TW201617436A - Core-shell structured fluorescent material and light source device thereof - Google Patents

Abstract

The present invention provides a core-shell structured fluorescent material and a light source device thereof, in which the core-shell structured fluorescent material is excited by light having a wavelength ranging from 370 nm to 500 nm to emit a light spectrum whose peak ranging from 520 nm to 800 nm. The core-shell structured fluorescent material of the present invention comprises a core and a shell layer, in which the core can be a yellow light-, a green light- or a red light-fluorescent powder, and the shell layer comprises a fluoride fluorescent powder containing manganese. The light source device mainly comprises the core-shell structured fluorescent material, an exciting light source, an electrical connection wire and a package, in which a power source is inputted to the electrical connection wire to supply the exciting light source, and the core-shell structured fluorescent material is coated on the package for receiving the light from the exciting light source to produce high-quality emitted light, which can be used as a light source for illumination or display.

Description

Core-shell structure fluorescent material and light source device thereof

The invention relates to a core-shell structure fluorescent material and a light source device thereof, in particular, a core-shell structure fluorescent material comprising a core having yellow, green or red phosphor powder and having a manganese-containing fluoride phosphor powder The shell layer, and the manganese-containing fluoride phosphor contains tetravalent manganese ions and has the chemical formula A _x MF _6-y Z _y : Mn ⁴⁺ , and the core-shell structured fluorescent material can receive excitation light of ultraviolet and blue light, and Radiation composite spectroscopy to achieve high color rendering white light.

In recent years, white light-emitting diodes (LEDs), which have the dual characteristics of "energy saving" and "environmental protection", are generally considered to be revolutionary light sources for replacing heat lamps and fluorescent lamps as their luminous efficiency continues to increase. Fluorescent materials are indispensable optical conversion materials for single-wafer white LEDs. They are the most important key materials in single-chip white LED systems due to their luminous efficiency, stability, color rendering, color temperature and lifetime.

In general, white light devices need to have high color rendering to present the true color of the object. However, in the prior art, 550 nm Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ green powder or 560 nm Y ₃ Al ₅ O is excited by 440-460 nm blue light. ₁₂ : Ce ⁺³ yellow powder, the resulting white light color rendering is between 70 and 75, making the blue light wafer can not match the single fluorescent powder to meet the needs of the current light source.

Therefore, there is a need for a novel core-shell structured fluorescent material having a composite spectrum and a light source device using the same, which utilizes a core-structure fluorescent powder having a composite spectrum characteristic, that is, can be effectively packaged in a single phosphor powder. Enhancing the color rendering of white light, wherein the core-shell structure fluorescent material comprises a core having yellow, green or red phosphor powder and a shell layer containing fluorinated powder containing manganese fluoride, which can absorb wavelengths of 370 nm to 500 nm. The light is excited to be converted into emission light between 520 nm and 800 nm, and the core-structure fluorescent material is used to fabricate a light source device, thereby providing a light source having high quality, thereby solving the problems of the above-mentioned conventional techniques.

The main object of the present invention is to provide a core-shell structure fluorescent material, which comprises a core and a shell layer, and the core has yellow, green or red fluorescent powder, and the shell layer has manganese fluoride fluorescent powder. In particular, the manganese-containing fluoride phosphor contains a first element, a second element, a fluorine element, a halogen element, and a tetravalent manganese ion, and has a chemical formula of A _x MF _6-y Z _y :Mn ⁴⁺ , wherein A is the first The element further comprises at least one of lithium, sodium, potassium, rubidium, strontium, magnesium, calcium, strontium, barium, and zinc, and M is a second element and includes bismuth, antimony, tin, titanium, zirconium, aluminum, gallium, and indium. At least one of 钪, 钇, 钇, 镧, 铌, 钽, 铋, and 釓, F is fluorine, Z is a halogen element and contains at least one of chlorine, bromine, and iodine, and 0<x≦2,0≦ Y≦6.

The shell-containing manganese-containing fluoride phosphor can be excited by light of a wavelength of 370 nm to 500 nm, and emits light having a peak between 520 nm and 800 nm, and can be applied to an illumination or liquid crystal display with an appropriate fluorescent material. Thereby providing a light source with a suitable spectrum, such as a white light source.

Further, the core is a metal oxide containing trivalent europium and a compound containing divalent europium, and the chemical formula of the metal oxide containing trivalent europium is (Y, Gd, Tb, La, Sm, Pr, Lu) ₃ (Sc , Al, Ga) ₅ O ₁₂ :Ce ⁺³ , mainly comprising ruthenium, osmium, iridium, osmium, iridium, osmium, iridium, osmium, aluminum, gallium. The chemical formula of the divalent europium compound is strontium calcium strontium oxide ((Sr, Ca)Si ₂ O ₂ N ₂ :Eu ⁺² ), Alpha-矽 aluminum oxynitride (Alpha-SiAlON:Eu ⁺² ), Beta - bismuth oxynitride (Beta-SiAlON: Eu ^{+ 2} ), strontium calcium citrate compound ((Ba _, Sr, Ca) ₂ SiO ₄ : Eu ²⁺ ), calcium strontium nitride ((Ca, Sr, Ba) ₂ Si ₅ N ₈ :Eu ⁺² ), calcium barium aluminum strontium nitride ((Ca,Sr)AlSiN ₃ :Eu ⁺² ), in particular, the core particle size is from 0.01 um to 200 um.

In addition, the core-shell structure fluorescent material of the present invention may further comprise at least one of a yellow fluorescent material, a green fluorescent material, and a red fluorescent material, and is uniformly mixed, and the yellow fluorescent material, the green fluorescent material, The red fluorescent material can receive the excitation light and emit yellow, green, and red light, respectively. Specifically, the yellow fluorescent material includes trivalent europium-containing yttrium aluminum oxide (Y ₃ Al ₅ O ₁₂ :Ce ⁺³ ), and divalent europium-containing Alpha-yttrium aluminum oxynitride (Alpha-SiAlON:Eu ⁺²⁾ And strontium calcium citrate compound (Ba _, Sr, Ca) ₂ SiO ₄ :Eu ⁺² ), the green fluorescent material includes yttrium aluminum oxide containing trivalent europium (Lu ₃ Al ₅ O ₁₂ :Ce ^{+ 3} ) Beta-tellurium oxynitride (Beta-SiAlON:Eu ⁺² ) containing divalent europium and strontium calcium strontium oxide ((Sr,Ca)Si ₂ O ₂ N ₂ :Eu ⁺² ) The red fluorescent material includes a barium-strontium-strontium-containing nitrogen compound containing divalent europium ((Ba, Sr, Ca) ₂ Si ₅ N ₈ :Eu ⁺² ), and a calcium barium aluminum barium nitrogen compound ((Ca,Sr)AlSiN ₃ ) :Eu ⁺² ).

Another object of the present invention is to provide a light source device comprising a core-shell structure fluorescent material, an excitation light source, an electrical connection line, and a package, and the electrical connection line inputs a power source to supply an excitation light source, thereby generating emission light, and the core structure The phosphor material is coated on the package to receive the original emitted light of the excitation source to produce high quality radiation. In particular, the light source device of the present invention may further comprise at least one of a yellow fluorescent material, a green fluorescent material, and a red fluorescent material, wherein the yellow fluorescent material, the green fluorescent material, and the red fluorescent material can receive The excitation light emits yellow light, green light, and red light, respectively. In addition, the yellow fluorescent material, the green fluorescent material, and the red fluorescent material are uniformly mixed with the core-shell fluorescent material and coated in the package, so that a specific spectrum of light source can be provided to provide illumination or display fields. High quality light source required.

1‧‧‧Shell core structure fluorescent material

2‧‧‧Light source device

10‧‧‧ core

20‧‧‧ shell

22‧‧‧Yellow fluorescent material

24‧‧‧Green fluorescent material

26‧‧‧Red light fluorescent material

30‧‧‧Excitation source

A‧‧‧Local enlargement area

B‧‧‧Package

CN‧‧‧Electrical cable

L1‧‧‧Excited light

L2‧‧‧ emitted light

L3‧‧‧ emitting light source

PLE‧‧‧excitation spectroscopy

PL‧‧‧radiation spectrum

The first figure is a schematic view of a phosphorescent material of a core-shell structure according to an embodiment of the invention.

The second figure is a schematic diagram of a phosphorescent material mixed with a yellow fluorescent material, a green fluorescent material, and a red fluorescent material according to an embodiment of the present invention.

The third figure is a schematic view of a light source device using a core-shell structured fluorescent material in accordance with another embodiment of the present invention.

The fourth figure is the elemental analysis of Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ /K ₂ SiF ₆ :Mn ⁺⁴ core-shell structured phosphor powder of Example 1.

The fifth figure is an excitation and emission spectrum of the Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ /K ₂ SiF ₆ :Mn ⁺⁴ core-shell phosphor of Example 1.

The sixth figure shows the emission spectrum of Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ /K ₂ SiF ₆ :Mn ⁺⁴ core-shell structured phosphor powder synthesized by different concentrations of K ₂ SiF ₆ :Mn ⁺⁴ precursor. .

The seventh figure is the excitation and emission spectrum of the Beta-SiAlON/K ₂ SiF ₆ :Mn ⁺⁴ core-shell phosphor of Example 2.

The eighth figure shows the fluorescence emission spectrum of Beta-SiAlON/K ₂ SiF ₆ :Mn ⁺⁴ core-shell structured fluorescent powder synthesized by different concentrations of K ₂ SiF ₆ :Mn ⁺⁴ precursor.

The ninth graph is an excitation and emission spectrum of the Y ₃ Al ₅ O ₁₂ :Ce ⁺³ /K ₂ SiF ₆ :Mn ⁺⁴ core-shell phosphor of Example 3.

The tenth graph is the excitation and radiation spectrum of the (Ba, Sr, Ca) ₂ SiO ₄ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ core-shell phosphor of Example 4.

Figure 11 is an excitation and emission spectrum of the (Sr,Ca)Si ₂ O ₂ N ₂ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ core-shell phosphor of Example 5.

Figure 12 is an excitation and emission spectrum of the (Ca,Sr,Ba) ₂ Si ₅ N ₈ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ core-shell fluorescing powder of Example 6.

The thirteenth image is an excitation and emission spectrum of the (Ca,Sr)AlSiN ₃ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ core-shell phosphor of Example 7.

The embodiments of the present invention will be described in more detail below with reference to the drawings and the reference numerals, which can be implemented by those skilled in the art after having studied this specification.

Please refer to the first figure, a schematic diagram of a shell-core structure fluorescent material according to an embodiment of the invention. As shown in the first figure, the core-shell structured fluorescent material 1 of the present invention is mainly formed into a particulate or powdery phosphor, comprising a core 10 and a shell layer 20, wherein the core 10 has a particle size of 0.01 um to 200 um. It is sized and contains yellow, green or red fluorescent powder, while the shell 20 is coated on the core 10 and has a manganese-containing fluoride phosphor.

In general, the core-shell structured fluorescent material 1 of the present invention can emit light L2 having a peak between 520 nm and 800 nm after being excited by the excitation light L1 of a wavelength of 370 nm to 500 nm, which is suitable for illumination or display. The light source required for the device.

Further, the yellow, green or red phosphor of the core 10 may comprise a metal oxide of a trivalent europium and a compound containing a divalent europium. The metal oxide containing trivalent europium has the chemical formula (Y, Gd, Tb, La, Sm, Pr, Lu) ₃ (Sc, Al, Ga) ₅ O ₁₂ : Ce ⁺³ , mainly containing lanthanum, cerium, lanthanum , 镧, 钐, 鐠, 鑥, 钪, aluminum, gallium. The chemical formula of the divalent europium compound is strontium calcium strontium oxide ((Sr, Ca)Si ₂ O ₂ N ₂ :Eu ⁺² ), Alpha-矽 aluminum oxynitride (Alpha-SiAlON:Eu ⁺² ), Beta - bismuth oxynitride (Beta-SiAlON: Eu ^{+ 2} ), strontium calcium citrate compound ((Ba _, Sr, Ca) ₂ SiO ₄ : Eu ²⁺ ), calcium strontium nitride ((Ca, Sr, Ba) ₂ Si ₅ N ₈ :Eu ⁺² ), or calcium barium aluminum strontium nitride ((Ca,Sr)AlSiN ₃ :Eu ⁺² ).

The manganese-containing fluoride phosphor of the shell layer 20 mainly contains the first element A, the second element M, the fluorine element F, the halogen element Z, and the tetravalent manganese ion, and has the chemical formula A _x MF _6-y Z _y : Mn ⁴⁺ , wherein the first element A comprises at least one of lithium, sodium, potassium, rubidium, strontium, magnesium, calcium, strontium, barium, and zinc, and the second element M comprises bismuth, antimony, tin, titanium, zirconium, aluminum At least one of gallium, indium, antimony, bismuth, antimony, bismuth, antimony, bismuth and antimony, the halogen element Z comprises at least one of chlorine, bromine and iodine, and 0<x≦2,0≦y≦ 6.

In order to further adjust the emitted light L2 to form a colored light having a specific spectrum, such as white light, reference may be made to the second figure. In the embodiment of the present invention, the core-structure fluorescent material is mixed with a yellow fluorescent material, a green fluorescent material, and a red fluorescent device. The rear view of the material, wherein the present invention may further comprise at least one of a yellow fluorescent material 22, a green fluorescent material 24, and a red fluorescent material 26, wherein the yellow fluorescent material 22, the green fluorescent material 24, and the red light The phosphor material 26 can receive the light emission L1 and emit yellow light, green light, and red light, respectively.

More specifically, the yellow fluorescent material 22 may include a trivalent europium-containing lanthanum aluminum oxide, a divalent europium-containing Alpha-lanthanum aluminide compound, and a barium calcium telluride compound, and a trivalent europium compound. The chemical formula of aluminum oxide is Y ₃ Al ₅ O ₁₂ :Ce ⁺³ , and the chemical formula of Alpha-SiAlON:Eu ⁺² and strontium calcium citrate compound containing divalent europium is ( Ba, Sr, Ca) ₂ SiO ₄ :Eu ⁺² . The green fluorescent material 24 includes a trivalent europium-containing lanthanum aluminum oxide, a divalent europium Beta-yttrium aluminum oxynitride compound, and a lanthanum calcium lanthanum oxide, and the chemical formula of the lanthanum aluminum oxide containing trivalent europium is Lu. ₃ Al ₅ O ₁₂ :Ce ⁺³ , and the chemical formula of Beta-yttrium aluminum oxynitride containing divalent europium is Beta-SiAlON:Eu ⁺² , and the chemical formula of lanthanum strontium oxynitride is ((Sr,Ca)Si ₂ O ₂ N ₂ :Eu ⁺² ). In addition, the red phosphor material 26 includes a barium-strontium-strontium-nitrogen compound containing divalent europium, a calcium-strontium-aluminum-niobium compound, and the chemical formula of the barium-strontium-niobium compound of the divalent europium is (Ba, Sr, Ca) ₂ Si. ₅ N ₈ :Eu ⁺² , the chemical formula of calcium strontium aluminum bismuth compound is (Ca,Sr)AlSiN ₃ :Eu ⁺² °

With further reference to the third figure, a schematic diagram of a light source device using a core-shell structure fluorescent material according to another embodiment of the present invention is shown, wherein the light source device 2 includes a core-shell structure fluorescent material 1, an excitation light source 30, an electrical connection line CN, and The package body B, wherein the electrical connection line CN inputs a power source to supply the excitation light source 30, thereby generating the emission light L1, and the core-core structure fluorescent material 1 is coated on the package body B for receiving the original emission light L1 of the excitation light source. Produce high quality emissions Light source L3, such as white light. The package B encloses the excitation light source 30 and the electrical connection line CN to provide insulation protection, and is generally constructed of a resin or glass that is highly transparent and electrically insulating.

The technical features of the core-shell structure fluorescent material 1 are as described in the first and second embodiments, and therefore will not be described again.

The light source device 2 of the present invention may further comprise at least one of a yellow fluorescent material 22, a green fluorescent material 24, and a red fluorescent material 26, wherein the yellow light The technical features of the optical material 22, the green fluorescent material 24, and the red fluorescent material 26 have been proposed in the first and second embodiments, and will not be described again.

Therefore, the emission source L3 produced by the present invention can be used as a light source required for an illumination or display device.

In addition, the excitation light source 30 may include a light emitting diode (LED), a laser diode (LD), an organic light emitting diode (OLED), and a cold cathode lamp. Cold cathode fluorescent lamp (CCFL) or external electrode fluorescent lamp (EEFL).

In order to further clarify the characteristics exhibited by the present invention, in particular, the core-shell structured fluorescent material 1 composed of the core 10 and the shell 20 of different compositions, for the overall fluorescence effect and efficacy of the excitation light L1 having a wavelength of 370 nm to 500 nm, Specific examples 1 through 10 will be utilized below to illustrate different specific implementation means and technical contents. However, it is to be noted that the examples are merely illustrative and are not intended to limit the scope of the invention.

First, the core-shell structure fluorescent material 1 used in Example 1 is mainly a core 10 containing Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ and a shell 20 containing K ₂ SiF ₆ :Mn ⁺⁴ , which is synthesized in such a manner Take 100mL~1L HF solution at a specific chemical dose ratio, then add 5~10g SiO ₂ powder and 5~10g Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ phosphor powder, then add 20~50g K ₂ MnO ₄ powder until the solution After changing from transparent to dark purple, it was titrated with 10 to 60 mL of H ₂ O ₂ until an orange-yellow powder appeared. Thereafter, various necessary analyses and tests are performed, including the SEM image of Annex I, the elemental analysis of the fourth figure, and the excitation spectrum PLE and the emission spectrum PL of the fifth figure. As shown in Annex 1, the core-shell structure fluorescent material 1 is an irregular powder with particles of 15-30um, and the fourth figure shows elements of Lu, Al, O, Ce, K, Si, F, Mn, and the fifth figure. Fluorescence excitation emission spectrum of Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ /K ₂ SiF ₆ :Mn ⁺⁴ core-shell structured fluorescent powder fluorescence, wherein the excitation spectrum is a double band between 300 and 535 nm The peak is composed of 440~460nm blue excitation light L1 which is commonly used at present, and the emitted light L2 generated by Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ and K ₂ SiF ₆ :Mn ⁺⁴ , the red portion thereof The spectrum is contributed by K ₂ SiF ₆ :Mn ⁺⁴ of the shell layer 20, and its emission band is at 600-700 nm, and the highest peak position is at 630 nm, which is linear red light, so it is a fluorescent material with high saturation red light. The part of the green light in the spectrum is contributed by Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ of the core 10, and its light-emitting position is 480-750 nm, which is the green light material with the highest position at 550 nm.

In addition, the sixth figure shows the emission spectra of 0.2M, 0.4M, and 0.8M precursors of different concentrations of K ₂ SiF ₆ :Mn ⁺⁴ precursors. The results show that the required luminescence spectra can be adjusted with different concentrations of precursors to achieve blue light. LEDs with high color rendering requirements for single fluorescent materials.

In Example 2, the core 10 is Beta-SiAlON:Eu ⁺² and the shell is K ₂ SiF ₆ :Mn ⁺⁴ . The synthesis method is to take 100mL~1L HF solution at a stoichiometric ratio, then add 5~10g SiO ₂ powder and 5~10g Beta-SiAlON:Eu ⁺² phosphor powder, then add 20~50g K ₂ MnO ₄ powder until After the solution turned from transparent to dark purple, it was titrated with 10 to 60 mL of H ₂ O ₂ until an orange-yellow powder appeared. Thereafter, perform the necessary analysis and testing. The picture shows a seventh _{Beta-SiAlON / K 2 SiF 6} : Mn +4 core-shell structure of the phosphor excitation and fluorescence emission spectrum, and excitation spectrum is composed of a doublet, which is interposed between the band of 535 nm to 300, It is also suitable for the 440~460nm blue excitation currently used. The emission spectrum is composed of Beta-SiAlON:Eu ⁺² and K ₂ SiF ₆ :Mn ⁺⁴ . The red part spectrum is the K ₂ SiF of the shell 20. ₆ : Mn ⁺⁴ contribution, its emission band is at 600-700nm, the highest peak position is linear red light at 630nm, it is a fluorescent material with high saturation red light, and the part of green light in the spectrum is core 10 Beta-SiAlON: contributed by the emission spectrum of Eu ^{+ 2} , which is a green light material with a light-emitting position of 480-750 nm and a highest position of 540 nm.

In addition, the eighth figure shows the emission spectra of different concentrations of K ₂ SiF ₆ :Mn ⁺⁴ precursors 0.2M, 0.4M, 0.6M, 0.8M, 1.0M, 1.2M. The results show that different concentrations of precursors can be used. Adjust the required luminescence spectrum to achieve the high color rendering requirements of blue LEDs with a single fluorescent material.

Example 3 is a core-shell structured fluorescent material 1 composed of Y ₃ Al ₅ O ₁₂ :Ce ⁺³ /K ₂ SiF ₆ :Mn ⁺⁴ , which is synthesized in a stoichiometric ratio of 100 mL to 1 L of HF solution, followed by 5 ~10g SiO ₂ powder and 5~10g Y ₃ Al ₅ O ₁₂ :Ce ⁺³ phosphor powder, then add 20~50g K ₂ MnO ₄ powder until the solution changes from transparent to dark purple, then 10~60mL H ₂ O _{2 is} titrated until an orange powder appears. Subsequent analysis and testing are performed. The ninth picture shows the excitation and emission spectra of the Y ₃ Al ₅ O ₁₂ :Ce ⁺³ /K ₂ SiF ₆ :Mn ⁺⁴ core-shell structured fluorescent material, in which the excitation spectrum is composed of double peaks and the band is between 300 and Between 535nm, it is suitable for the 440~460nm blue light excitation currently used, and the emission spectrum is composed of the radiation of Y ₃ Al ₅ O ₁₂ :Ce ⁺³ and K ₂ SiF ₆ :Mn ⁺⁴ . The shell layer 20 is contributed by K ₂ SiF ₆ : Mn ⁺⁴ , and its emission band is located at 600-700 nm, and the highest peak position is linear red light at 630 nm. It is a fluorescent material with high saturation red light, and the spectrum is green. The portion of the light is contributed by the Y ₃ Al ₅ O ₁₂ :Ce ⁺³ emission spectrum of the core 10, which is a yellow light material having a light-emitting position at 480-750 nm and a highest position at 560 nm.

The core 10/shell 20 of Example 4 is combined into (Ba, Sr, Ca) ₂ SiO ₄ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ , and the synthesis thereof is taken in a stoichiometric ratio of 100 mL to 1 L of HF solution, followed by Add 5~10g SiO ₂ powder and 5~10g (Ba,Sr,Ca) ₂ SiO ₄ :Eu ⁺² phosphor powder, then add 20~50g K ₂ MnO ₄ powder until the solution turns from transparent to deep purple, then 10~60mL H ₂ O _{2 was} titrated and an orange powder appeared. The tenth picture shows the excitation and emission spectra of (Ba,Sr,Ca) ₂ SiO ₄ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ core-shell structured fluorescent material. The excitation spectrum is composed of double peaks. Between 300 and 535 nm, it is suitable for the 440-460 nm blue light excitation currently used. The emission spectrum is composed of (Ba, Sr, Ca) ₂ SiO ₄ :Eu ⁺² and K ₂ SiF ₆ :Mn ⁺⁴ . The red light partial spectrum is contributed by K ₂ SiF ₆ :Mn ⁺⁴ of the shell layer 20, and its emission band is at 600-700 nm, and the highest peak position is linear red light at 630 nm, which is a fluorescent material with high saturation red light. The portion of the green light in the spectrum is contributed by the (Ba, Sr, Ca) ₂ SiO ₄ :Eu ⁺² emission spectrum of the core 10, which is a yellow light material having a light-emitting position at 480-750 nm and a highest position at 570 nm.

Example 5 is a core 10/shell 20 combination of (Sr,Ca)Si ₂ O ₂ N ₂ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ , taking a 100 mL~1 L HF solution at a stoichiometric ratio, followed by 5~10g SiO ₂ powder and 5~10g (Sr,Ca)Si ₂ O ₂ N ₂ :Eu ⁺² phosphor powder, then add 20~50g K ₂ MnO ₄ powder to make the solution change from transparent to deep purple, then An orange powder appeared in the titration of 10~60mL H ₂ O ₂ . The eleventh image shows the excitation and emission spectra of (Sr,Ca)Si ₂ O ₂ N ₂ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ core-shell structured fluorescent material, and the excitation spectrum is composed of double peaks. The wavelength range is between 300 and 535 nm, which is suitable for the 440-460 nm blue light excitation currently used. The emission spectrum is emitted by (Sr, Ca)Si ₂ O ₂ N ₂ :Eu ⁺² and K ₂ SiF ₆ :Mn ⁺⁴ . The red light partial spectrum is contributed by K ₂ SiF ₆ :Mn ⁺⁴ of the shell layer 20, and the emission band is at 600-700 nm, and the highest peak position is linear red light at 630 nm, which is a high saturation red light. Fluorescent material, and the part of the green light in the spectrum is contributed by the (Sr,Ca)Si ₂ O ₂ N ₂ :Eu ⁺² emission spectrum of the core 10, which is the luminescence position at 480-750 nm and the highest position at 545 nm. Yellow light material.

The core 10/shell 20 of Example 6 is combined into (Ca,Sr,Ba) ₂ Si ₅ N ₈ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁴⁺ , and a 100 mL to 1 L HF solution is taken in a stoichiometric ratio, followed by Add 5~10g SiO ₂ powder and 5~10g (Ca,Sr,Ba) ₂ Si ₅ N ₈ :Eu ⁺² core structure phosphor powder, then add 20~50g K ₂ MnO ₄ powder, the solution changes from transparent to deep purple Then, an orange powder appeared by titration with 10 to 60 mL of H ₂ O ₂ . Thereafter, various necessary analyses and tests were carried out: the twelfth picture shows (Ca, Sr, Ba) ₂ Si ₅ N ₈ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁴⁺ core-structure fluorescent material excitation and emission The spectrum, in which the excitation spectrum is composed of double peaks, the wavelength range is between 300 and 535 nm, suitable for the currently widely used 440-460 nm blue light excitation, and the emission spectrum is (Ca, Sr, Ba) ₂ Si ₅ N ₈ :Eu ⁺² And K ₂ SiF ₆ : Mn ⁺⁴ composed of radiation, the emission spectrum is located at 500-750nm, the highest position is 630nm.

The core 10/shell 20 of Example 7 is combined into (Ca,Sr)AlSiN ₃ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ , which is a stoichiometric ratio of 100 mL to 1 L of HF solution, followed by 5 to 10 g of SiO. ₂ powder and 5~10g (Ca,Sr)AlSiN ₃ :Eu ⁺² core structure phosphor powder, then add 20~50g K ₂ MnO ₄ powder, the solution changes from transparent to deep purple, then 10~60mL H ₂ O ₂ An orange powder appeared in the titration. The thirteenth picture shows the excitation and emission spectra of (Ca,Sr)AlSiN ₃ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ core-shell structured fluorescent materials. The excitation spectrum consists of double peaks with a band of 300. Between 535nm, it is suitable for the 440~460nm blue excitation currently used. The emission spectrum is composed of (Ca, Sr)AlSiN ₃ :Eu ⁺² and K ₂ SiF ₆ :Mn ⁺⁴ . The emission spectrum is at 500-750nm, the highest position is 630nm.

Example 8 is the encapsulation result for the combination of (Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ /K ₂ SiF ₆ :Mn ⁴⁺ ).

Table 1 below shows the results of the fluorescent material packaging test. Comparative Examples 1 to 5 are 460 nm blue wafers with Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ , Y ₃ Al ₅ O ₁₂ :Ce ⁺³ , (Sr , Ca)Si ₂ O ₂ N ₂ :Eu ⁺² , (Ba,Sr,Ca) ₂ SiO ₄ :Eu ⁺² and Beta-SiAlON:Eu ⁺² for single phosphor powder encapsulation, and Example 8 is an example of utilization The core-shell structured fluorescent material Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ /K ₂ SiF ₆ :Mn ⁺⁴ mentioned in 1 is packaged with a 460 nm blue light wafer.

The results showed that the color rendering index (CRI) obtained in the comparative examples 1 to 5 package was between 60 and 75, and Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ /K ₂ SiF ₆ :Mn ^{4 was used. +} The single-fluorescent powder package of the core-shell structured phosphor material has a color rendering (CRI) of up to 80.

Further, Example 9 is a result of encapsulation of a core-shell structured fluorescent material of (Ca,Sr,Ba) ₂ Si ₅ N ₈ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ , as shown in Table 2.

In the fluorescent material packaging test results of Table 2, Comparative Example 6 is a 460 nm blue light wafer with Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ phosphor powder and (Ca,Sr,Ba) ₂ Si ₅ N ₈ :Eu ^{+ 2} fluorescent powder for encapsulation, Example 9 is a core-shell structured fluorescent material using (Ca, Sr, Ba) ₂ Si ₅ N ₈ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ mentioned in Example 6. It is packaged with Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ phosphor and 460 nm blue wafer. The results show that the color rendering of the package of Comparative Example 6 is 84, and the core-shell structured fluorescent material using (Ca, Sr, Ba) ₂ Si ₅ N ₈ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ The color rendering property of the package of Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ phosphor powder is 87, therefore, (Ca,Sr,Ba) ₂ Si ₅ N ₈ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ The core-shell structured fluorescent material can significantly improve color rendering.

Finally, Example 10 is the encapsulation result of the core-shell structured fluorescent material (Ca,Sr)AlSiN ₃ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ , as shown in Table 3.

table 3

Comparative Example 7 was packaged with a 460 nm blue wafer with Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ phosphor powder and (Ca,Sr)AlSiN ₃ :Eu ⁺² phosphor powder. Example 10 is referred to in Example 7 A core-shell structured fluorescent material of (Ca,Sr)AlSiN ₃ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ , packaged with Lu ₃ Al ₅ O ₁₂ :Ce ⁺³ phosphor and 460 nm blue wafer . The results show that the color rendering property of the package of Comparative Example 7 is 85, using (Ca, Sr)AlSiN ₃ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ core-shell structured fluorescent material and Lu ₃ Al ₅ O ₁₂ :Ce ^The color rendering of the ⁺³ phosphor powder package is 88. Therefore, the (Ca,Sr)AlSiN ₃ :Eu ⁺² /K ₂ SiF ₆ :Mn ⁺⁴ core-shell structured fluorescent material can significantly improve color rendering.

In summary, the main feature of the present invention is to use a core-shell and a shell-shell fluorescent material to achieve the purpose of adjusting the fluorescence and efficacy, especially the core has yellow, green, or red fluorescent Powder, while the shell layer has fluorinated powder containing manganese fluoride. The method further includes at least one of a yellow fluorescent material, a green fluorescent material, and a red fluorescent material, wherein the yellow, green, and red fluorescent materials can receive the light and emit yellow, green, and Red light, which in turn adjusts the emitted light, to be mixed into a high-quality color light with a specific spectrum, such as white light. In addition, another feature of the present invention is the use of a core-shell structured phosphor material to create a light source device that produces a high color rendering light source that provides the original source of light required in the field of illumination or display.

Since the technology of the present invention is not found in published publications, periodicals, magazines, media, exhibition venues, and thus is novel, and can be implemented by breaking through the current technical bottlenecks, it is indeed progressive. In addition, the present invention can solve the problems of the conventional technology, improve the overall use efficiency, and can achieve the value of industrial utilization.

The above is only a preferred embodiment for explaining the present invention, and is not intended to limit the present invention in any way, and any modifications or alterations to the present invention made in the spirit of the same invention. All should still be included in the scope of the intention of the present invention.

1‧‧‧Shelf core structure fluorescent material

10‧‧‧ core

20‧‧‧ shell

L1‧‧‧Excited light

L2‧‧‧ emitted light

Claims (9)

A core-shell structured fluorescent material for emitting light having a peak between 520 nm and 800 nm after excitation by light of a wavelength of 370 nm to 500 nm, comprising: a core having yellow, green or red light a phosphor powder; and a shell layer coated on the core, having a manganese-containing fluoride phosphor powder comprising a first element, a second element, a fluorine element, a halogen element, and a tetravalent Manganese ion, and having the chemical formula A _x MF _6-y Z _y :Mn ⁴⁺ , wherein A is the first element and contains at least one of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, and zinc First, M is a second element and comprises at least one of lanthanum, cerium, tin, titanium, zirconium, aluminum, gallium, indium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, and lanthanum, F is fluorine, and Z is The halogen element further contains at least one of chlorine, bromine and iodine, and 0 < x ≦ 2, 0 ≦ y ≦ 6. The core-shell structured fluorescent material according to claim 1, wherein the core has a particle size of 0.01 um to 200 um. The core-shell structured fluorescent material according to claim 1, wherein the core phosphor comprises a metal oxide containing trivalent europium, and the chemical formula of the trivalent europium-containing metal oxide is (Y, Gd, Tb, La, Sm, Pr, Lu) ₃ (Sc, Al, Ga) ₅ O ₁₂ :Ce ⁺³ , mainly containing yttrium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, aluminum, gallium, including Barium strontium strontium oxynitride ((Sr,Ca)Si ₂ O ₂ N ₂ :Eu ⁺² ), Alpha-矽Al oxynitride (Alpha-SiAlON:Eu ⁺² ), Beta-Aluminum oxynitride Compound (Beta-SiAlON:Eu ⁺² ), strontium calcium citrate compound ((Ba,Sr,Ca) ₂ SiO ₄ :Eu ⁺² ), strontium calcium strontium nitrogen compound ((Ba,Sr,Ca) ₂ Si ₅ N ₈ :Eu ⁺² ), calcium barium aluminum strontium nitrogen compound ((Ca, Sr)AlSiN ₃ :Eu ⁺² ). The shell-nuclear structure fluorescent material according to the first aspect of the patent application, further comprising at least one of a yellow fluorescent material, a green fluorescent material, and a red fluorescent material, wherein the yellow light of the yellow fluorescent material, the green light The green light of the fluorescent material and the red light of the red fluorescent material are used to blend the emitted light to have a specific spectrum of colored light, and the colored light contains white light. The core-shell structured fluorescent material according to claim 4, wherein the yellow fluorescent material comprises trivalent europium-containing lanthanum aluminum oxide, divalent europium-containing Alpha-rhenium oxynitride, and barium calcium strontium silicate a compound, and the trivalent europium yttrium aluminum oxide has a chemical formula of Y ₃ Al ₅ O ₁₂ :Ce ⁺³ , and the chemical formula of the divalent europium-containing Alpha-tellurium oxynitride is Alpha-SiAlON:Eu ⁺² , 钡The chemical formula of the strontium calcium citrate compound is ((Ba, Sr, Ca) ₂ SiO ₄ :Eu ⁺² ), and the green fluorescent material includes yttrium aluminum oxide containing trivalent cerium and Beta-containing cerium chemical formula silicon aluminum oxynitride, silicon oxynitride, and calcium, strontium and the trivalent cerium oxide is aluminum Lu _{Lu 3 Al 5 O 12: Ce} +3, Beta- silicon aluminum oxynitride containing divalent europium The chemical formula of the compound is Beta-SiAlON: Eu ⁺² , the chemical formula of strontium calcium strontium oxide is (Sr, Ca)Si ₂ O ₂ N ₂ :Eu ⁺² , and the red fluorescent material includes divalent europium. a calcium strontium nitrogen compound, a calcium strontium aluminum strontium nitrogen compound, and the bismuth calcium strontium nitrogen compound of the divalent cerium is (Ba, Sr, Ca) ₂ Si ₅ N ₈ :Eu ⁺² , calcium lanthanum aluminum lanthanum nitrogen Chemical Composition formula _{(Ca, Sr) AlSiN 3:} Eu +2. A light source device comprising: an excitation light source for emitting excitation light having a wavelength of 370 nm to 500 nm; and a core-shell structured fluorescent material according to claim 1 for receiving excitation from the excitation light source Light, and emits light having a characteristic spectrum; an electrical connection line for connecting the excitation light source and an external power source to power the external power source Inputting the excitation light source to generate the excitation light; and a package for coating the excitation light source and the electrical connection line to provide isolation protection, and the core-shell structure fluorescent material is coated on the package body, The emitted light having a radiation peak of a characteristic spectrum of between 520 nm and 800 nm is emitted by receiving the excitation light. The light source device according to claim 6 , wherein the excitation light source comprises a light emitting diode (LED), a laser diode (LD), an organic light emitting diode (organic light emitting diode) , OLED), cold cathode fluorescent lamp (CCFL) or external electrode fluorescent lamp (EEFL). The light source device according to claim 6 , further comprising at least one of a yellow fluorescent material, a green fluorescent material, and a red fluorescent material, which is mixed with the core-shell fluorescent material and coated to the package a body, wherein the yellow light of the yellow fluorescent material, the green light of the green fluorescent material, and the red light of the red fluorescent material are used to blend the emitted light to have a specific spectrum of colored light, and the colored light comprises white light. The light source device of claim 8, wherein the yellow fluorescent material comprises trivalent europium-containing lanthanum aluminum oxide, divalent europium-containing Alpha-lanthanum oxynitride compound, and barium calcium citrate compound, and The chemical formula of trivalent europium yttrium aluminum oxide is Y ₃ Al ₅ O ₁₂ :Ce ⁺³ , and the chemical formula of the Alpha-tellurium oxynitride containing divalent europium is Alpha-SiAlON:Eu ⁺² , strontium calcium citrate The chemical formula of the salt compound is ((Ba,Sr,Ca) ₂ SiO ₄ :Eu ⁺² ), and the green fluorescent material includes yttrium aluminum oxide containing trivalent cerium, Beta-cerium aluminum oxynitride and divalent chemical formula europium strontium barium calcium silicon oxynitride, and the trivalent cerium oxide is aluminum Lu _{Lu 3 Al 5 O 12: Ce} +3, chemical formula Beta- silicon aluminum oxynitride of Beta-SiAlON, The chemical formula of the divalent europium-containing barium calcium strontium oxide is (Ba _, Sr _, Ca)Si ₂ O ₂ N ₂ :Eu ⁺² , and the red fluorescent material comprises barium calcium containing divalent europium. a nitrogen compound, a calcium strontium aluminum strontium nitrogen compound, and the bismuth calcium strontium nitrogen compound of the divalent cerium is (Ba, Sr, Ca) ₂ Si ₅ N ₈ :Eu ⁺² , the calcium lanthanum lanthanide compound The formula is (Ca,Sr)AlSiN ₃ :Eu ⁺² .