CN114350348A - Nitride fluorescent powder and preparation method and application thereof - Google Patents
Nitride fluorescent powder and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides nitride fluorescent powder and a preparation method and application thereof. The nitride fluorescent material has small chromaticity change under high temperature and high humidity conditions and good durability. The composition of the nitride fluorescent material includes at least one element selected from the group consisting of Ca, Sr, Ba and Mg; at least one element selected from the group consisting of Li, Na and k; at least one element selected from the group consisting of Eu, Ce, Tb and Mn; al and N. The method comprises preparing a calcined product having the composition, contacting the calcined product with a fluorine-containing substance, and heat-treating the calcined product at a temperature of 200 to 500 ℃. Also provided is a light emitting device using the nitride fluorescent material.
Description
Technical Field
The invention belongs to the technical field of fluorescent powder manufacturing, and particularly relates to nitride fluorescent powder and a preparation method and application thereof.
Background
Light emitting devices, which are a combination of laser Light (LD) and fluorescent materials, have been increasingly used as lighting devices and backlights for liquid crystal displays, and the like. For example, in the case of using a light-emitting device in a liquid crystal display device, a fluorescent material of a narrow half band width is required to provide a wider range of color reproducibility.
Examples of such a fluorescent material include red-emitting phosphors (hereinafter abbreviated as "red-emitting phosphors") of SrLiAl3N4: EuIs "SLAN fluorophor"). The current patent art discloses SLAN phosphors having a narrow half-band width of 70nm or less and a peak fluorescence wavelength around 650 nm. A SLAN phosphor described in the literature is prepared to include lithium aluminum hydride (LiAlH)4) Aluminum nitride (AlN), strontium hydride (SrH)2) And europium fluoride (EuF)3) The raw material powders inside were weighed in a stoichiometric ratio and mixed with Eu in a proportion of 0.4 mol%, and the mixture was placed in a crucible and calcined at 1000 ℃ under atmospheric pressure in a mixed atmosphere of hydrogen and nitrogen for two hours.
However, in the process of implementing the technical solution of the invention in the embodiments of the present application, the inventors of the present application find that the above-mentioned technology has at least the following technical problems: since it is known that the SLAN phosphor is easily deteriorated by oxygen, heat, water, etc., there is a need for further improvement of a durable light-emitting device using the SLAN phosphor.
An object of the present invention is to provide a method for preparing a nitride fluorescent material capable of providing a light emitting device having excellent durability, a nitride fluorescent material, and a light emitting device using the same.
Disclosure of Invention
Since it is known that the SLAN phosphor is easily deteriorated by oxygen, heat, water, etc., there is a need for further improvement of a durable light-emitting device using the SLAN phosphor. An object of the present invention is to provide a method for manufacturing a nitride fluorescent material capable of providing a light emitting device having excellent durability, a nitride fluorescent material, and a light emitting device using the method
1. Embodiments of the present application include configurations as shown below. In the first embodiment, a composition and a manufacturing method of manufacturing a nitride fluorescent material are described. The molecular formula of the core of the fluorescent material is AvBwCxAl3-ySiyNzWherein A represents at least one element selected from the group consisting of Ca, Sr, Ba and Mg; b represents at least one element selected from the group consisting of Li, Na and k; c represents at least one element selected from the group Eu, Ce, Tb and Mn; v, w, x, y and z respectively satisfy 0.90-1.00-0.90≤w≤1.00,0.001<x is less than or equal to 0.1, y is less than or equal to 0 and less than or equal to 0.5, and z is more than or equal to 3.0 and less than or equal to 5.0; the surface of the shell of the fluorescent material is a layer containing fluorine-containing compounds;
the preparation method comprises the following steps: preparation of the formula AvBwCxAl3-ySiyNzAnd contacting the calcined product with a fluorine-containing substance and heat-treating the calcined product at a temperature of 200 ℃ or more and 500 ℃ or less.
Preferably, the fluorine-containing substance is at least one selected from the group consisting of F2, CHF3, CF4, NH4HF2, NH4F, SiF4, KrF2, XeF2, XeF4, and NF 3.
Preferably, the calcined product is subjected to heat treatment in an inert gas.
Preferably, the fluorine-containing substance is in a gaseous state, and the calcined product is heat-treated in a gas atmosphere containing an inert gas and the fluorine-containing substance.
Preferably, the fluorine-containing substance is fluorine gas.
Preferably, the fluorine-containing species is ammonium fluoride.
Preferably, the thickness of the layer containing a fluorine-containing compound is 0.05 μm to 0.8. mu.m.
According to a second object of the present invention, there is provided a nitride phosphor prepared by the above method.
According to a third object of the present invention, there is provided a use of a light emitting device of a nitride fluorescent glass.
The invention has the following beneficial effects:
1. the nitride fluorescent material retains good reliability and suppresses the change in chromaticity even after storage under the above-described environment.
2. The nitride fluorescent material produced according to the embodiment of the present invention has excellent durability, and thus a light emitting device having high reliability can be provided using the nitride fluorescent material.
3. The light-emitting device can be applied to an illumination light source having remarkably excellent light-emitting characteristics, which includes a laser as an excitation light source, an LED display device, a backlight of a liquid crystal display device, a traffic signal, an illumination switch, various sensors, and various indicators.
Drawings
Fig. 1 is a comparison graph of x-ray diffraction patterns of an example nitride fluorescent material according to the present invention and a comparative example nitride fluorescent material and a reference compound.
Fig. 2 is a graph of emission spectra of nitride fluorescent materials of examples and comparative examples.
Detailed Description
Methods of manufacturing a nitride fluorescent material, the nitride fluorescent material, and a light emitting device according to the present invention will be described below. However, the examples shown below exemplify a method for producing a nitride fluorescent material for implementing the technical concept of the present invention, and the scope of the present invention is not limited to the method for producing the nitride fluorescent material described below. In the specification, the relationship between the chromaticity name and the chromaticity coordinate, the relationship between the wavelength range of light and the color name of monochromatic light, and the like all conform to JIS Z8110. In the case where a composition contains a plurality of substances corresponding to one component, the content of the component in the composition means the total amount of the plurality of substances contained in the composition unless otherwise specified.
The nitride phosphor prepared in this example includes a phosphor core having a formula of AvBwCxAl3-ySiyNz, wherein a represents at least one element selected from the group consisting of Ca, Sr, Ba and Mg; b represents at least one element selected from the group consisting of Li, Na and k; c represents at least one element selected from the group Eu, Ce, Tb and Mn; v, w, x, y and z respectively satisfy that v is more than or equal to 0.90 and less than or equal to 1.00, w is more than or equal to 0.90 and less than or equal to 1.00, x is more than 0.001 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 0.5, and z is more than or equal to 3.0 and less than or equal to 5.0; the surface of the shell of the fluorescent material is a layer containing fluorine-containing compounds;
the preparation method comprises the following steps: a calcined product having a molecular formula of AvBwCxAl3-ySiyNz is prepared, and the calcined product is contacted with a fluorine-containing substance and heat-treated at 200 ℃ or more and 500 ℃ or less.
From the viewpoint of stability of the crystal structure, the parameter v is preferably 0.90 or more, 1.00 or less, preferably 0.90 or more, 1.00 or less. The parameter x represents the activation amount of at least one element selected from the group consisting of Eu, Ce, Tb, and Mn, and may be appropriately selected to achieve the target characteristics. The parameter x preferably satisfies 0.001< x ≦ 0.020, preferably satisfies 0.002 ≦ x ≦ 0.015.
The core part of the fluorescent material is formed by burning the mixture in a nitrogen atmosphere. For example, firing may be performed using a gas-pressurized electric furnace. The firing temperature may be 1,000 ℃ or more and 1,400 ℃ or less, preferably 1,000 ℃ or more and 1,300 ℃ or less, more preferably 1,100 ℃ or more and 1,300 ℃ or less. When the light emission temperature is too low, the target fluorescent compound is difficult to form, and when the light emission temperature is too high, the fluorescent compound may be decomposed, thereby deteriorating the light emission characteristics. Two-step firing (or multi-step firing), wherein the firing temperature in the first step is 800 ℃ or above 1000 ℃ or below, and after gradually raising the temperature, the firing temperature in the second step is 1000 ℃ or above 1400 ℃ or below. The material mixture may be sintered from graphite, Boron Nitride (BN), or alumina (Al)2O3) And a crucible, a boat or the like formed of a carbonaceous material such as W, molybdenum or the like. The atmosphere of combustion is sufficient to be an atmosphere of a nitrogen-containing gas, possibly an atmosphere of at least one selected from the group consisting of hydrogen, argon, carbon dioxide, carbon monoxide, ammonia, in addition to the nitrogen-containing gas. The proportion of nitrogen gas in the firing atmosphere is preferably 70% by volume or more, more preferably 80% by volume or more. The ignition may be performed under a pressure atmosphere of 0.2MPa or more, 200MPa or less. When the target nitride fluorescent material tends to decompose at an elevated temperature, the pressurized atmosphere may inhibit the decomposition to facilitate achievement of excellent light emission characteristics. The pressurized atmosphere calculated as the gauge pressure is preferably in the range of 0.2MPa or more and 1.0MPa or less, more preferably in the range of 0.8MPa or more and 1.0MPa or less. By increasing the atmospheric pressure at the time of combustion, the decomposition of the fluorescent compound at the time of combustion can be suppressed, thereby providing a fluorescent material having high characteristics. The firing time may be appropriately selected depending on the firing temperature, gas components, and other conditions. For example, the time may be 0.5 hour or more and 20 hours or less, preferably 1 hour or more and 10 hours or less. The ignition can be 0.2MPa or more, 200MPa or lessIs carried out under atmospheric pressure. When the target nitride fluorescent material tends to decompose at an elevated temperature, the pressurized atmosphere may inhibit the decomposition to facilitate achievement of excellent light emission characteristics. The pressurized atmosphere calculated as the gauge pressure is preferably in the range of 0.2MPa or more and 1.0MPa or less, more preferably in the range of 0.8MPa or more and 1.0MPa or less. By increasing the atmospheric pressure at the time of combustion, the decomposition of the fluorescent compound at the time of combustion can be suppressed, thereby providing a fluorescent material having high characteristics. The firing time may be appropriately selected depending on the firing temperature, gas components, and other conditions. For example, the shooting time may be 0.5 hour or more and 20 hours or less, preferably 1 hour or more and 10 hours or less.
The phosphor outer shell portion brings the above calcined product into contact with a fluorine-containing substance and heat-treats the calcined product at 200 ℃ or more and 500 ℃ or less, and the fluorine-containing compound is expected to function as a protective film. The use of the nitride fluorescent material can provide a light-emitting device having excellent durability and less chromaticity variation even under an environment where temperature and humidity are relatively high.
The fluorine-containing substance is not particularly limited as long as it is a fluorine-containing substance, and examples thereof include fluorine gas (F2) and fluorine compounds. Examples of the fluorine compounds include CF4、CHF3、NH4HF2、NH4F、SiF4、KrF2、XeF2And NF3. Preferably, the fluorine-containing species is selected from the group consisting of2、CHF3、CF4、NH4F2、NH4F、SiF4、KrF2、XeF2、XeF4And NF3At least one selected from the group of (1). The fluorine-containing substance is more preferably fluorine gas (F)2) Or ammonium fluoride (NH)4F)。
The temperature of the calcined product in contact with the solid or liquid fluorine-containing substance at room temperature (20 ℃. + -. 5 ℃) or higher, lower than the heat treatment temperature, or the heat treatment temperature. Specifically, the temperature may be less than 200 degrees celsius at or above 20 degrees celsius, or may be at or above 20 degrees celsius and 500 degrees celsius or below. If the environmental temperature at which the calcined product is contacted with the fluorine-containing substance in a solid state or in a liquid state at normal temperature is 20 ℃ or more and 200 ℃ or less, the calcined product is subjected to heat treatment at temperatures of 200 ℃ or more and 500 ℃ or less after being contacted with the fluorine-containing substance.
If the fluorine-containing substance is in a solid or liquid state at ordinary temperature, the calcined product is preferably contacted with the fluorine-containing substance in an amount of 1% by mass or more, 10% by mass or less, and 100% by mass based on the total amount of the calcined product and the fluorine-containing substance. The amount of the fluorine-containing substance brought into contact with the calcined product is more preferably in the range of 2% by mass or more and 8% by mass or less, and further preferably in the range of 3% by mass or more and 7% by mass or less, based on 100% by mass of the total amount of the calcined product and the fluorine-containing substance. It is advantageous to form a layer of the fluorine-containing compound on or near the surface of the calcined product. In the nitride fluorescent material according to this embodiment, the layer functions as a protective layer, and thus the nitride fluorescent material mounted on the light emitting device is less susceptible to the external environment, thereby improving the durability of the light emitting device.
In the case where the fluorine-containing substance is in a gaseous state, the calcined product may be contacted with the fluorine-containing substance by treating the calcined product in an atmosphere containing the fluorine-containing substance. In the case where the fluorine-containing substance is in a gaseous state, the calcined product may be disposed in an atmosphere containing the fluorine-containing substance, and the calcined product may be subjected to heat treatment in an atmosphere containing the fluorine-containing substance at a temperature of 200 ℃ or more and 500 ℃ or less. If the fluorine-containing substance is F2(fluorine gas), and the calcined product contains F2Is heat-treated in an atmosphere of 200 ℃ or more and 500 ℃ or less, F in the atmosphere2The concentration is preferably in the range of 2% by volume or more and 25% by volume or less, more preferably in the range of 5% by volume or more and 20% by volume or less. F2The concentration in the atmosphere is below a prescribed value, the target durability may not be provided. When F is present2At concentrations above the specified values, fluorination of the phosphor core may occur, which may significantly reduce the luminous emission coefficient.
The heat treatment is preferably carried out in an inert gas atmosphere. The inert gas atmosphere is an atmosphere containing argon, helium, nitrogen, or the like as a main component. In some cases, the inert gas air may contain oxygen as an inevitable impurity, and herein, the inert gas air containing 15% or less by volume of oxygen is referred to as inert gas air. The oxygen concentration in the inert gas atmosphere is preferably ten percent by volume or less, more preferably five percent by volume or less, and further preferably one percent by volume or less. If the oxygen concentration exceeds a prescribed value, it is possible to excessively oxidize the particles of the fluorescent material. If the fluorine-containing substance is in a gaseous state, it is preferable to perform the heat treatment in an atmosphere containing an inert gas and the fluorine-containing substance, rather than in an atmosphere containing only the fluorine-containing substance, for safety reasons.
The temperature of the calcined product which is brought into contact with the fluorine-containing substance and subjected to heat treatment is 200 ℃ or higher and 500 ℃ or lower. The temperature of the heat treatment is preferably in the range of 250 ℃ or more and 450 ℃ or less, further preferably in the range of 250 ℃ or more and 400 ℃ or less, further preferably in the range of 250 ℃ or more and 350 ℃ or less. In the case where the heat treatment temperature is lower than the prescribed temperature, it is difficult to form a fluorine-containing compound on the surface of the calcined product or in the vicinity of the surface thereof, and thus a nitride fluorescent material having durability cannot be provided. In the case where the heat treatment temperature exceeds the prescribed temperature, it is considered that the crystal structure of the calcined product is easily broken, and thus a nitride fluorescent material having high durability cannot be provided.
The time for the heat treatment is not particularly limited, but is preferably in the range of 1 hour or more or 10 hours or less, more preferably 2 hours or more or 8 hours or less. If the heat treatment time is within 1 hour or 10 hours, it is considered that a layer of the fluorine-containing compound is formed on the surface of the calcined product or in the vicinity of the surface thereof by the contact of the calcined product with the fluorine-containing substance and the heat treatment, and the layer functions as a protective layer to improve the durability of the light-emitting device containing the fluorescent material.
And (3) post-processing: the method of preparing a nitride fluorescent material according to this embodiment may further include post-treatment of cracking, pulverizing, classifying, and other treatments on the resulting nitride fluorescent material after the heat treatment.
The compound layer containing fluorine of the nitride fluorescent material according to this embodiment preferably has a thickness ranging from 0.05 μm to 0.8 μm, and more preferably has a thickness ranging from 0.05 μm to 0.6 μm. If the fluorine compound layer containing the nitride fluorescent material has a first layer and a second layer, the total thickness of the first layer and the second layer is preferably in the range of 0.05 μm to 0.8 μm. In the case where the thickness of the compound layer containing fluorine of the nitride fluorescent material is small by 0.05 μm, its function as a protective film may be lowered due to the small thickness, and in some cases, even if a layer containing a fluorine compound is provided, the core of the nitride fluorescent material tends to be affected by the external environment such as temperature and humidity, thereby providing lower durability than the nitride material of the compound layer containing fluorine having a thickness of 0.05 μm or more of the fluorine compound. In the case where the fluoride-containing layer thickness of the fluorine-containing nitride fluorescent material according to the embodiment exceeds 0.8 μm, reflection of light or the like may increase due to the large thickness of the fluoride-containing layer, and in the case where the nitride fluorescent material is applied to a light emitting device, a target emission coefficient cannot be obtained in some cases.
The light emitting device using the prepared nitride fluorescent material as a wavelength conversion element and an excitation device constituting element, wherein the emission wavelength range of the excitation device is 400-450nm, and specifically, the light emitting device emitting mixed color light of light from the light emitting element and fluorescent light from the fluorescent material can be constituted by using an excitation band having a main emission wavelength of the fluorescent material as an excitation light source.
The above light-emitting device may further include a second layer of a light-emitting material having an emission peak wavelength different from that of the first layer, which is appropriately selected, so that the light-emitting device can have a wide color reproducibility and a high color rendering property.
The second fluorescent material more preferably contains at least one fluorescent material having a composition represented by formula (IIa), (IId), (IIf) or (IIg) from the viewpoint of providing high color rendering properties.
(Y，Gd，Tb，Lu)3(Al，Ga)5O12:Ce (IIa)
(Ba、Sr、Ca)2SiO4:Eu (IIb)
Si6-pAlpOpN8-pEu (wherein 0)<p≦4.2) (IIc)
(Ca，Sr)8MgSi4O16(Cl，F，Br)2:Eu (IId)
(Ba，Sr，Ca)Ga2S4:Eu (IIe)
(Ba，Sr，Ca)2Si5N8:Eu (IIf)
(Sr，Ca)AlSiN3：Eu (IIg)
K2(Si，Ge，Ti)F6:Mn (IIh)
(Ba，Sr)MgAl10O17:Mn (IIi)
The average particle diameter of the second fluorescent material is preferably 2 μm or more, 35 μm or less, more preferably 5 μm or more, 30 μm or less. The emission coefficient may be further enhanced when the average particle size reaches or exceeds a prescribed value. When the average particle diameter is less than or equal to a prescribed value, workability in the production process of the light-emitting device can be improved.
In order to better understand the technical solution, the technical solution will be described in detail with reference to the drawings and the specific embodiments.
Example one
A fluorescent material containing strontium, lithium, europium, aluminum and N is prepared. Specifically, for a phosphor consisting of the formula AvBwCxAl3-ySiyNz, where A is Sr, B is Li, C is Eu, SrNu (where u corresponds to 2/3 and is Sr)2Mixture of N and SrN) using SrF2,，LiAlH4AlN and EuF3As a material. In this example, the parameter y in the formula is 0. Weighing the materials to make the molar ratio of Sr/Li/Eu/Al 0.9925/1.2000/0.0075/3.0000, and then placing the materials into a glove box to be mixed in an inert atmosphere to obtain a materialAnd (3) mixing. SrNu and SrF2Is 94/6. Since Li (lithium) tends to fly during baking, the amount of Li (lithium) is larger than the theoretical value. The material mixture was controlled in a crucible and heat-treated in a nitrogen atmosphere at a gauge pressure of 0.92MPa (absolute pressure of 1.02 MPa) at a temperature of 1100 ℃ for 3 hours to provide a calcined product material component Sr0.9925LiEu0.075Al3N4As shown. The calcined product was then diffused and classified to obtain calcined product 1.
Comparative example 1
The calcined product 1 was designated as the nitride fluorescent material of comparative example 1.
Example two
A nitride fluorescent material in the form of powder was prepared in the same manner as in example 1, except that the temperature was changed to 250 ℃.
EXAMPLE III
A powdery nitride phosphor was produced in the same manner as in example 1, except that the concentration of the fluorine gas was changed to 10 vol%.
Example four
A powdery nitride phosphor was prepared in the same manner as in example 1, except that the concentration of the fluorine gas was changed to 5 vol%.
EXAMPLE five
A powdery nitride fluorescent material was prepared in the same manner as in example 1, except that the temperature was changed to 350 ℃.
Comparative example II
A powdery nitride fluorescent material was prepared in the same manner as in example 1, except that the temperature was changed to 30 ℃.
Comparative example III
A nitride fluorescent material in a powder form was prepared in the same manner as in example 1, except that the temperature was changed to 150 ℃.
EXAMPLE six
The fluorescent material obtained in comparative example 2 was heat-treated in air at a temperature of 300 c for a treatment time of 10 hours, thereby providing a nitride fluorescent material in the form of powder.
EXAMPLE seven
The fluorescent material obtained in comparative example 3 was heat-treated in air at a temperature of 300 c for a treatment time of 10 hours, thereby providing a nitride fluorescent material in the form of powder.
Example eight
Calcining the product 1 in the presence of ammonium fluoride (NH)4F) 1 ammonium fluoride was added to the calcined product at a concentration of 5% by mass based on the total mass of the calcined product to give 100% by mass, and nitrogen (N) gas was contained2The treatment is performed at a temperature of 200 c at a concentration of 90 vol% or more for 2) hours to provide the nitride fluorescent material in the form of powder.
Example nine
A nitride fluorescent material in a powder form was prepared in the same manner as in example 8, except that the temperature was changed to 300 ℃.
Example ten
A powdery nitride fluorescent material was prepared in the same manner as in example 9, except that the atmosphere was changed to air.
Comparative example four
A nitride fluorescent material in a powder form was prepared in the same manner as in example 8, except that the temperature was changed to 150 ℃.
Luminescence property
The light emitting characteristics of the resultant nitride fluorescent material were measured. The luminescence property of the nitride fluorescent material was measured by spectrofluorometry, and the wavelength of excitation light was 450 nm. A luminescence spectrum was obtained. The results are reported in Table 1.
Examples 1 to 5 are cases where the calcined product is brought into contact with fluorine gas and heat treatment is carried out in an inert gas atmosphere containing fluorine gas. Examples 6 and 7 are the case where the calcined product was brought into contact with fluorine gas and heat-treated in air. Examples 8 to 10 are cases where the calcined product was contacted with ammonium fluoride in a solid state at ordinary temperature, followed by heat treatment in air. As shown in table 1, after storage under the above conditions, the chromaticity x of all the samples was slightly changed from those of comparative samples 1 to 4, and it was confirmed that the durability was improved. As shown in table 1, the nitride fluorescent material of comparative example 1 contains 0.6% by mass of fluorine element due to the influence of the fluorine compound contained in the material, but after storage in a temperature environment of 85 ℃, the chromaticity change ratio of x 1 is greater than 85% in the relative humidity of the nitride fluorescent material, and the durability is not improved since the product is not in contact with the fluorine-containing substance and is not subjected to heat treatment. In the nitride fluorescent material of comparative example 2, although the calcined product was in contact with the fluorine-containing substance, it is considered that a layer of the fluorine-containing compound was not formed on the surface of the calcined product or in the vicinity of the surface thereof because the heat treatment was not performed, and the nitride fluorescent material showed a large change in the chromium environment x after storage in the above-mentioned environment. In the nitride fluorescent materials of comparative examples 3 and 4, the calcined product was brought into contact with a fluorine-containing substance and heat-treated, but the heat-treatment temperature was 150 ℃ C, which is lower than that of the examples, and it was considered that the formation of the protective film of the fluorine-containing compound was insufficient. For the nitride fluorescent material in comparative example 3, a layer containing a fluorine compound was not formed.
The production method can obtain the nitride fluorescent material with high durability, and is well applied to a light-emitting device, thereby being better applied to an illumination light source. In particular, the light-emitting device can be applied to an illumination light source having remarkably excellent light-emitting characteristics with a laser as an excitation light source, a LED display device, a backlight of a liquid crystal display device, a traffic signal, an illumination switch, various sensors, and various indicators.
Claims (8)
1. The preparation method of the nitride fluorescent powder is characterized in that the fluorescent powder comprises a fluorescent material core and a shell surface, and the molecular formula of the fluorescent material core is AvBwCxAl3-ySiyNzWherein A represents at least one element selected from the group consisting of Ca, Sr, Ba and Mg; b represents at least one element selected from the group consisting of Li, Na and k; c represents at least one element selected from the group Eu, Ce, Tb and Mn; v, w, x, y and z respectively satisfy 0.90-1.00 v, 0.90-1.00 w and 0.001<x≤Y is more than or equal to 0.1 and less than or equal to 0.5, and z is more than or equal to 3.0 and less than or equal to 5.0; the surface of the shell of the fluorescent material is a layer containing fluorine-containing compounds;
the preparation method comprises the following steps: preparation of the formula AvBwCxAl3-ySiyNzAnd contacting the calcined product with a fluorine-containing substance and heat-treating the calcined product at a temperature of 200 ℃ or more and 500 ℃ or less.
2. The method of claim 1, wherein the fluorine-containing substance is at least one selected from the group consisting of F2, CHF3, CF4, NH4HF2, NH4F, SiF4, KrF2, XeF2, XeF4, and NF 3.
3. The method of claim 1, wherein the calcined product is heat-treated in an inert gas.
4. The method of claim 1, wherein the fluorine-containing substance is in a gaseous state, and the calcined product is heat-treated in a gas atmosphere containing an inert gas and the fluorine-containing substance.
5. The method of claim 1, wherein the fluorine-containing substance is fluorine gas.
6. The method of claim 1, wherein the fluorine-containing material is ammonium fluoride.
7. The method of claim 1, wherein the layer containing a fluorine-containing compound has a thickness of 0.05 μm to 0.8 μm.
8. Use of the nitride phosphor of claim 1 in an LD.
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| CN109423284A (en) * | 2017-08-31 | 2019-03-05 | 日亚化学工业株式会社 | Manufacturing method, nitride phosphor and the light emitting device of nitride phosphor |
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| US20170250320A1 (en) * | 2016-02-29 | 2017-08-31 | Nichia Corporation | Method of producing nitride fluorescent material, nitride fluorescent material, and light emitting device using the same |
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