KR102592398B1 - Composite fluorescent structure and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a composite fluorescent structure and a method of manufacturing the same, and more specifically, to a composite fluorescent structure that can protect the phosphor from external factors such as moisture while maintaining the excellent luminous performance of the phosphor and a method of manufacturing the same.
The composite fluorescent structure of the present invention includes a core containing a manganese-doped fluoride-based phosphor; a first shell coated with silica on the core surface; and a second shell coated with a metal oxide on the surface of the first shell.

Description

Composite fluorescent structure and manufacturing method thereof}

The present invention relates to a composite fluorescent structure and a method of manufacturing the same, and more specifically, to a composite fluorescent structure that can protect the phosphor from external factors such as moisture, while maintaining the excellent luminous performance of the phosphor and a method of manufacturing the same.

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.

Common methods for producing metal fluoride-based phosphors include solid-phase method and liquid-phase method. The solid-state method is a method of producing phosphors 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 most widely used liquid method is the so-called precipitation method, which synthesizes fluoride phosphors by dissolving a fluoride precursor in a solvent and then precipitating it using the solubility of each solution.

Like the Korean Patent No. 10-1854114, “Metal fluoride red phosphor and light-emitting device using the same,” and the Korean Patent No. 10-2182241, “Method for manufacturing metal fluoride-based phosphor,” previously applied by the applicant, light is emitted in the red region. Metal fluoride red phosphors with a peak are being developed, but when in contact with moisture, MnF ₆ is easily hydrolyzed into MnO ₂ or MnOH ₂ , the phosphor is discolored, and fluorescence performance is deteriorated.

As such, as the fluorescence performance is easily degraded by moisture, there is a problem that it is practically impossible to use it industrially.

(Patent Document 1): Republic of Korea Patent No. 10-1854114 (Patent Document 2): Republic of Korea Patent No. 10-2182241

The purpose of the present invention is to provide a composite fluorescent structure that can protect the phosphor from external factors such as moisture, while maintaining the excellent luminous performance of the phosphor.

The composite fluorescent structure according to the present invention includes a core containing a manganese-doped fluoride-based phosphor; a first shell coated with silica on the core surface; and a second shell coated with a metal oxide on the surface of the first shell.

In the composite fluorescent structure according to an embodiment of the present invention, the manganese-doped fluoride-based phosphor may be a red phosphor.

In the composite fluorescent structure according to an embodiment of the present invention, the manganese-doped fluoride-based phosphor may have the composition of Formula 1 below.

[Formula 1]

A ₃ MF ₇ : Mn _x ⁴⁺ or A ₂ MF ₆ : Mn _x ⁴⁺

(The A is Li, Na, K, Rb, Cs, NH ₄ or a combination thereof, M is an element selected from Si, Ge, Ti or a combination thereof, and x is 0<x≤0.15)

In the composite fluorescent structure according to an embodiment of the present invention, the average diameter of the core may be 1 to 50㎛.

In the composite fluorescent structure according to an embodiment of the present invention, the metal of the metal oxide is aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), tin (Sn), silicon (Si), It may be any one selected from hafnium (Hf), boron (B), potassium (K), magnesium (Mg), and indium (In).

In the composite fluorescent structure according to an embodiment of the present invention, the thickness of the second shell may be 1 to 5 nm.

In the composite fluorescent structure according to an embodiment of the present invention, the maximum emission center wavelength may be 620 to 650 nm.

The method for manufacturing a composite fluorescent structure according to the present invention includes (S1) preparing a core containing a manganese-doped phosphor; (S2) coating the core with silica to form a first cell on the core; and (S3) coating a metal oxide on the core coated with the first cell to form a second cell on the first cell.

In the method for manufacturing a composite fluorescent structure according to an embodiment of the present invention, the (S2) step includes (S2-1) adding the core and the amine-based catalyst to alcohol and stirring to obtain a mixed solution, (S2- 2) adding distilled water and a silica precursor to the mixed solution and stirring to obtain a core coated with the first cell, and (S2-3) washing the core coated with the first cell and drying it. It can be included.

In the method of manufacturing a composite fluorescent structure according to an embodiment of the present invention, the silica precursor is tetramethyl orthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropyl orthosilicate (TPOS), tetrabutyl orthosilicate (TBOS) ), methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy silane, vinylmethyldimethoxysilane, butyltri Methoxysilane, diphenylethoxyvinylsilane, methyltriisopropoxysilane, methyltriacetoxysilane, tetraphenoxysilane, tetrapropoxysilane, vinyltriisopropoxysilane, 3-glycidoxypropyl trimethoxy Silane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethylmethoxysilane, 3-glycidoxypropylmethylethoxysilane and beta-(3,4-epoxycyclohexyl)ethyltrimethoxy It may be any one or two or more selected from the group consisting of silanes.

In the method of manufacturing a composite fluorescent structure according to an embodiment of the present invention, in step (S2-2), the weight ratio of the core to the silica precursor may be 1:0.02 to 0.05.

In the method of manufacturing a composite fluorescent structure according to an embodiment of the present invention, the step (S3) is performed by alternately exposing the core coated with the first cell to a gaseous metal supply source and a gaseous oxygen supply source to form a second cell. can be formed.

In the method of manufacturing a composite fluorescent structure according to an embodiment of the present invention, the metal supply source is aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), tin (Sn), and silicon (Si). , hafnium (Hf), boron (B), potassium (K), magnesium (Mg), and indium (In), and the oxygen source is H ₂ O or O ₂ It can be.

In the composite optical structure according to the present invention, a first cell containing silica and a second cell containing metal oxide are sequentially formed on the phosphor to prevent the phosphor from being hydrolyzed by exposure to moisture and at the same time provide excellent fluorescence performance. It can be maintained.

The method for manufacturing a composite fluorescent structure according to the present invention is advantageous for mass production and has excellent industrial feasibility as it can manufacture a composite fluorescent structure from a phosphor through the sol-gel method and atomic layer deposition (ALD). There is an advantage.

1 is a diagram showing the results of EDS (Energy Dispersive X-Ray Spectroscopy) mapping of a composite fluorescent structure according to an embodiment of the present invention;
Figure 2 is a diagram illustrating the emission spectra of composite fluorescent structures according to Examples and Comparative Examples of the present invention before and after moisture and heat exposure;
Figure 3 is a diagram showing the results of a thermal stability test of a composite fluorescent structure according to examples and comparisons of the present invention.

Unless otherwise defined, the technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art to which this invention pertains, and the gist of the present invention is summarized in the following description and accompanying drawings. Descriptions of known functions and configurations that may unnecessarily obscure are omitted.

Additionally, as used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly dictates otherwise.

In addition, units used without special mention in this specification are based on weight, and as an example, the unit of % or ratio means weight % or weight ratio, and weight % refers to the amount of any one component of the entire composition unless otherwise defined. It refers to the weight percent occupied in the composition.

In addition, the numerical range used in this specification includes the lower limit and upper limit and all values within the range, increments logically derived from the shape and width of the defined range, all double-defined values, and the upper limit of the numerical range defined in different forms. and all possible combinations of the lower bounds. Unless otherwise specified in the specification of the present invention, values outside the numerical range that may occur due to experimental error or rounding of values are also included in the defined numerical range.

The term 'comprise' in this specification is an open description with the same meaning as expressions such as 'comprising', 'contains', 'has' or 'characterized by', and includes elements that are not additionally listed, Does not exclude materials or processes.

Conventionally developed manganese-doped fluoride-based phosphors with an emission peak in the red region are easily hydrolyzed when in contact with moisture, and have the disadvantage of discoloring the phosphor and deteriorating fluorescence performance.

The composite fluorescent structure according to the present invention includes a core containing a manganese-doped fluoride-based phosphor; a first shell coated with silica on the core surface; and a second shell coated with a metal oxide on the surface of the first shell, thereby preventing the core (phosphor) from being hydrolyzed by exposure to moisture and maintaining excellent fluorescence performance.

Specifically, the core includes a manganese-doped fluoride-based phosphor. Preferably, the manganese-doped fluoride-based phosphor may be a red phosphor having an emission peak in the red region.

In one embodiment, the manganese-doped fluoride-based phosphor may have the composition of Formula 1 below.

[Formula 1]

A ₃ MF ₇ : Mn _x ⁴⁺ or A ₂ MF ₆ : Mn _x ⁴⁺

Here, A is Li, Na, K, Rb, Cs, NH ₄ or a combination thereof, M is an element selected from Si, Ge, Ti or a combination thereof, and x is 0<x≤0.15.

The manganese-doped fluoride-based phosphor having the composition of Formula 1 may have a tetragonal crystal structure. In one embodiment, in the composition of Formula 1, A may be potassium (K), and M may be silicon (Si) or titanium (Ti). Such a manganese-doped fluoride-based phosphor may have an emission center wavelength in the range of 610 to 670 nm and may have high brightness emission performance.

The shape and size of the core are not limited as long as it maintains an emission peak in the red region, but in one embodiment, it may have a faceted shape. Specifically, the faceted shape may be a polyhedron including a hexahedron, As a non-limiting example, it may have the shape of a rectangular parallelepiped or cube, but is not limited thereto. The average diameter of the core may be 1 to 50㎛, specifically 10 to 40㎛.

The first shell and the second shell are formed on the surface of the core described above, and are intended to protect the core from external factors such as moisture without reducing the fluorescence performance of the core. Specifically, it may be located in the order of core-first shell-second shell.

The first shell is formed by coating silica on the surface of the core, and may be a silica layer formed on the core. The first shell is formed between the core and the second shell, and together with the second shell, it protects the core from external factors such as moisture and serves to strengthen the bond between the second shell and the core.

The second shell is formed by coating a metal oxide on the surface of the core where the first shell is formed, and may be a metal oxide layer formed on the first shell.

The metals of the metal oxide that makes up the second shell are aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), tin (Sn), silicon (Si), hafnium (Hf), boron (B), It may be any one selected from potassium (K), magnesium (Mg), and indium (In). In one specific example, the second shell may be made of aluminum oxide.

The thickness formed by the first shell and the second shell is not limited as long as it does not deteriorate the fluorescence performance of the core, but in detail, the thickness of the first shell is 10㎚ to 10㎛, more specifically, 500㎚ to 5㎛. The thickness of the second shell may be 1 nm to 5 nm, specifically, 2 to 4 nm. In the above range, the fluorescence performance of the core is maintained and thermal stability can be high.

The composite fluorescent structure including the structure of the core-first shell-second cell described above has a maximum emission center wavelength of 620 to 650 nm, even though the first and second shells are coated to protect the phosphor. , it can have an excellent red emission spectrum from 630 nm to 640 nm. In other words, such a composite fluorescent structure can prevent fluorescence performance from deteriorating when exposed to moisture and at the same time maintain excellent fluorescence performance.

The method for manufacturing a composite fluorescent structure according to the present invention includes (S1) preparing a core containing a manganese-doped phosphor; (S2) coating the core with silica to form a first cell on the core; and (S3) coating a metal oxide on the core coated with the first cell to form a second cell on the first cell. This manufacturing method can manufacture the above-described composite fluorescent structure, and steps (S1), (S2), and (S3) are preferably performed sequentially. If step (S3) is preceded by step (S2), there is a problem in that the luminescence characteristics of the phosphor disappear.

Specifically, step (S1) is a step of preparing a core containing a manganese-doped phosphor, and is performed through the method disclosed in Korean Patent Publication Nos. 10-1854114 and 10-2182241 previously filed by the present applicant. You can. As a specific example, weighing raw materials consisting of A precursor, M precursor, and manganese (Mn) precursor and dissolving them in acid; Obtaining a solid by distilling the acid solution in which the raw material is dissolved under reduced pressure; Drying the obtained solid in an oven at 80 to 150°C; and heat treating the dried solid at 200 to 1,000° C. in an atmosphere of hydrogen gas, nitrogen gas, or a mixture thereof, where A is Li, Na, K, Rb, Cs, NH ₄ or these. It may be a combination of, and M may be selected from Si, Ge, Ti, or a combination thereof.

The (S2) step is a step for forming a first cell made of silica on the core. There is no limitation as long as the method can coat silica on the core, but preferably, the silica can be coated without damaging the phosphor. Silica can be coated through the sol-gel method.

In one embodiment, step (S2) includes (S2-1) adding the core and amine-based catalyst to alcohol and stirring to obtain a mixed solution, (S2-2) adding distilled water and silica precursor to the mixed solution. and stirring to obtain a core coated with the first cell, and (S2-3) washing the core coated with the first cell and drying it. In this (S2) step, after the core and amine-based catalyst are evenly dispersed in the (S2-1) step, the silica precursor is added and stirred, resulting in hydrolysis and condensation reactions with the silica precursor uniformly over the entire surface of the core. This occurs, and a first shell with silica coated more uniformly on the core can be formed.

Specifically, step (S2-1) is a step of obtaining a mixed solution in which the core and amine-based catalyst are uniformly dispersed. The core and amine-based catalyst prepared in step (S1) are added to alcohol and then stirred. Accordingly, a mixed solution in which the amine-based catalyst is relatively uniformly located across the entire core can be obtained.

In step (S2-1), the alcohol may be at least one selected from the group consisting of methanol, ethanol, isopropyl alcohol, n-butanol, and n-pentanol, but is not limited thereto.

Amine-based catalysts include hydrazine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, piperazine, aminoethylpiperazine, and aminoethylethanol. Amine, spermidine, spermine, tris(2-aminoethyl)amine, bis(aminoethyl)piperazine, bis(3-aminopropyl)amine, N-(2-(1-piperazyl)ethyl)ethylene Diamine, N-(1-naphthyl)ethylenediamine, N-(2-hydroxyethyl)ethylenediamine, N,N-dimethyldipropylenetriamine, 1,3-diaminopropane, 1,4-diaminobutane , 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminoctane, 1,9-diaminononane and 1,10-diaminodecane. It may be any one or two or more selected from the group consisting of.

In step (S2-1), the amount of alcohol is not limited as long as it can disperse the added core and amine-based catalyst. The amine-based catalyst can be adjusted by the amount of silica precursor to be added in step (S2-2), but in order to mix relatively uniformly with the core in the mixed solution, the weight ratio of the core: amine-based catalyst is 1: 0.001 to 0.030, specific It can be 1:0.015~0.025.

In step (S2-1), stirring is not limited as long as the core and amine-based catalyst can be uniformly dispersed in ethanol, but stirred at 100 rpm to 3,000 rpm for 10 minutes to 3 hours at room temperature (4°C to 30°C). It can be done in rpm.

Step (S2-2) is a step in which distilled water and a silica precursor are added to the mixed solution prepared in step (S2-1) and stirred to cause hydrolysis and condensation reactions of the silica precursor on the surface of the core.

In step (S2-2), the silica precursor is tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropylorthosilicate (TPOS), tetrabutylorthosilicate (TBOS), methyltrimethoxysilane, methyl Triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy silane, vinylmethyldimethoxysilane, butyltrimethoxysilane, diphenylethoxyvinyl Silane, methyltriisopropoxysilane, methyltriacetoxysilane, tetraphenoxysilane, tetrapropoxysilane, vinyltriisopropoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyltri Any one selected from the group consisting of ethoxysilane, 3-glycidoxypropylmethylmethoxysilane, 3-glycidoxypropylmethylethoxysilane and beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane or There may be more than one.

In the step (S2-2), distilled water can be added without limitation as long as it is the amount necessary for the reaction of the silica precursor.

In the step (S2-2), when adding the silica precursor to the mixed solution, the weight ratio of core: silica precursor may be 1: 0.02 ~ 0.05, specifically 1: 0.025 ~ 0.045, more specifically 1: 0.03 ~ 0.040. there is. Within the above range, a first cell with an appropriate thickness of 1 to 5 nm can be easily formed on the core.

In step (S2-2), stirring is not limited as long as the conditions allow hydrolysis and condensation reaction of the silica precursor to occur and sufficiently form the first cell on the core, but are carried out at room temperature (4°C to 30°C). It can be performed at 100 rpm to 3,000 rpm for 20 minutes to 6 hours.

Step (S2-3) is a step of washing and drying the core coated with the first cell. Drying is not limited as long as the core coated with the solid first cell can be obtained, but is specifically 30 It can be carried out at a temperature of ℃ to 1,000 ℃ for 10 minutes to 24 hours. As a non-limiting example, drying may be performed in an oven at 30°C to 100°C for 30 minutes to 2 hours, or pre-dried at a temperature of 50°C to 60°C for 1 hour to 3 hours and then dried at 100°C to 100°C. Drying can be performed at a temperature of 150°C for 4 to 20 hours.

Step (S3) is a step for forming a second cell on the first cell of the core on which the first cell is formed, and is not limited as long as it can be coated with a metal oxide, but is preferably atomic layer thin film deposition. Metal oxide can be coated through Deposition·ALD).

Specifically, in step (S3), the core coated with the first cell may be alternately exposed to a vapor phase metal supply source and a vapor phase oxygen supply source to form a second cell. Of course, when the metal supply source and the oxygen supply source are supplied alternately, purging can be performed using an inert gas such as nitrogen or argon.

In step (S3), metal sources include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), tin (Sn), silicon (Si), hafnium (Hf), boron (B), and potassium. It may contain one or more metals selected from the group consisting of (K), magnesium (Mg), and indium (In).

Specifically, the metal source may be a metal halide, such as a metal tetrachloride, a metal oxide, an elemental metal, a metal hydroxide, a metal nitrate, a metal acetate, an organometallic compound, or a combination thereof. Organometallic compounds include diethyl metal, triethyl metal, metallocene (M(C ₅ H ₅ ) ₂ ), or (CH ₃ C ₅ H ₄ )M(CH ₃ ) ₃ , where M is the above-mentioned Suitable metal sources include dichlorosilane (SiH ₂ Cl ₂ ), silicon tetrachloride (SiCl ₄ ), titanium tetrachloride (TiCl ₄ ), trimethylaluminum (TMA), triethylzinc, or titanium isopropoxide (Ti(OiPr). ) ₄ ) includes.

The oxygen source is vapor containing oxygen and may be gaseous H ₂ O or O ₂ .

This manufacturing method can produce the above-described composite fluorescent structure that can maintain excellent fluorescence performance even when exposed to moisture, and can produce composite fluorescence through a relatively simple sol-gel method and atomic layer deposition (ALD). As the structure can be manufactured, it is advantageous for mass production and has excellent industrial feasibility.

The present invention will be described in more detail below based on examples and comparative examples. However, the following Examples and Comparative Examples are only one example to explain the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

(Example 1)

Add 1.5 g of manganese-doped fluorinated phosphor with the formula K ₃ SiF ₇ :Mn ⁴⁺ and 0.03 mL of diethylenetriamine (DETA) to 30 mL of ethanol, stir for 1 hour at 500 rpm at room temperature, and then add 0.2 mL of distilled water and 0.06 mL of Tetraethyl orthosilicate (TEOS). Then, it was stirred at room temperature at 500 rpm for 2 hours.

Afterwards, the product was washed with ethanol until the pH became neutral and then dried in an oven at 80°C for 1 hour to obtain a phosphor coated with a particle-like first cell.

Afterwards, 0.5 g of the phosphor coated with the first cell was placed in the fluidized bed reactor, and 500 sccm of Ar was supplied from the bottom of the container, and Trimethylaluminium (TMA) vapor and H ₂ O vapor were alternately injected at a process pressure of 1 Torr to produce the first cell. A composite fluorescent structure in which a second shell was formed on the shell was obtained. At this time, when TMA vapor and H ₂ O vapor were alternately replaced, purging was performed with Ar.

(Comparative Example 1)

A composite fluorescent structure was manufactured in the same manner as Example 1, except that the second shell was not formed and only the first shell was formed on the manganese-doped fluoride-based phosphor.

(Comparative Example 2)

In Example 1, a composite fluorescent structure was manufactured in the same manner as Example 1, except that the first shell was not formed and only the second shell was formed on the manganese-doped fluoride-based phosphor.

(Comparative Example 3)

In Example 1, a manganese-doped fluoride-based phosphor that did not form a first cell or a second cell was prepared.

division 1st cell
(Silica) 2nd cell
(Metal oxide) Example 1 O O Comparative Example 1 O - Comparative example 2 - O Comparative example 3 - -

Table 1 above indicates whether the first cell and the second cell of Example 1 and Comparative Examples 1 to 3 are included.

Figure 1 is a diagram showing the results of EDS (Energy Dispersive there was.

Figure 2 shows the heat and moisture stability test results of the composite fluorescent structure. Specifically, 1 mL of water was added to 0.1 g of the composite fluorescent structure prepared in Examples and Comparative Examples 1 to 3, and then the emission spectrum of the phosphor was measured before and after storage at 90°C for 3 hours, and PL (Photoluminescence) was measured. ) The amount of reduction was compared.

Referring to Figure 2, in the case of the example of the present invention, when compared to Comparative Example 3, it was confirmed that the maximum emission center wavelength was 635 nm, emitting red light in the same wavelength range, and it was confirmed that there was no PL reduction at all. there was.

Figure 3 is a diagram showing the intensity change according to temperature of the composite fluorescent structure prepared in Example 1 and the phosphor of Comparative Example 3 after exposure to high temperature (25 to 200°C).

Referring to FIG. 3, it was confirmed that in the case of the composite fluorescent structure of the example, there was no substantial decrease in luminous intensity even in a high temperature environment compared to the phosphor in which the first shell and the second shell were not formed.

As described above, the present invention has been described with specific details, limited embodiments, and drawings, but these are provided only to facilitate a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention Anyone skilled in the art can make various modifications and variations from this description.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and the scope of the patent claims described below as well as all modifications that are equivalent or equivalent to the scope of this patent claim shall fall within the scope of the spirit of the present invention. .

Claims (13)

A core containing a manganese-doped fluoride-based phosphor having the composition of Formula 1 below;
a first shell coated with silica on the core surface; and
A composite fluorescent structure comprising; a second shell coated on the surface of the first shell with a metal oxide different from the first shell.
[Formula 1]
A ₃ MF ₇ : Mn _x ⁴⁺ or A ₂ MF ₆ : Mn _x ⁴⁺
(The A is Li, Na, K, Rb, Cs, NH ₄ or a combination thereof, M is an element selected from Si, Ge, Ti or a combination thereof, and x is 0<x≤0.15)
According to paragraph 1,
A composite fluorescent structure in which the manganese-doped fluoride-based phosphor is a red phosphor.
delete According to paragraph 1,
The average diameter of the core is 1 to 50㎛, a composite fluorescent structure.
According to paragraph 1,
The metals of the metal oxides include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), tin (Sn), silicon (Si), hafnium (Hf), boron (B), and potassium (K). , a composite fluorescent structure selected from magnesium (Mg) and indium (In).
According to paragraph 4,
A composite fluorescent structure wherein the second shell has a thickness of 1 to 5 nm.
According to paragraph 1,
A composite fluorescent structure having a maximum emission center wavelength of 620 to 650 nm.
(S1) preparing a core containing a manganese-doped fluoride-based phosphor having the composition of Formula 1 below;
(S2) coating the core with silica to form a first cell on the core; and
(S3) coating a core coated with the first cell with a metal oxide different from the first shell to form a second cell on the first cell.
[Formula 1]
A ₃ MF ₇ : Mn _x ⁴⁺ or A ₂ MF ₆ : Mn _x ⁴⁺
(The A is Li, Na, K, Rb, Cs, NH ₄ or a combination thereof, M is an element selected from Si, Ge, Ti or a combination thereof, and x is 0<x≤0.15)
According to clause 8,
In the step (S2),
(S2-1) adding the core and amine-based catalyst to alcohol and stirring to obtain a mixed solution,
(S2-2) adding distilled water and a silica precursor to the mixed solution and stirring to obtain a core coated with the first cell, and
(S2-3) A method of manufacturing a composite fluorescent structure, comprising the step of washing and drying the core coated with the first cell.
According to clause 9,
The silica precursor is tetramethyl orthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropyl orthosilicate (TPOS), tetrabutyl orthosilicate (TBOS), methyltrimethoxysilane, methyltriethoxysilane, and vinyltrimethoxysilane. Methoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy silane, vinylmethyldimethoxysilane, butyltrimethoxysilane, diphenylethoxyvinylsilane, methyltriisopropoxy Silane, methyltriacetoxysilane, tetraphenoxysilane, tetrapropoxysilane, vinyltriisopropoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-gly One or more of the composite fluorescent structures selected from the group consisting of sidoxypropylmethylmethoxysilane, 3-glycidoxypropylmethylethoxysilane, and beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Manufacturing method.
According to clause 9,
In step (S2-2) above,
A method of manufacturing a composite fluorescent structure, wherein the weight ratio of the core to the silica precursor is 1:0.02 to 0.05.
According to clause 8,
In the step (S3),
A method of manufacturing a composite fluorescent structure, wherein the core coated with the first cell is alternately exposed to a gaseous metal supply source and a gaseous oxygen supply source to form a second cell.
According to clause 12,
The metal supply sources include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), tin (Sn), silicon (Si), hafnium (Hf), boron (B), potassium (K), and magnesium. Contains one or more metals selected from the group consisting of (Mg) and indium (In),
The oxygen source is H ₂ O or O ₂ , a method of manufacturing a composite fluorescent structure.