing cost of the phosphor by using an oxide as a raw material. As it can be manufactured, there is an advantage of excellent commerciality.

1 is a view showing an X-ray diffraction pattern of the matrix prepared in Preparation Example 1.
Figure 2 is a view showing the X-ray diffraction pattern of the parent prepared in Preparation Example 2.
3 is a diagram illustrating an X-ray diffraction pattern of the phosphor prepared in Preparation Example 3. Referring to FIG.
4 is a view showing an X-ray diffraction pattern of the parent prepared in Preparation Example 4.
5 is a scanning electron microscope photograph of the parent body prepared in Preparation Example 1.
6 is a scanning electron microscope photograph of the phosphor prepared in Preparation Example 5.
7 is a view showing an emission spectrum of the phosphor prepared in Preparation Example 3. Referring to FIG.
8 is a view showing an X-ray diffraction pattern of the parent prepared in Preparation Example 8.
9 is a view showing an X-ray diffraction pattern of the parent prepared in Preparation Example 9.

Hereinafter, a method of manufacturing a metal fluoride-based phosphor of the present invention will be described in detail with reference to the accompanying drawings. The drawings introduced below are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, if there is no other definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the technical field to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted. Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise. In the present specification and the appended claims, the units used without special mention are based on weight, and for example, the unit of % or ratio means weight % or weight ratio.

In the method for manufacturing a metal fluoride-based phosphor according to the present invention, a metal fluoride-based phosphor is prepared through a solution process using a raw material containing an oxide of an element belonging to a phosphor host and a fluoride of an alkali metal and a liquid containing an organic solvent.

In detail, in the manufacturing method according to the present invention, a metal fluoride-based phosphor is prepared by heating a reaction solution containing a raw material and an organic solvent including a first precursor satisfying the following Chemical Formula 1 and a second precursor satisfying the following Chemical Formula 2 do.

(Formula 1)

MOx

In Formula 1, M is a host element selected from the group of metalloids, post-transition metals and transition metals, and x is a real number satisfying charge neutralization according to the oxidation number of the host element M.

(Formula 2)

AHF ₂

In Formula 2, A is an alkali metal.

In this case, the first precursor according to Chemical Formula 1 may be crystalline, amorphous, or a mixed phase of crystalline and amorphous, and may be crystalline in terms of a more rapid and stable reaction.

As described above, the production method according to the present invention does not use a strong acid including hydrofluoric acid, but only an oxide of a host element (first precursor), a fluorine-based compound of an alkali metal (second precursor), and a reaction containing an organic solvent There is an advantage in that a metal fluoride-based red phosphor that is excited by ultraviolet or blue light and emits red light can be manufactured through a simple and single process of heating the liquid.

In Formula 1, M, which is a host element, may be Si, Ge, Ti, Zr, Al, Ga, In, Sc, Y La, Nb, Ta, Bi, Gd, or a combination thereof. M may be Si, Ge, Ti, or a combination thereof in terms of excellent light emitting characteristics of being excited and emitting high-purity red, but is not necessarily limited thereto.

In Formula 1, x may be a real number satisfying charge neutralization according to the oxidation number of M, specifically, a real number corresponding to (oxidation number of M)/2. For instance, x may be a real number from 1 to 3, and according to an advantageous example, x may be 1 or 2 when M is Si, Ge, Ti or a combination thereof.

In Chemical Formula 2, A, which is an alkali metal, may be Li, Na, K, Rb, Cs, or a combination thereof. In terms of excellent light emitting properties, A may be K, Rb, or a combination thereof, but is not necessarily limited thereto. .

The raw material may include a first precursor, which is an oxide of a host element, and a second precursor, which is an alkali metal fluoride-based compound. In addition to the first precursor and the second precursor, a third precursor that is a manganese precursor may be further included. The manganese precursor may be a manganese fluoride-based compound. The manganese fluoride-based compound may _{be an alkali metal-manganese fluoride such as A 2} MnF ₆ (A is the same as defined in Formula 2), but is not necessarily limited thereto.

As described above, only by controlling the type of precursor contained in the raw material, without using hydrofluoric acid, formula 3' A _m MF _n (A is the same as A in formula 2, M is the formula 3' A m MF n through a one-pot solution process _{Formula 3 A m} MF _n :Mn ⁴⁺ doped with manganese as the parent (host) or activator of 1, m is the same as M of 1, m is a real number of 2 to 3, and n is a real number of 6 to 7 (A is a real number of 6 to 7) 2, M is the same as M in Formula 1, m is a real number of 2 to 3, and n is a real number of 6 to 7). In Formula 3, Mn ^{4+ as an} activator may be 0.01 to 0.08 moles, specifically, 0.03 to 0.05 moles, with respect to 1 mole _{of A m} MF _{n as a} parent (host), but is not necessarily limited thereto. no.

Furthermore, when hydrofluoric acid is excluded and an oxide of a host element (first precursor) and a fluorine-based compound of an alkali metal (second precursor) are used as raw materials, the composition of the metal fluoride-based phosphor produced by controlling the type of the organic solvent This can be adjusted. That is, when hydrofluoric acid is excluded and an oxide of a host element (first precursor) and a fluorine-based compound of an alkali metal (second precursor) are used as raw materials, a metal fluoride-based compound having a different composition from each other by controlling the type of organic solvent in the reaction solution Phosphors may optionally be prepared.

Specifically, by controlling the type of organic solvent contained in the reaction solution, in Formula 3' or Formula 3, a metal fluoride-based phosphor having a composition of 216 in which m and n are 2 and 6 or a composition 317 in which m and n are 3 and 7 of metal fluoride-based phosphors can be selectively prepared.

In an embodiment, the organic solvent of the reaction solution is a C4 to C30 aliphatic amine, and a metal fluoride-based phosphor satisfying the following Chemical Formula 3-1 or a metal fluoride-based matrix satisfying 3-1′ may be prepared.

(Formula 3-1)

A ₃ MF ₇ :Mn ⁴⁺

(Formula 3-1')

A ₃ MF ₇

In Formula 3-1 or 3-1', A is the same as A in Formula 2, and M is the same as M in Formula 1.

Accordingly, in the manufacturing method according to an aspect of the present invention, a raw material containing a first precursor satisfying Formula 1 and a second precursor satisfying Formula 2 and a reaction solution containing C4 to C30 aliphatic amine as an organic solvent are heated to A metal fluoride-based phosphor having the host A ₃ MF _{7 may be prepared.}

The C4 to C30 aliphatic amine may be a C4 to C30 saturated aliphatic amine, a C4 to C30 unsaturated aliphatic amine, or a mixture thereof. In terms of preventing the production of substances of different compositions), the organic solvent may be a C10 to C30 aliphatic amine.

More preferably, the organic solvent may be an aliphatic amine having a boiling point (1 atm) of 250° C. or higher. When an aliphatic amine having a boiling point of 250°C or higher is used, AHF ₂ (Formula 2, A is an alkali metal), which is a fluoride-based precursor of alkali metal, promotes a decomposition reaction in which AF and HF are decomposed to supply a large amount of AF and high purity A metal fluoride-based phosphor having a composition of 317 can be stably prepared.

As an example of the aliphatic amine having a boiling point of 250° C. or higher, the aliphatic amine may include trioctylamine, dioctylamine, oleylamine, diethanolamine, triethanolamine, dodecylamine, or a mixture thereof, but is not limited thereto. it is not

In an embodiment, the organic solvent of the reaction solution is a C4 to C30 fatty acid, and a metal fluoride-based phosphor satisfying the following Chemical Formula 3-2 or a metal fluoride-based matrix satisfying 3-2′ may be prepared.

(Formula 3-2)

A ₂ MF ₆ :Mn ⁴⁺

(Formula 3-2')

A ₂ MF ₆

In Formula 3-2 or 3-2', A is the same as A in Formula 2, and M is the same as M in Formula 1.

Accordingly, in the manufacturing method according to another embodiment of the present invention, a raw material containing a first precursor satisfying Formula 1 and a second precursor satisfying Formula 2 and a reaction solution containing C4 to C30 fatty acids with an organic solvent are heated to A metal fluoride-based phosphor having a host of A ₂ MF _{6 may be prepared.}

C4 to C30 fatty acid may be C4 to C30 saturated fatty acid, C4 to C30 unsaturated fatty acid, or a mixture thereof, and maintains a stable liquid phase even when heating the reaction solution for synthesis, and maintains a stable liquid phase even when heating the reaction solution for synthesis. In terms of preventing the production of), the fatty acid may be a C10 to C30 fatty acid.

More preferably, the organic solvent may be a fatty acid having a boiling point (1 atm) of 250° C. or higher. When a fatty acid having a boiling point of 250 ° C or higher is used _{, the decomposition reaction in which AHF 2} (Formula 2, A is an alkali metal), which is a fluoride-based precursor of an alkali metal, is decomposed into AF and HF, is suppressed, unlike aliphatic amines, and By the reaction of the carboxyl group with the second precursor, a side reaction to form a COO-A+ salt is promoted, and the supply of AF is suppressed, so that a metal fluoride-based phosphor having a high purity 216 composition can be stably prepared.

As an example of a fatty acid having a boiling point of 250° C. or higher, the fatty acid is pelargonic acid, capric acid, undecylic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, ste aridonic acid, eicosapentaenoic acid, docosahexaenoic acid, paulinic acid, oleic acid, elaidic acid, erucic acid, or mixtures thereof, but is not limited thereto.

Each of the first precursor and the second precursor may be in the form of a powder. The sizes of the first precursor, the second precursor, and the third precursor, if necessary, may be any size that can be easily supplied and supplied. In an embodiment, the first precursor, the second precursor, and, if necessary, the third precursor may each independently have a size in the order of several tens of nanometers to several tens of micrometers, but the present invention provides for the spherical size of the precursor. is not limited by

When the reaction solution is heated, the temperature may be 250° C. or higher. According to one embodiment of the present invention, by heating a reaction solution containing a raw material and an organic solvent that is an aliphatic amine to a temperature of 250° C. or higher, it substantially does not contain unreacted residues or unwanted composition abnormalities and has high crystallinity. A metal fluoride-based phosphor having a composition of 317 may be prepared. In addition, according to another embodiment of the present invention, by heating the reaction solution containing the raw material and the organic solvent that is a fatty acid to a temperature of 250 ° C. or higher, substantially high crystallinity without containing unreacted residues or unwanted compositional abnormalities A metal fluoride-based phosphor having a composition of 216 having

The heating may be performed at 250° C. or higher, specifically 250 to 500° C., more specifically 250 to 400° C., and still more specifically 250 to 300° C. In particular, a temperature of 250° C. or higher is preferable because a faster reaction may occur because it is a temperature higher than the melting point of the second precursor satisfying Chemical Formula 2. The heating time (reaction time) is sufficient as long as it is sufficient to produce a desired phosphor from the input raw material in consideration of the synthesis capacity. As an example, the heating time may be 0.5 to 24 hours, but the present invention is not limited by the heating time (reaction time) of the reaction solution. In addition, the reaction may be carried out in air, but is not necessarily limited thereto.

In one embodiment, the molar ratio of the first precursor to the second precursor contained in the raw material may be 1: 2 to 10, specifically 1: 3 to 9. The molar ratio of the first precursor, which is an oxide of the host element, to the second precursor, which is a fluoride-based compound of an alkali metal, may be 1: 2 to 10, specifically 1: 3 to 9, and by controlling the organic solvent in this range, the desired The phosphor of the composition can be selectively and stably prepared. In this case, the molar ratio of the first precursor contained in the reaction solution to the organic solvent may be 1:1 to 100, specifically 1:1 to 50, and more specifically 1:4 to 20 level, but is not necessarily limited thereto.

When the raw material further contains a third precursor, which is a manganese precursor, the raw material is a real number in which 0.01≤z≤0.08, specifically 0.03≤z≤0.05, based on the formula _{of A m} MF _n :Mn ⁴⁺ _{z in which Mn doped into the parent material is} It may contain a third precursor to satisfy the phosphorus real number, but is not necessarily limited thereto.

The manufacturing method according to an embodiment may further include washing and drying the metal fluoride-based phosphor prepared by heating the reaction solution. Washing is performed with ethanol, acetone, 1-propanol, isopropyl alcohol, acetic acid, toluene, methanol, acetic acid, acetonitrile, benzene, butanol, butyl alcohol, chlorobenzene, chloroform, cyclohexane, 1,2-dichloroethane, diethyl ether. , 1,2-dimethoxyethane, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, 1,2-dioxane, ethyl acetate, heptane, ethylene dichloride, methylene chloride, nitromethane, pentane, tetrahydrofuran, Triethylamine, pyridine, trifluoroacetic acid, xylene, etc. may be carried out using a conventional organic solvent, but is not limited thereto. Drying may be performed at 80 to 150° C., but is not limited thereto.

The present invention includes a phosphor manufactured by the above-described manufacturing method. Specifically, the present invention is prepared by the above-described manufacturing method, is excited by ultraviolet to blue light, specifically 365 to 480 nm excitation wavelength, and emits red light of 610 to 670 nm wavelength A _m MF _n :Mn ⁴⁺ (A is an alkali metal, M is a host element selected from the group of metalloids, post-transition metals and transition metals, m is a real number of 2 to 3, and n is a real number of 6 to 7). In one embodiment, the phosphor prepared by the above-described manufacturing method may be in the form of particles having an average size of 100 nm to 100 μm, specifically, 0.5 to 10 μm.

(Production Examples 1 to 9)

Raw materials and organic solvents were weighed and mixed according to Table 1 below, and heated at 250° C. in the air for 5 hours (Preparation Examples 1 to 7), or heated at 250° C. for 4 hours (Preparation Examples 8 and 9). After heating, the prepared phosphor was recovered, washed several times with non-aqueous ethanol and acetone, and dried in an oven at 110° C. for 3 hours. At this time, the particle size of each precursor used as a raw material in Preparation Example was about 10 to 20 μm, and the first precursor was a crystalline phase.

(Table 1)

1 is an X-ray diffraction pattern of the parent prepared in Preparation Example 1, FIG. 2 is an X-ray diffraction pattern of the parent prepared in Preparation Example 2, FIG. 3 is an X-ray of the phosphor prepared in Preparation Example 3 It is a diagram showing the measurement of the diffraction pattern.

_{The K 3} SiF ₇ reference diffraction pattern (JCPDS #01-075-0694) and the reference diffraction pattern of the _{raw material KHF 2} (JCPDS #00-048-1666) together with the diffraction pattern of the phosphor or the matrix prepared in FIGS. 1 to 3 are shown together. 1 to 3, through a simple process of heating a reaction solution containing an organic solvent that is an oxide of a host element, an alkali fluoride-based compound, and an aliphatic amine, without using hydrofluoric acid, K in a one-pot process ₃ SiF or ₇ matrix K ₃ SiF of _7: it can be seen that the phosphor is prepared in the Mn ^4+, it can be seen that the phosphor composition is based on a derivative of the 317 selectively produce no unwanted unless (different phase).

4 is a view showing the measurement of the X-ray diffraction pattern of the parent prepared in Preparation Example 4. _{The reference diffraction pattern of the K 2} SiF ₆ reference diffraction pattern (#01-075-0694) and the raw material KHF ₂ (JCPDS #00-048-1666) are shown together with the diffraction pattern of the parent prepared in FIG. 4 . In this case, it was confirmed that in Preparation Examples 5 and 6, a parent or phosphor having an X-ray diffraction pattern substantially the same as in Preparation Example 4 was prepared. As can be seen from the X-ray diffraction analysis results, using the same raw materials as in Preparation Examples 1 to 3, but through a simple process of heating a reaction solution containing an organic solvent that is a fatty acid, without using hydrofluoric acid, one-pot As a process, the matrix _{of K 2} SiF ₆ It can be seen that a phosphor of K ₂ SiF ₆ :Mn ⁴⁺ is prepared, and a phosphor based on a matrix having a composition of 216 is selectively prepared without an unwanted different phase.

5 is a scanning electron microscope photograph of the parent body prepared in Preparation Example 1, and FIG. 6 is a scanning electron microscope photograph of the phosphor prepared in Preparation Example 5.

As can be seen from FIGS. 5 to 6 , it can be seen that the phosphor is manufactured in the form of aggregated particles having a size of several tens of micrometers as a result of the agglomeration of the fine particles.

7 is a diagram illustrating measurement of emission spectrum of the phosphor prepared in Preparation Example 3 by irradiating excitation light (450 nm wavelength). As can be seen from FIG. 7 , it can be seen that red light having an emission center wavelength of 610 to 670 nm is emitted, and a high-quality phosphor is manufactured.

8 and 9 are views showing the X-ray diffraction patterns of the parent prepared in Preparation Examples 8 and 9. Through Preparation Examples 1 to 9, only aliphatic amines or fatty acids having a boiling point of 250° C. or higher are organic By using as a solvent, it can be confirmed that a fluoride-based phosphor having a high-purity matrix of 317 composition or a fluoride-based phosphor having a matrix of high-purity 216 composition is selectively prepared.

As described above, the present invention has been described with specific matters and limited examples and drawings, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is not limited to the above embodiments. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (17)

A method of manufacturing a metal fluoride-based red phosphor by heating a reaction solution containing a raw material and an organic solvent including a first precursor satisfying Formula 1 and a second precursor satisfying Formula 2 below.
(Formula 1)
MOx
(In Formula 1, M is a host element that is Si, Ge, Ti, or a combination thereof, and x is a real number that satisfies charge neutralization according to the oxidation number of the host element M)
(Formula 2)
AHF ₂
(In Formula 2, A is an alkali metal K, Rb, or a combination thereof) The method of claim 1,
The metal fluoride-based red phosphor satisfies Formula 3 below.
(Formula 3)
A _m MF _n :Mn ⁴⁺
(In Formula 3, A is the same as A in Formula 2, M is the same as M in Formula 1, m is a real number from 2 to 3, n is a real number from 6 to 7) The method of claim 1,
A method of controlling the composition of the prepared metal fluoride-based red phosphor by controlling the type of the organic solvent to be C4 to C30 aliphatic amine or C4 to C30 fatty acid. The method of claim 1,
The organic solvent is a C4 to C30 aliphatic amine, and the metal fluoride-based red phosphor satisfies the following Chemical Formula 3-1.
(Formula 3-1)
A ₃ MF ₇ :Mn ⁴⁺
(In Formula 3-1, A is the same as A in Formula 2, and M is the same as M in Formula 1) 5. The method of claim 4,
wherein the organic solvent is a C10 to C30 aliphatic amine. 5. The method of claim 4,
The aliphatic amine has a boiling point (boiling point, 1 atm) of 250° C. or higher. 7. The method of claim 6,
wherein the aliphatic amine is trioctylamine, dioctylamine, oleylamine, diethanolamine, triethanolamine, dodecylamine, or a mixture thereof. The method of claim 1,
The organic solvent is a C4 to C30 fatty acid, and the metal fluoride-based red phosphor satisfies the following Chemical Formula 3-2.
(Formula 3-2)
A ₂ MF ₆ :Mn ⁴⁺
(In Formula 3-2, A is the same as A in Formula 2, and M is the same as M in Formula 1) 9. The method of claim 8,
The fatty acid has a boiling point (boiling point, 1 atm) of 250 °C or more. 10. The method of claim 9,
The fatty acids are pelargonic acid, capric acid, undecylic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, paulinic acid, oleic acid, elaidic acid, erucic acid, or a mixture thereof. The method of claim 1,
The raw material further comprises a third precursor, which is a manganese precursor. The method of claim 1,
The method does not use hydrofluoric acid. The method of claim 1,
The heating temperature is 250 to 500 ℃ method. The method of claim 1,
The molar ratio of the first precursor to the second precursor contained in the raw material is 1: 2 to 10. The method of claim 1,
The method further comprising; washing and drying the metal fluoride-based red phosphor prepared from the reaction solution. The method of claim 1,
The molar ratio of the first precursor contained in the reaction solution to the organic solvent is 1:1 to 100. delete

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