CN113677775A - Surface-coated phosphor particle, method for producing surface-coated phosphor particle, and light-emitting device - Google Patents
Surface-coated phosphor particle, method for producing surface-coated phosphor particle, and light-emitting device Download PDFInfo
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
Abstract
The surface-coated phosphor particle of the present invention comprises: particles containing a fluorescent material having a general formula M and a coating portion for coating the surface of the particles1 aM2 bM3 cAl3N4－dOd(wherein, M1Is more than 1 element selected from Sr, Mg, Ca and Ba, M2Is 1 or more elements selected from Li and Na, M3Is 1 or more elements selected from Eu and Ce), the above-mentioned a, b, c and dSatisfies the following formulae: a is 0.850. ltoreq. a.ltoreq.1.150, b is 0.850. ltoreq. b.ltoreq.1.150, c is 0.001. ltoreq. c.ltoreq.0.015, d is 0. ltoreq. d.ltoreq.0.40, and d/(a + d) < 0.30, and the fluorine element content is 15 to 30% by mass and the mass increase rate measured under predetermined conditions is 15% or less with respect to the entire surface-coated phosphor particles.
Description
Technical Field
The present invention relates to surface-coated phosphor particles, a method for producing surface-coated phosphor particles, and a light-emitting device.
Background
Light emitting devices formed by combining a Light Emitting Diode (LED) and a phosphor are widely used in lighting devices, backlights of liquid crystal display devices, and the like. In particular, when a light-emitting device is used in a liquid crystal display device, high color reproducibility is required, and therefore, it is desirable to use a phosphor having a narrow full width at half maximum (hereinafter, simply referred to as "half-width") of a fluorescence spectrum.
As a red phosphor having a narrow half-value width which has been conventionally used, Eu is known to be useful2+An activated nitride phosphor or oxynitride phosphor. As a typical pure nitride phosphor, there is Sr2Si5N8：Eu2+、CaAlSiN3：Eu2+(abbreviated as CASN), (Ca, Sr) AlSiN3：Eu2+(abbreviated as SCASN) and the like. The CASN phosphor and the SCASN phosphor have peak wavelengths in the range of 610-680 nm, and the half-peak widths of the CASN phosphor and the SCASN phosphor are 75-90 nm and are relatively narrow. However, when these phosphors are used as light emitting devices for liquid crystal displays, a further expansion of the color reproduction range is desired, and phosphors having a narrower half-value width are desired.
In recent years, as a red phosphor showing a narrow band of 70nm or less in half-width, SrLiAl has been known3N4：Eu2+(abbreviated as SLAN) phosphor, and a light-emitting device using the phosphor can be expected to have excellent color rendering properties and color reproducibility.
Patent document 1 discloses a SLAN phosphor having a specific composition.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2017-088881
Disclosure of Invention
The SLAN phosphor is easily decomposed when it is in contact with water. This property becomes an important factor in the decrease in emission intensity with the passage of time. In recent years, further improvement in reliability of a light-emitting device using a SLAN phosphor has been demanded, and further improvement in moisture resistance of the SLAN phosphor has also been demanded.
The results of the research of the inventor show that: the detailed mechanism of the particles including the SLAN phosphor and the nitride phosphor having a crystal structure similar thereto is not determined, but the moisture resistance of the particles can be stably evaluated by using the content of the fluorine element in the entire particles and the mass increase rate before and after the high temperature and high humidity test as an index, and the decrease in the fluorescence intensity when exposed to the water environment can be suppressed by setting the content of the fluorine element to a predetermined value or more and the mass increase rate to a predetermined value or less, and the moisture resistance can be improved.
According to the present invention, there is provided a surface-coated phosphor particle comprising: particles containing a fluorescent material having a general formula M and a coating portion for coating the surface of the particles1 aM2 bM3 cAl3N4－dOd(wherein, M1Is more than 1 element selected from Sr, Mg, Ca and Ba, M2Is 1 or more elements selected from Li and Na, M3Is 1 or more elements selected from Eu and Ce), and the a, b, c and d satisfy the following formulae: a is more than or equal to 0.850 and less than or equal to 1.150, b is more than or equal to 0.850 and less than or equal to 1.150, c is more than or equal to 0.001 and less than or equal to 0.015, d is more than or equal to 0 and less than or equal to 0.40, d/(a + d) is more than or equal to 0 and less than 0.30,
the content of fluorine element in the entire surface-coated phosphor particles is 15 to 30% by mass,
the mass increase rate measured under the following conditions was 15% or less.
(conditions for measuring Mass increase Rate)
The initial mass of the powder composed of the surface-coated phosphor particles was W1, and the mass of the powder after 50 hours at a temperature of 60 ℃ and a humidity of 90% RH was W2, and the mass increase rate was calculated as (W2-W1)/W1 × 100 (%).
Further, according to the present invention, there is provided a method for producing surface-coated phosphor particles, the method for producing surface-coated phosphor particles comprising the steps of: a mixing step of mixing raw materials, a firing step of firing the mixture obtained in the mixing step, and an acid treatment step of mixing the fired product obtained in the firing step with an acid solution;
in the mixing step, when the molar ratio of Al is 3, M is present1The amount of the additive (A) is 1.10 to 1.20.
Further, according to the present invention, there is provided a light-emitting device having the above surface-coated phosphor particles and a light-emitting element.
According to the present invention, there can be provided a technique relating to nitride phosphor particles having improved moisture resistance.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
The surface-coated phosphor particle according to the embodiment includes: particles containing a fluorescent material and a coating portion for coating the surface of the particles. The surface-coated phosphor particles will be described in detail below.
The phosphor constituting the particle of the present embodiment is represented by the general formula M1 aM2 bM3 cAl3N4－dOdAnd (4) showing. a. b, c, 4-d and d represent the molar ratio of the respective elements.
In the above formula, M1Is more than 1 element selected from Sr, Mg, Ca and Ba. Preferably M1At least contains Sr. M1The lower limit of the molar ratio a of (a) is preferably 0.850 or more, more preferably 0.950 or more. On the other hand, M1The upper limit of the molar ratio a of (a) is preferably 1.150 or less, more preferably 1.100 or less, and still more preferably 1.050 or lessThe following steps. By making M1The molar ratio a of (a) is in the above range, whereby the stability of the crystal structure can be improved.
In the above formula, M2Is 1 or more elements selected from Li and Na. Preferably M2Containing at least Li. M2The lower limit of the molar ratio b of (a) is preferably 0.850 or more, more preferably 0.950 or more. On the other hand, M2The upper limit of the molar ratio b of (a) is preferably 1.150 or less, more preferably 1.100 or less, and still more preferably 1.050 or less. By mixing M2The molar ratio b of (a) is in the above range, whereby the stability of the crystal structure can be improved.
In the above formula, M3The element which is an activator added to the mother crystal, i.e., an element constituting an emission center ion of the phosphor, is 1 or more elements selected from Eu and Ce. M3It is selected according to the desired emission wavelength, and preferably contains at least Eu.
M3The lower limit of the molar ratio c of (a) is preferably 0.001 or more, more preferably 0.005 or more. On the other hand, M3The upper limit of the molar ratio c of (a) is preferably 0.015 or less, more preferably 0.010 or less. By mixing M3The lower limit of the molar ratio c of (a) to (b) is set to the above range, whereby sufficient emission intensity can be obtained. In addition, by mixing M3The upper limit of the molar ratio c of (a) is set to the above range, whereby concentration quenching can be suppressed and the emission intensity can be maintained at a sufficient value.
In the above formula, the lower limit of the molar ratio d of oxygen is preferably 0 or more, and more preferably 0.05 or more. On the other hand, the upper limit of the molar ratio d of oxygen is preferably 0.40 or less, and more preferably 0.35 or less. By setting the molar ratio d of oxygen within the above range, the crystal state of the phosphor can be stabilized, and the emission intensity can be maintained at a sufficient value.
The content of the oxygen element in the phosphor is preferably less than 2 mass%, more preferably 1.8 mass% or less. When the content of oxygen is less than 2 mass%, the crystal state of the phosphor is stabilized, and the emission intensity can be maintained at a sufficient value.
By M1The lower limit of the molar ratio of the oxygen to the d/(a + d) calculated from a and d is preferably 0 or more, and more preferablyPreferably 0.05 or more. On the other hand, the upper limit of the value of d/(a + d) is preferably less than 0.30, and more preferably 0.25 or less. By setting d/(a + d) to the above range, the crystal state of the phosphor is stabilized, and the emission intensity can be maintained at a sufficient value.
The surface-coated phosphor particles of the present embodiment have a mass increase rate of 15% or less, measured under the following conditions.
(measurement conditions for the Rate of increase in Mass)
The initial mass of the powder composed of the surface-coated phosphor particles was W1, and the mass of the powder composed of the surface-coated phosphor particles after 50 hours at a temperature of 60 ℃ and a humidity of 90% RH was W2. The mass increase rate was calculated using the formula (W2-W1)/W1X 100 (%).
The surface-coated phosphor particles before measurement are preferably stored in an ultra-low humidity drying oven with a humidity of 1% RH or less in the storage for a predetermined time.
The mass increase rate can be adjusted by controlling the composition and coating form of the coating portion formed on the surface of the phosphor particle.
The surface-coated phosphor particles of the present embodiment include the coating portion, and the rate of increase in mass before and after the durability test is set to 15% or less, whereby the moisture resistance of the phosphor can be improved, and the emission intensity can be maintained for a long period of time. It is considered that the increase in the mass of the surface-coated phosphor particles is caused by hydrolysis and a hydrogen oxidation reaction of the uncoated portion.
In the surface-coated phosphor particles of the present embodiment, the rate of mass increase before and after the durability test is preferably 12% or less, and more preferably 5% or less. By setting the mass increase rate before and after the durability test to the above range, the moisture resistance of the phosphor can be further improved, and the emission intensity can be further maintained for a long period of time.
In the present embodiment, the content of fluorine element in the entire surface-coated phosphor particles is 15 to 30% by mass. The moisture resistance can be improved by setting the content of fluorine element in the entire surface-coated phosphor particles to 15 mass% or more. When the content of fluorine element in the entire surface-coated phosphor particles is 30% by mass or less, the moisture resistance can be improved and the emission intensity can be maintained at a sufficient value.
The lower limit of the content of the fluorine element in the entire surface-coated phosphor particles is more preferably 18 mass% or more, and still more preferably 20 mass% or more. The upper limit of the content of the fluorine element in the entire surface-coated phosphor particles is more preferably 27 mass% or less, and still more preferably 25 mass% or less. When the lower limit of the fluorine element content is set to the above range, the moisture resistance can be further improved. Further, by setting the upper limit of the fluorine content to the above range, the moisture resistance can be further improved and the emission intensity can be maintained at a sufficient value.
The fluorine element is derived from a fluoride of a metal element used as a raw material described later, or is added through a fluorine treatment step described later, and does not form a crystal structure of the phosphor.
In the present embodiment, the content of fluorine elements in the particles and the mass increase rate can be controlled within desired ranges by appropriately adjusting the types of the acid and the solvent in the acid treatment step, the concentration of the acid, the concentration of hydrofluoric acid in the hydrofluoric acid treatment step, the time of the hydrofluoric acid treatment, the heating temperature and the heating time in the heating step performed after the hydrofluoric acid treatment, and the like.
According to the surface-coated phosphor particles of the present embodiment, the fluorescence intensity in a water-exposed environment can be suppressed, and preferably, the decrease in fluorescence intensity in a high-humidity environment such as 90% RH or more can be suppressed, and more preferably, the decrease in fluorescence intensity in a high-temperature high-humidity environment can be suppressed.
The coating portion preferably constitutes at least a part of the surface of the particle including the phosphor. The coating portion preferably contains a fluorine compound containing a fluorine element, and more preferably contains a fluorine compound containing a fluorine element and an aluminum element.
In the fluorine-containing compound, it is preferable that fluorine and aluminum elements are directly covalently bonded, and more specifically, the fluorine-containing compound preferably contains (NH)4)3AlF6Or AlF3Either or both. The fluorine-containing compound may be composed of a single compound containing fluorine and aluminum.
The coating portion constitutes at least a part of the outermost surface of the particle including the phosphor, and thus the moisture resistance of the phosphor constituting the particle can be improved. From the viewpoint of further improving the moisture resistance of the phosphor, it is more preferable that the coating portion contains AlF3。
The form of the coating portion is not particularly limited, and the coating portion may be configured to cover at least a part of the particle surface, or may be configured to cover the entire particle surface. Examples of the form of the coating portion include a form in which a large amount of a particulate fluorine-containing compound is distributed on the surface of the particles containing the fluorescent material, and a form in which the surface of the particles containing the fluorescent material is continuously coated with the fluorine-containing compound.
The surface-coated phosphor particles of the present embodiment have a diffuse reflectance of, for example, 56% or more, more preferably 58% or more, and still more preferably 60% or more, when irradiated with light having a wavelength of 300 nm.
The surface-coated phosphor particles have a diffuse reflectance of, for example, 85% or more, preferably 86% or more, with respect to light irradiation at a peak wavelength of a fluorescence spectrum. By providing such characteristics, the light emission efficiency is further improved, and the light emission intensity is improved.
In the case where the surface-coated phosphor particles of the present embodiment are excited by blue light having a wavelength of 455nm, it is preferable that the peak wavelength is in the range of 640nm to 670nm and the half-width is 45nm to 60 nm. By having such characteristics, excellent color developability and color reproducibility can be expected.
In one example of the surface-coated phosphor particles of the present embodiment, when the surface-coated phosphor particles are excited by blue light having a wavelength of 455nm, the x value of the color purity of the emission color preferably satisfies 0.680. ltoreq. x < 0.735 in the CIE-xy chromaticity diagram. By having such characteristics, excellent color developability and color reproducibility can be expected. A red emission with good color purity can be expected if the value of x is 0.680 or more, and a value of x of 0.735 or more exceeds the maximum value in the CIE-xy chromaticity diagram, and therefore the above range is preferably satisfied.
(method for producing surface-coated phosphor particles)
The surface-coated phosphor particles of the present embodiment can be produced by the following steps: a mixing step of mixing the raw materials; a firing step of firing the mixture obtained in the mixing step; and an acid treatment step of mixing the fired product obtained in the firing step with an acid solution. In addition to the above steps, it is preferable to add a fluorine treatment step of mixing the calcined product subjected to the acid treatment step with a compound containing fluorine; and a heating step of performing a heating treatment on the product obtained in the fluorine treatment step.
(mixing Process)
The mixing step is a step of mixing raw materials weighed so as to obtain the target surface-coated phosphor particles to obtain a powdery raw material mixture. The method of mixing the raw materials is not particularly limited, and for example, there is a method of sufficiently mixing the raw materials using a mixing device such as a mortar, a ball mill, a V-type mixer, or a planetary mill. Strontium nitride, lithium nitride, or the like, which reacts vigorously with moisture and oxygen in the air, is preferably treated in a glove box or a mixing apparatus, the interior of which is replaced with an inert atmosphere.
In the mixing step, M is preferably set to a molar ratio of Al of 31The amount of (2) is 1.10 or more in terms of a molar ratio. By making M1By setting the molar ratio of M to 1.10 or more in the firing step1M in the phosphor1Deficiency of (A) M1Defects are not easily generated, and the crystallinity of the crystal structure can be well maintained. As a result, a fluorescence spectrum in a narrow band region was obtained, and it was estimated that the emission intensity could be improved. In the mixing step, it is preferable that M be 3 as the molar ratio of Al1The amount of (3) is 1.20 or less in terms of a molar ratio. By mixing M1Is 1.20 or less in terms of a molar ratio, so that inclusion of M can be suppressed1The addition of the hetero-phase in (2) makes it easy to remove the hetero-phase by the acid treatment process, and the light emission intensity can be improved.
Each raw material used in the mixing step may contain 1 or more kinds selected from a simple metal of a metal element contained in the composition of the phosphor and a metal compound containing the metal element. Examples of the metal compound include a nitride, a hydride, a fluoride, an oxide, a carbonate, and a chloride. Among them, M is contained as a component for improving the emission intensity of the phosphor1And M2The metal compound of (2) is preferably a nitride. Specifically, as containing M1As the metal compound of (2), Sr is mentioned3N2、SrN2SrN, etc. As containing M2The metal compound of (2) includes Li3N、LiN3And the like. As containing M3The metal compound of (1) includes Eu2O3、EuN、EuF3. As the metal compound containing Al, AlN and AlH are exemplified3、AlF3、LiAlH4And the like. A flux may be added as necessary. Examples of the flux include LiF and SrF2、BaF2、AlF3And the like.
(firing Process)
In the firing step, the mixture of the raw materials is filled into a firing vessel and fired. The firing container preferably has a structure for improving airtightness, and the inside of the firing container is preferably filled with an atmosphere gas of a non-oxidizing gas such as argon, helium, hydrogen, or nitrogen. The firing vessel is preferably made of a material which is stable in a high-temperature atmosphere and hardly reacts with the mixture of the raw materials and the reaction product thereof, and for example, a vessel made of boron nitride or carbon, or a vessel made of a high-melting-point metal such as molybdenum, tantalum, or tungsten is preferably used.
[ firing temperature ]
The lower limit of the firing temperature in the firing step is preferably 900 ℃ or higher, more preferably 1000 ℃ or higher, and still more preferably 1100 ℃ or higher. On the other hand, the upper limit of the firing temperature is preferably 1500 ℃ or less, more preferably 1400 ℃ or less, and still more preferably 1300 ℃ or less. By setting the firing temperature in the above range, unreacted raw materials after the completion of the firing step can be reduced, and decomposition of the main crystal phase can be suppressed.
[ kinds of firing atmosphere gas ]
As a kind of the firing atmosphere gas in the firing step, for example, a gas containing nitrogen as an element is preferably used. Specifically, nitrogen and/or ammonia may be mentioned, and nitrogen is particularly preferable. In addition, inert gases such as argon and helium can be used preferably. The firing atmosphere gas may be composed of 1 gas, or may be a mixed gas of a plurality of gases.
[ pressure of firing atmosphere gas ]
The pressure of the firing atmosphere gas is selected depending on the firing temperature, and is usually in a pressurized state in the range of 0.1 MPa.G to 10 MPa.G. The higher the pressure of the firing atmosphere gas, the higher the decomposition temperature of the phosphor, but considering industrial productivity, it is preferably 0.5MPa G to 1MPa G.
[ firing time ]
The firing time in the firing step may be selected within a time range in which the following disadvantages do not occur: a large amount of unreacted materials, insufficient particle growth of the phosphor, or a decrease in productivity. In the method for producing surface-coated phosphor particles according to the embodiment, the lower limit of the firing time is preferably 0.5 hours or more, more preferably 1 hour or more, and still more preferably 2 hours or more. The upper limit of the firing time is preferably 48 hours or less, more preferably 36 hours or less, and still more preferably 24 hours or less.
The state of the fired product obtained in the firing step may be in various forms such as powder and block depending on the raw material mixture and firing conditions. When the phosphor particles are prepared for practical use as surface-coated phosphor particles, the method may further include a crushing/pulverizing step and/or a classifying step of forming the obtained fired product into a powder having a predetermined size. In view of absorption efficiency of excitation light and obtaining sufficient light emission efficiency, the average particle size of the surface-coated phosphor particles is preferably adjusted to 5 μm to 30 μm when used as surface-coated phosphor particles for LEDs. In the crushing/pulverizing step, in order to prevent the mixing of impurities resulting from the treatment, the parts of the equipment that come into contact with the fired product are preferably made of high-toughness ceramics such as silicon nitride, alumina, and sialon.
(acid treatment Process)
The acidic solution used in the acid treatment step is preferably an aqueous solution, and the contact with the acidic solution is usually a method of dispersing the baked product in an acidic aqueous solution containing 1 or more of nitric acid, hydrochloric acid, acetic acid, sulfuric acid, formic acid, and phosphoric acid, and stirring the solution for several minutes to several hours.
Specifically, the fired product may be dispersed in a mixed solution of an organic solvent and an acidic solution, stirred for several minutes to several hours, and then washed with the organic solvent. By the acid treatment, the impurity elements contained in the raw material, the impurity elements derived from the firing vessel, the heterogeneous phase generated in the firing step, and the impurity elements mixed in the pulverization step can be dissolved and removed. At the same time, the fine powder can be removed, so that the scattering of light can be suppressed and the light absorption rate of the phosphor can be improved.
The organic solvent may be methanol, ethanol, alcohol such as 2-propanol, or ketone such as acetone. The acidic solution is more than 1 of nitric acid, hydrochloric acid, acetic acid, sulfuric acid, formic acid and phosphoric acid. The mixing ratio of these solutions is adjusted to a concentration of 0.1 to 3 vol% of the acidic solution with respect to the organic solvent, for example.
(fluorine treatment Process)
In the fluorine treatment step, a hydrofluoric acid aqueous solution is preferably used as the compound containing a fluorine element to be mixed with the burned product subjected to the acid treatment step. The lower limit of the concentration of the hydrofluoric acid aqueous solution is preferably 25% or more, more preferably 27% or more, and further preferably 30% or more. On the other hand, the upper limit of the concentration of the hydrofluoric acid aqueous solution is preferably 38% or less, more preferably 36% or less, and still more preferably 34% or less. By setting the concentration of the hydrofluoric acid aqueous solution to 25% or more, it is possible to form inclusion (NH) on at least a part of the outermost surface of the phosphor-containing particle4)3AlF6The coating portion of (1). On the other hand, by setting the concentration of the hydrofluoric acid aqueous solution to 38% or less, the particles and the hydrofluoric acid can be suppressedThe reaction of the acid becomes overexcited.
The mixture of the calcined product subjected to the acid treatment step and the hydrofluoric acid aqueous solution may be carried out by a stirring device such as a stirrer. The lower limit of the mixing time of the fired product and the hydrofluoric acid aqueous solution is preferably 5 minutes or more, more preferably 10 minutes or more, and still more preferably 15 minutes or more. On the other hand, the upper limit of the mixing time of the fired product and the hydrofluoric acid aqueous solution is preferably 30 minutes or less, more preferably 25 minutes or less, and further preferably 20 minutes or less. By setting the mixing time of the fired product and the hydrofluoric acid aqueous solution within the above range, inclusion (NH) can be stably formed on at least a part of the outermost surface of the phosphor-containing particle4)3AlF6The coating portion of (1).
(heating step)
The product obtained by the fluorine treatment contains (NH) as a coating portion4)3AlF6In the case of (3), the heating step may be performed after the above step. The lower limit of the heating temperature in the heating step is preferably 220 ℃ or higher, and more preferably 250 ℃ or higher. On the other hand, the upper limit of the heating temperature is preferably 500 ℃ or less, more preferably 450 ℃ or less, and still more preferably 400 ℃ or less.
(NH) can be converted by setting the heating temperature to 220 ℃ or higher and causing the following reaction formula (1) to proceed4)3AlF6Conversion to AlF3。
(NH4)3AlF6→AlF3+3NH3+3HF……(1)
On the other hand, by setting the heating temperature to 500 ℃ or lower, the crystal structure of the phosphor can be favorably maintained, and the emission intensity can be improved.
The lower limit of the heating time is preferably 1 hour or more, more preferably 1.5 hours or more, and further preferably 2 hours or more. On the other hand, the upper limit of the heating time is preferably 6 hours or less, more preferably 5.5 hours or less, and further preferably 5 hours or less. By setting the heating time within the above range, (NH) can be adjusted4)3AlF6Reliable conversion to moisture resistanceHigh AlF3。
The heating step is preferably performed in the atmosphere or in a nitrogen atmosphere. Accordingly, the substance of the heating atmosphere itself can generate the target substance without inhibiting the reaction formula (1).
In the present embodiment, the following surface-coated phosphor particles can be obtained by appropriately adjusting the types of acid and solvent in the acid treatment step, the acid concentration, the hydrofluoric acid concentration in the fluorine treatment step, the fluorine treatment time, the heating temperature and heating time in the heating step performed after the fluorine treatment, and the like: a coating portion is formed to coat the surface of the phosphor-containing particle, and the fluorine element content is 15 to 30% by mass relative to the entire surface-coated phosphor particle, and the mass increase rate measured under the above conditions is 15% or less.
According to the above-described method for producing surface-coated phosphor particles, nitride phosphor particles having improved moisture resistance and further capable of maintaining emission intensity for a long period of time can be produced.
(light-emitting device)
The light-emitting device according to the embodiment includes the surface-coated phosphor particles and the light-emitting element according to the above-described embodiment.
As the light emitting element, an ultraviolet LED, a blue LED, a fluorescent lamp, or a combination thereof can be used alone. The light emitting element preferably emits light having a wavelength of 250nm to 550nm, and particularly preferably a blue LED light emitting element having a wavelength of 420nm to 500 nm.
As the phosphor particles used for the light emitting device, in addition to the surface-coated phosphor particles of the above embodiment, phosphor particles having other emission colors may be used in combination. Examples of the phosphor particles of other emission colors include blue-emitting phosphor particles, green-emitting phosphor particles, yellow-emitting phosphor particles, orange-emitting phosphor particles and red phosphors, and examples thereof include Ca3Sc2Si3O12：Ce、CaSc2O4：Ce、β－SiAlON：Eu、Y3Al5O12：Ce、Tb3Al5O12：Ce、(Sr、Ca、Ba)2SiO4：Eu、La3Si6N11：Ce、α－SiAlON：Eu、Sr2Si5N8: eu, and the like. The phosphor particles that can be used in combination with the surface-coated phosphor particles of the above-described embodiments are not particularly limited, and can be appropriately selected according to the luminance, color rendering properties, and the like required for the light-emitting device. By mixing the surface-coated phosphor particles of the above embodiment with phosphor particles of another luminescent color, white color of various color temperatures such as daylight color and bulb color can be realized.
Examples of the light-emitting device include a lighting device, a backlight device, an image display device, and a signal device.
The light-emitting device of the present embodiment can achieve high emission intensity and can improve reliability by using the surface-coated phosphor particles of the above embodiments.
While the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above-described configurations may be adopted.
Examples
The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.
(example 1)
To obtain a compound having M1 aM2 bM3 cAl3N4－dOdShown composition and satisfies M1＝Sr、M2＝Li、M3Eu phosphor, Sr3N2(manufactured by Taiheiyo Cement Co., Ltd.), Li3N (manufactured by Material Co., Ltd.), AlN (manufactured by Tokuyama Corporation), Eu (manufactured by Tokuyama Corporation)2O3(manufactured by shin-Etsu chemical Co., Ltd.) was used as each raw material, and LiF (manufactured by Wako pure chemical industries, Ltd.) was used as a flux. When the molar ratio of Al is 3, the amount of Sr charged is 1.15 in terms of molar ratio, and the amount of Eu charged is 0.0115 in terms of molar ratio. 5 mass% of LiF was added to 100 mass% of the total amount of the raw material mixture and the flux. Eu is added in a molar ratio of 3, as described above, where Al is present in the molar ratioIs 0.0115.
The method for producing the surface-coated phosphor particles of example 1 is described below in detail.
In the atmosphere, AlN and Eu were weighed and mixed2O3After LiF, the coagulation was released by using a nylon sieve having a mesh size of 150 μm to obtain a premix.
The premix is transferred to a glove box which maintains an inert atmosphere having a moisture content of 1ppm or less and an oxygen content of 1ppm or less. Then, the Sr was weighed so that the stoichiometric ratio (a 1, b 1) was 15% in excess of the value of a and 20% in excess of the value of b3N2And Li3After N, the mixture was additionally blended and mixed, and then the coagulation was released by a nylon sieve having a mesh size of 150 μm to obtain a raw material mixture of a phosphor. Sr and Li are more than the theoretical value because Sr and Li are easily scattered during firing.
Subsequently, the raw material mixture was charged into a cylindrical BN container (available from electrochemical co., ltd.) with a lid.
Next, the container filled with the raw material mixture of the phosphor was taken out from the glove box, and then set in an electric furnace (manufactured by fuji electric wave industries, ltd.) with a carbon heater provided with a graphite heat insulating material, and a firing step was performed.
In the firing step, the inside of the electric furnace was once degassed to a vacuum state, and then firing was started from room temperature under a pressurized nitrogen atmosphere of 0.8MPa · G. After the temperature in the electric furnace reached 1100 ℃, firing was continued for 8 hours while maintaining the temperature, and thereafter, cooling was performed to room temperature. The fired material obtained was pulverized in a mortar, and then classified by a nylon sieve having a mesh size of 75 μm and collected.
As an acid treatment step, HNO was added to MeOH (99%) (manufactured by Kokai chemical Co., Ltd.)3(60%) (Wako pure chemical industries, Ltd.) was added to the resulting mixture, and the mixture was stirred for 3 hours and classified to obtain a phosphor powder.
The obtained phosphor powder was added to a 30% hydrofluoric acid aqueous solution, and stirred for 15 minutes to perform a fluorine treatment step. After the fluorine treatment step, the solution was washed with MeOH by decantation until the solution became neutral, and after solid-liquid separation by filtration, the solid content was dried and all of the solid content was passed through a sieve having a mesh size of 45 μm to release the aggregation, thereby obtaining surface-coated phosphor particles of example 1.
(example 2)
After the fluorine treatment, the phosphor powder, from which the aggregation was released by passing the entire powder through a sieve having a mesh size of 45 μm, was subjected to a heat treatment at 300 ℃ for 4 hours in an atmospheric atmosphere, and the surface-coated phosphor particles of example 2 were obtained in the same amounts and in the same steps as those of example 1.
(example 3)
The surface-coated phosphor particles of example 3 were obtained in the same manner as in example 1 except that the phosphor powder, from which the coagulation was released by passing the entire powder through a sieve having a mesh size of 45 μm after the fluorine treatment, was subjected to a heat treatment at 400 ℃ for 4 hours in an atmospheric atmosphere.
Comparative example 1
Phosphor particles of comparative example 1 were obtained according to the same charging amounts and procedures of the raw materials as in example 1 except that a 20% hydrofluoric acid aqueous solution was used for the fluorine treatment.
Comparative example 2
Phosphor particles of comparative example 2 were obtained in accordance with the same charging amounts and procedures of the raw materials as in example 1, except that the phosphor powder was subjected to a fluorine treatment using a 20% hydrofluoric acid aqueous solution, and then all of the phosphor powder, from which the aggregation was released by passing through a sieve having a mesh size of 45 μm, was subjected to a heating treatment at 400 ℃ for 4 hours in an atmospheric atmosphere.
The chemical composition (i.e., general formula: M) was determined for the total of all crystal phases of the surface-coated phosphor particles of each example and the phosphor particles of each comparative example1 aM2 bM3 cAl3N4－dOd) Subscripts a to d of each element (a) to (d).
When the subscripts a to d are obtained, the obtained phosphor particles are analyzed by the following method. That is, Sr, Li, Al and Eu were calculated by an ICP emission spectrometer (CIROS-120, manufactured by SPECTRO corporation), and O and N were calculated by using the analysis results of an oxynitride analyzer (EMGA-920, manufactured by horiba, Ltd.). The values of a to d relating to the phosphors of the examples and comparative examples are shown in table 1.
(content of fluorine element)
The fluorine element content in the entire surface-coated phosphor particles of each example and the fluorine element content in the entire phosphor particles of each comparative example were calculated using the analysis results obtained by using a sample combustion apparatus (AQF-2100H, manufactured by mitsubishi chemical ANALYTECH) and an ion chromatography (ICS 1500, manufactured by DIONEX, japan).
(analysis based on X-ray diffraction method)
The surface-coated phosphor particles of each example and the phosphor particles of each comparative example were confirmed for their crystal structures by a powder X-ray diffraction pattern using CuK α rays using an X-ray diffraction apparatus (UltimaIV, manufactured by ltd. In example 1, (NH) was observed in the range of 16.5 ° to 17.5 ° in 2 θ4)3AlF6The corresponding peak. In examples 2 and 3, AlF was observed in the range of 2. theta. from 14 to 15 °3The corresponding peak.
In comparative example 1, the same as (NH) was observed4)3AlF6The corresponding small peak was weaker than that in example 1, and the amount of the product was considered to be considerably small. In comparative example 2, AlF was observed3The corresponding peak was weaker than those in examples 2 and 3, and the amount of the produced product was considered to be considerably small.
(surface analysis based on XPS)
Surface analysis by XPS was performed on the surface-coated phosphor particles of each example and the phosphor particles of each comparative example. In the surface-coated phosphor particles of each example, Al and F were present on the outermost surface of the phosphor particles, and it was confirmed that Al and F were covalently bonded. In the surface-coated phosphor particles of example 1, (NH) was obtained from the results of XPS-based surface analysis and X-ray diffraction-based analysis4)3AlF6Constituting at least a part of the outermost surface of the phosphor particleIn the surface-coated phosphor particles of examples 2 and 3, AIF3Constituting at least a part of the outermost surface of the phosphor particles.
(diffuse reflectance)
An integrating sphere device (ISV-469) was attached to a UV-visible spectrophotometer (V-550) manufactured by Nippon spectral Co., Ltd., and the diffuse reflectance was measured. The base line was corrected by a standard reflection plate (Spectralon), and a solid sample holder filled with the surface-coated phosphor particles of each example or the phosphor particles of each comparative example was mounted, and the diffuse reflectance for light having a wavelength of 300nm and the diffuse reflectance for light having a peak wavelength were measured.
(luminescent Property)
The chroma x was measured with a spectrophotometer (MCPD-7000, manufactured by Otsuka Denshi Co., Ltd.) and calculated according to the following procedure.
The surface-coated phosphor particles of each example or the phosphor particles of each comparative example were filled so that the surface of the concave cuvette became smooth, and an integrating sphere was attached. Blue monochromatic light split from a light emitting source (Xe lamp) into 455nm wavelength is introduced into the integrating sphere using an optical fiber. The sample of the phosphor is irradiated with the blue monochromatic light as an excitation source, and the fluorescence spectrum of the sample is measured.
The peak wavelength and the half width of the peak were determined from the obtained fluorescence spectrum data.
Further, the chromaticity x is calculated as follows: according to the wavelength region data in the range from 465nm to 780nm of the fluorescence spectrum data, based on JIS Z8724: 2015, calculating the ratio of JIS Z8781-3: 2016 (chromaticity x) of CIE chromaticity coordinates of an XYZ color system.
(measurement of Mass increase Rate)
The powder comprising the surface-coated phosphor particles of each example was stored in an ultra-low humidity drying oven having an in-house humidity of 1% RH or less, in which the powder was not deteriorated. 1g of powder comprising the surface-coated phosphor particles of each example was uniformly spread in a 40mm phi petri dish. The mass was measured together with the petri dish on which the powder was placed, and the mass of the petri dish measured in advance was subtracted from the measured mass, thereby measuring the initial mass W1 of the powder in the petri dish.
Next, a high temperature and high humidity test was performed by using a constant temperature and humidity apparatus (IW-222, manufactured by Yamaduo scientific Co., Ltd.) under conditions of a temperature of 60 ℃ and a humidity of 90% RH for 50 hours. Thereafter, the petri dish was taken out from the thermo-hygrostat, the mass was measured together with the petri dish on which the powder was placed for 10 minutes, and the mass of the petri dish measured in advance was subtracted from the measured mass, thereby measuring the initial mass W2 of the powder in the petri dish.
The mass increase rate was calculated from the obtained W1 and W2 by using the formulae (W2-W1)/W1X 100 (%). The mass increase rate of the phosphor particles of the comparative example was also calculated by the same method as described above. The obtained results are shown in table 1.
(luminous intensity ratio)
The surface-coated phosphor particles of each example and the phosphor particles of each comparative example were measured for emission intensity I before the start of the high-temperature high-humidity test0. Subsequently, the emission intensity I after a high temperature and high humidity test was measured under an atmosphere of 60 ℃ and 90% RH for 50 hours. Calculating the luminous intensity ratio I/I from the obtained measured values0(%). With respect to the luminous intensity ratio I/I0The results are shown in Table 1.
The emission intensity was measured using a spectrofluorometer (F-7000, manufactured by Hitachi high tech., Ltd.) calibrated with rhodamine B and a secondary standard light source. Namely, the fluorescence spectrum at an excitation wavelength of 455nm was measured using a solid sample holder attached to a photometer.
The peak wavelength of the fluorescence spectrum of the surface-coated phosphor particles of each example and the phosphor particles of each comparative example was 656 nm. The intensity value of the peak wavelength of the fluorescence spectrum is set as the emission intensity of the surface-coated phosphor particles or the phosphor particles.
As shown in table 1, it was confirmed that in the surface-coated phosphor particles of examples 1 to 3 in which the mass increase rate was suppressed to 15% or less, the decrease in emission intensity after the high-temperature high-humidity test was suppressed as compared with comparative examples 1 and 2. It is considered that in examples 1 to 3, the moisture resistance is improved by providing the coating portion having a mass increase rate of 15% or less, and the light emission intensity can be maintained for a long period of time. In contrast, it was confirmed that the phosphor particles of comparative examples 1 and 2 had a mass increase rate of more than 15% and significantly reduced the emission intensity after the high-temperature and high-humidity test.
The present application claims priority based on japanese application No. 2019-074460, filed on 9/4/2019, the entire disclosure of which is incorporated herein by reference.
Claims (10)
1. A surface-coated phosphor particle comprising: a particle containing a fluorescent material and a coating portion for coating the surface of the particle,
the phosphor has a general formula M1 aM2 bM3 cAl3N4－dOdThe composition shown in the specification, wherein M1Is more than 1 element selected from Sr, Mg, Ca and Ba, M2Is 1 or more elements selected from Li and Na, M3Is 1 or more elements selected from Eu and Ce, and a, b, c and d satisfy the following formulae: a is more than or equal to 0.850 and less than or equal to 1.150, b is more than or equal to 0.850 and less than or equal to 1.150, c is more than or equal to 0.001 and less than or equal to 0.015, d is more than or equal to 0 and less than or equal to 0.40, d/(a + d) is more than or equal to 0 and less than 0.30,
the content of fluorine element in the surface-coated phosphor particles is 15 to 30% by mass based on the whole surface-coated phosphor particles,
the mass increase rate measured under the following conditions is 15% or less,
mass increase rate measurement conditions:
the initial mass of the powder composed of the surface-coated phosphor particles was W1, and the mass of the powder after 50 hours at a temperature of 60 ℃ and a humidity of 90% RH was W2, and the mass increase rate was calculated as (W2-W1)/W1 × 100 (%).
2. The surface-coated phosphor particle according to claim 1, wherein the coating portion constitutes at least a part of the outermost surface of the particle and contains a fluorine compound containing a fluorine element.
3. The surface-coated phosphor particle according to claim 1 or 2, wherein the coating portion contains a fluorine compound containing a fluorine element and an aluminum element.
4. The surface-coated phosphor particle according to any one of claims 1 to 3,
the M is1At least contains Sr, M2Containing at least Li, said M3At least comprising Eu.
5. The surface-coated phosphor particle according to any one of claims 1 to 4, wherein the diffuse reflectance upon light irradiation at a wavelength of 300nm is 56% or more, and the diffuse reflectance upon light irradiation at a peak wavelength of a fluorescence spectrum is 85% or more.
6. The surface-coated phosphor particle according to any one of claims 1 to 5, wherein the peak wavelength is in the range of 640nm to 670nm and the half-width is 45nm to 60nm when the particle is excited by blue light having a wavelength of 455 nm.
7. The surface-coated phosphor particle according to any one of claims 1 to 6, wherein an x value of color purity of a luminescent color in a CIE-xy chromaticity diagram satisfies 0.680. ltoreq. x < 0.735 when excited by blue light having a wavelength of 455 nm.
8. A method for producing surface-coated phosphor particles according to any one of claims 1 to 7, comprising the steps of:
a mixing step of mixing the raw materials,
a firing step of firing the mixture obtained in the mixing step, and
an acid treatment step of mixing the fired product obtained in the firing step with an acid solution;
in the mixing step, when the molar ratio of Al is 3, M is1The amount of (b) is 1.10 to 1.20 in terms of molar ratio.
9. The method for producing surface-coated phosphor particles according to claim 8, wherein in the acid treatment step, a hydrofluoric acid aqueous solution having a fluorine concentration of 25% or more is used as the acidic solution.
10. A light-emitting device comprising the surface-coated phosphor particles according to any one of claims 1 to 7 and a light-emitting element.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2019074460 | 2019-04-09 | ||
| JP2019-074460 | 2019-04-09 | ||
| PCT/JP2020/014911 WO2020209148A1 (en) | 2019-04-09 | 2020-03-31 | Surface-coated fluorescent particles, production method for surface-coated fluorescent particles, and light-emitting device |
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| KR (1) | KR20210150475A (en) |
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| JP2023166642A (en) * | 2020-10-13 | 2023-11-22 | デンカ株式会社 | Phosphor, method for producing phosphor, and luminescence device |
| JP2023166643A (en) * | 2020-10-13 | 2023-11-22 | デンカ株式会社 | Phosphor and luminescence device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1351640A (en) * | 1999-03-24 | 2002-05-29 | 萨尔诺夫公司 | Long persistence alkaline earth sulfide phosphors |
| JP2017155209A (en) * | 2016-02-29 | 2017-09-07 | 日亜化学工業株式会社 | Manufacturing method of nitride phosphor, nitride phosphor and light-emitting device |
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| US6242043B1 (en) * | 1999-03-24 | 2001-06-05 | Sarnoff Corporation | Method of improving moisture resistance for inorganic materials that are sensitive to moisture |
| JP5578597B2 (en) * | 2007-09-03 | 2014-08-27 | 独立行政法人物質・材料研究機構 | Phosphor, method for manufacturing the same, and light emitting device using the same |
| US9570655B2 (en) * | 2011-01-18 | 2017-02-14 | Sharp Kabushiki Kaisha | Semiconductor light-emitting device |
| US9546319B2 (en) * | 2012-05-22 | 2017-01-17 | Koninklijke Philips N.V. | Phosphors, such as new narrow-band red emitting phosphors for solid state lighting |
| US10266766B2 (en) * | 2012-11-13 | 2019-04-23 | Denka Company Limited | Phosphor, light-emitting element and lighting device |
| JP2015224339A (en) * | 2014-05-30 | 2015-12-14 | 株式会社東芝 | Phosphor, production method thereof, and light emitting device |
| CN105400513A (en) * | 2015-07-21 | 2016-03-16 | 杭州萤鹤光电材料有限公司 | Red phosphor powder and preparation method thereof |
| JP6291675B2 (en) | 2015-11-11 | 2018-03-14 | 日亜化学工業株式会社 | Nitride phosphor manufacturing method, nitride phosphor and light emitting device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1351640A (en) * | 1999-03-24 | 2002-05-29 | 萨尔诺夫公司 | Long persistence alkaline earth sulfide phosphors |
| JP2017155209A (en) * | 2016-02-29 | 2017-09-07 | 日亜化学工業株式会社 | Manufacturing method of nitride phosphor, nitride phosphor and light-emitting device |
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| WO2020209148A1 (en) | 2020-10-15 |
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