WO2012036016A1 - 蛍光体および発光装置 - Google Patents

蛍光体および発光装置 Download PDF

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Publication number
WO2012036016A1
WO2012036016A1 PCT/JP2011/070206 JP2011070206W WO2012036016A1 WO 2012036016 A1 WO2012036016 A1 WO 2012036016A1 JP 2011070206 W JP2011070206 W JP 2011070206W WO 2012036016 A1 WO2012036016 A1 WO 2012036016A1
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Prior art keywords
phosphor
light
general formula
light emitting
sialon
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PCT/JP2011/070206
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English (en)
French (fr)
Japanese (ja)
Inventor
大地 碓井
康博 白川
博文 竹村
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株式会社東芝
東芝マテリアル株式会社
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Application filed by 株式会社東芝, 東芝マテリアル株式会社 filed Critical 株式会社東芝
Priority to KR1020137006644A priority Critical patent/KR101476561B1/ko
Priority to JP2012533950A priority patent/JPWO2012036016A1/ja
Priority to CN201180044441.6A priority patent/CN103119126B/zh
Publication of WO2012036016A1 publication Critical patent/WO2012036016A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L33/50—Wavelength conversion elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials

Definitions

  • Embodiments described herein relate generally to a phosphor and a light emitting device.
  • the phosphor powder is used, for example, in a light-emitting device such as a light-emitting diode (LED).
  • the light emitting device includes, for example, a semiconductor light emitting element that is arranged on a substrate and emits light of a predetermined color, and a phosphor that emits visible light when excited by light such as ultraviolet light and blue light emitted from the semiconductor light emitting element.
  • the semiconductor light emitting element of the light emitting device for example, GaN, InGaN, AlGaN, InGaAlP or the like is used.
  • the phosphor of the phosphor powder include a blue phosphor, a green phosphor, and a yellow phosphor that are excited by light emitted from the semiconductor light emitting element and emit blue light, green light, yellow light, and red light, respectively.
  • a phosphor, a red phosphor or the like is used.
  • the light emitting device can adjust the color of the emitted light by including various phosphor powders such as a red phosphor in the sealing resin. That is, by using a combination of a semiconductor light emitting element and a phosphor powder that absorbs light emitted from the semiconductor light emitting element and emits light in a predetermined wavelength region, the light emitted from the semiconductor light emitting element and the phosphor powder are used. It becomes possible to emit light in the visible light region and white light by the action of the light emitted from.
  • a phosphor having a europium activated sialon (Si—Al—O—N) structure containing strontium is known as the phosphor.
  • phosphors with a sialon (Si—Al—O—N) structure have a problem that when used in a high temperature region of about 100 ° C., the emission intensity is lower than when used in a normal temperature (25 ° C.) region. was there.
  • the fact that the emission intensity of the phosphor does not decrease or the degree of decrease when used in a high temperature region of about 100 ° C. compared to when used in a normal temperature region is referred to as good temperature characteristics.
  • the fact that the emission intensity of the phosphor is greatly reduced when used in a high temperature region of about 100 ° C. compared to the case where it is used in a normal temperature region is referred to as poor temperature characteristics.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a phosphor and a light-emitting device having good temperature characteristics.
  • the phosphor and the light emitting device of the embodiment have been completed by finding that the temperature characteristics are improved by adding a specific amount of carbon to a phosphor having a specific composition.
  • the phosphor of the embodiment solves the above-mentioned problems, and the following general formula (1)
  • the light-emitting device of the embodiment solves the above-described problems.
  • a substrate, a semiconductor light-emitting element that is arranged on the substrate and emits ultraviolet light to blue light, and a light-emitting surface of the semiconductor light-emitting element are provided.
  • a light emitting unit including a phosphor that emits visible light when excited by light emitted from the semiconductor light emitting element, and the phosphor includes the phosphor of the embodiment. .
  • An example of the emission spectrum of a light-emitting device. 6 shows another example of an emission spectrum of the light emitting device.
  • the phosphor and the light emitting device of the embodiment will be described.
  • the phosphor of the embodiment includes a green phosphor that emits green light when excited by ultraviolet light to blue light, and a red phosphor that emits red light when excited by ultraviolet light to blue light.
  • Green phosphor The green phosphor has the following general formula (1)
  • Sr sialon green phosphor Is a phosphor that emits green light when excited by ultraviolet to blue light.
  • the europium-activated sialon phosphor containing Sr is also referred to as “Sr sialon green phosphor”.
  • the crystal system of Sr sialon green phosphor is orthorhombic.
  • x is a number that satisfies 0 ⁇ x ⁇ 1, preferably 0.025 ⁇ x ⁇ 0.5, and more preferably 0.25 ⁇ x ⁇ 0.5.
  • the fired body obtained in the firing step is not a phosphor, and when x is 1, the luminous efficiency of the green phosphor powder is low.
  • x is preferably a number satisfying 0.025 ⁇ x ⁇ 0.5, and more preferably a number satisfying 0.25 ⁇ x ⁇ 0.5, even if 0 ⁇ x ⁇ 1.
  • the total subscript (1-x) ⁇ of Sr is a number satisfying 0 ⁇ (1-x) ⁇ ⁇ 4.
  • the total subscript x ⁇ of Eu is a number satisfying 0 ⁇ x ⁇ ⁇ 4. That is, in the general formula (1), the total subscripts of Sr and Eu are numbers exceeding 0 and less than 4, respectively.
  • ⁇ , ⁇ , ⁇ and ⁇ are numerical values converted when ⁇ is 3.
  • ⁇ , which is a subscript of Si is a number satisfying 9 ⁇ ⁇ 15 as a numerical value converted when ⁇ is 3.
  • ⁇ , which is a subscript of Al is a number satisfying 1 ⁇ ⁇ ⁇ 5 as a numerical value converted when ⁇ is 3.
  • ⁇ , which is a subscript of O is a number satisfying 0.5 ⁇ ⁇ ⁇ 3 when a value of ⁇ is 3.
  • ⁇ , which is a subscript of N is a number satisfying 10 ⁇ ⁇ ⁇ 25 when the numerical value converted when ⁇ is 3.
  • the composition of the phosphor obtained by firing is an orthorhombic system represented by the general formula (1).
  • the Sr sialon green phosphor may be different.
  • the Sr sialon green phosphor represented by the general formula (1) usually takes the form of a single crystal powder.
  • the Sr sialon green phosphor represented by the general formula (1) contains carbon in a proportion of 1 ppm to 5000 ppm, preferably 5 ppm to 1000 ppm, more preferably 50 ppm to 300 ppm.
  • the carbon content is the ratio of the mass of carbon to the total mass of the green phosphor including carbon.
  • the Sr sialon green phosphor usually takes the form of a single crystal powder, but a large amount of carbon exists in the vicinity of the surface of each particle constituting the phosphor powder.
  • the Sr sialon green phosphor is preferable because the luminance at room temperature (25 ° C.) is high and the decrease in luminance at a high temperature of about 150 ° C. is small. If the carbon content is less than 1 ppm, the Sr sialon green phosphor may have a significant decrease in luminance at high temperatures. If the carbon content exceeds 5000 ppm, the Sr sialon green phosphor may have low brightness at room temperature.
  • the Sr sialon green phosphor powder has an average particle size of preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 20 ⁇ m, and even more preferably 10 ⁇ m to 20 ⁇ m.
  • the average particle diameter is a value measured by the Coulter counter method, it means the median D 50 of the cumulative volume distribution.
  • the Sr sialon green phosphor powder or other color phosphor powders are dispersed in the cured transparent resin, and the semiconductor light emission
  • a light-emitting device having a structure in which green light or other color light is emitted by irradiation of ultraviolet light to blue light from the element the light extraction efficiency from the light-emitting device may be reduced.
  • the Sr sialon green phosphor represented by the general formula (1) is excited when it receives ultraviolet light to blue light and emits green light.
  • ultraviolet light to blue light means light having a peak wavelength in the wavelength range of ultraviolet light to blue light.
  • the ultraviolet light to blue light is preferably light having a peak wavelength in the range of 370 nm to 470 nm.
  • Red phosphor [Red phosphor] The red phosphor has the following general formula (2)
  • Sr sialon red phosphor Is a phosphor that emits red light when excited by ultraviolet to blue light.
  • the europium activated sialon phosphor containing Sr is also referred to as “Sr sialon red phosphor”.
  • the crystal system of Sr sialon red phosphor is orthorhombic.
  • x is a number that satisfies 0 ⁇ x ⁇ 1, preferably 0.025 ⁇ x ⁇ 0.5, and more preferably 0.25 ⁇ x ⁇ 0.5.
  • the fired body obtained in the firing step is not a phosphor, and when x is 1, the luminous efficiency of the red phosphor powder is low.
  • x is preferably a number satisfying 0.025 ⁇ x ⁇ 0.5, and more preferably a number satisfying 0.25 ⁇ x ⁇ 0.5, even if 0 ⁇ x ⁇ 1.
  • the total subscript (1-x) ⁇ of Sr is a number satisfying 0 ⁇ (1-x) ⁇ ⁇ 3.
  • the overall subscript x ⁇ of Eu is a number satisfying 0 ⁇ x ⁇ ⁇ 3. That is, in the general formula (2), the total subscripts of Sr and Eu are numbers exceeding 0 and less than 3, respectively.
  • ⁇ , ⁇ , ⁇ , and ⁇ are numerical values converted when ⁇ is 3.
  • ⁇ , which is a subscript of Si is a number satisfying 5 ⁇ ⁇ ⁇ 9 when the numerical value converted when ⁇ is 3.
  • ⁇ , which is a subscript of Al is a number satisfying 1 ⁇ ⁇ ⁇ 5 when the numerical value converted when ⁇ is 3.
  • ⁇ , which is a subscript of O is a number satisfying 0.5 ⁇ ⁇ ⁇ 2 when the value ⁇ is 3.
  • ⁇ , which is a subscript of N is a number satisfying 5 ⁇ ⁇ ⁇ 15 as a numerical value converted when ⁇ is 3.
  • the composition of the phosphor obtained by firing is an orthorhombic system represented by the general formula (2).
  • the Sr sialon red phosphor may be different.
  • the Sr sialon red phosphor represented by the general formula (2) is usually in the form of a single crystal powder.
  • the Sr sialon red phosphor represented by the general formula (2) contains carbon in a proportion of 1 ppm to 5000 ppm, preferably 5 ppm to 1000 ppm, more preferably 50 ppm to 300 ppm.
  • the carbon content is the ratio of the mass of carbon to the total mass of the red phosphor including carbon.
  • the Sr sialon red phosphor usually takes the form of a single crystal powder, but a large amount of carbon exists in the vicinity of the surface of each particle constituting the phosphor powder.
  • the Sr sialon red phosphor is preferable because the luminance at room temperature (25 ° C.) is high and the decrease in luminance at a high temperature of about 150 ° C. is small. If the carbon content is less than 1 ppm, the Sr sialon red phosphor may have a significant decrease in luminance at high temperatures. If the carbon content exceeds 5000 ppm, the Sr sialon red phosphor may have low brightness at room temperature.
  • the Sr sialon red phosphor powder has an average particle size of preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 20 ⁇ m, and even more preferably 10 ⁇ m to 20 ⁇ m.
  • the average particle diameter is a value measured by the Coulter counter method, it means the median D 50 of the cumulative volume distribution.
  • the Sr sialon red phosphor powder or other color phosphor powders are dispersed in the cured transparent resin, and the semiconductor light emission
  • a light-emitting device having a structure in which red light or other color light is emitted by irradiation of ultraviolet light to blue light from the element the light extraction efficiency from the light-emitting device may be reduced.
  • the Sr sialon red phosphor represented by the general formula (2) is excited when it receives ultraviolet light to blue light and emits red light.
  • ultraviolet light to blue light means light having a peak wavelength in the wavelength range of ultraviolet light to blue light.
  • the ultraviolet light to blue light is preferably light having a peak wavelength in the range of 370 nm to 470 nm.
  • the Sr sialon green phosphor represented by the general formula (1) and the Sr sialon red phosphor represented by the general formula (2) are, for example, strontium carbonate SrCO 3 , aluminum nitride AlN, silicon nitride Si 3 N 4 ,
  • Each phosphor raw material such as europium oxide Eu 2 O 3 and silicon carbide SiC can be dry-mixed to prepare a phosphor raw material mixture, and this phosphor raw material mixture can be produced by firing in a nitrogen atmosphere.
  • the Sr sialon green phosphor represented by the general formula (1) contains more nitrogen N than the Sr sialon red phosphor represented by the general formula (2).
  • the Sr sialon green phosphor represented by the general formula (1) and the Sr sialon red phosphor represented by the general formula (2) are SrCO 3 , AlN, Si 3 N in the phosphor raw material mixture. 4 , Eu 2 O 3 , SiC, and other raw materials can be mixed, or the amount of nitrogen gas in the furnace during firing can be changed.
  • the Sr sialon red phosphor represented by the general formula (2) when the pressure of nitrogen gas in the furnace during firing is lowered to about 1 atm, the Sr sialon red phosphor represented by the general formula (2) can be easily obtained, and when the pressure is increased to about 7 atm, the general formula ( The Sr sialon green phosphor represented by 1) is easily obtained.
  • the phosphor raw material mixture may further contain strontium chloride SrCl 2 as a reaction accelerator as a fluxing agent.
  • the phosphor raw material mixture is filled in a refractory crucible.
  • a boron nitride crucible, a carbon crucible or the like is used as the refractory crucible.
  • the phosphor raw material mixture filled in the refractory crucible is fired.
  • the baking apparatus an apparatus is used in which the composition and pressure of the internal baking atmosphere in which the refractory crucible is arranged, the baking temperature and the baking time are maintained under predetermined conditions.
  • an electric furnace is used as such a baking apparatus.
  • N 2 -containing gas is used as the firing atmosphere.
  • N 2 gas or a mixed gas of N 2 and H 2 is used.
  • N 2 in the firing atmosphere has a function of eliminating an appropriate amount of oxygen O from the phosphor raw material mixture when the phosphor powder is fired from the phosphor raw material mixture.
  • H 2 in the firing atmosphere acts as a reducing agent when the phosphor powder is fired from the phosphor raw material mixture, and more oxygen O is lost from the phosphor raw material mixture than N 2 .
  • the composition of the obtained phosphor powder is represented by the Sr sialon green phosphor represented by the general formula (1) or the general formula (2). This is different from the Sr sialon red phosphor, and for this reason, the emission intensity of the phosphor powder may be weakened.
  • N 2 containing gas if a mixed gas of N 2 gas or N 2 and H 2,, the molar ratio of N 2 and H 2 in N 2 containing gas is, N 2: H 2 is usually 10 : 0 to 1: 9, preferably 8: 2 to 2: 8, more preferably 6: 4 to 4: 6.
  • the molar ratio of N 2 and H 2 in N 2 containing gas is a N 2 and H 2 which is continuously fed into the chamber of the calciner, N 2 and the ratio of the flow rate the ratio of H 2
  • the above ratio that is, usually 10: 0 to 1: 9, can be obtained by continuously supplying the gas in the chamber and continuously discharging the mixed gas in the chamber.
  • the N 2 -containing gas as the firing atmosphere be circulated in a chamber of the firing apparatus so as to form an air flow because firing is performed uniformly.
  • the pressure of the N 2 -containing gas that is the firing atmosphere is usually 0.1 MPa (approximately 1 atm) to 1.0 MPa (approximately 10 atm).
  • the composition of the phosphor powder obtained after firing is represented by the general formula (1) as compared with the phosphor raw material mixture charged in the crucible before firing. This is likely to be different from the green phosphor or the Sr sialon red phosphor represented by the general formula (2), which may cause the emission intensity of the phosphor powder to be weak.
  • the firing conditions are not particularly changed even when the pressure is 1.0 MPa or less, which is not preferable because energy is wasted.
  • the pressure of the N 2 -containing gas that is the firing atmosphere is preferably 0.5 MPa to 0.8 MPa, more preferably 0.8 MPa. 6 MPa to 0.8 MPa.
  • the pressure of the N 2 -containing gas that is the firing atmosphere is preferably 0.1 MPa to 0.4 MPa, more preferably 0. 1 MPa to 0.2 MPa.
  • the firing temperature is usually 1400 ° C. to 2000 ° C., preferably 1700 ° C. to 1900 ° C. When the firing temperature is in the range of 1400 ° C. to 2000 ° C., a high-quality single crystal phosphor powder with few crystal structure defects can be obtained by firing in a short time.
  • the resulting phosphor powder may be excited by ultraviolet to blue light and the emitted light may not have a desired color. That is, when it is desired to manufacture the Sr sialon green phosphor represented by the general formula (1), the color of light emitted by being excited by ultraviolet to blue light becomes a color other than green, or the general formula (2) When it is desired to produce the Sr sialon red phosphor represented, the color of the light that is excited and emitted by ultraviolet to blue light may be other than red.
  • the composition of the phosphor powder obtained by increasing the degree of disappearance of N and O during firing is Sr sialon green phosphor represented by the general formula (1) or the general formula ( It is easy to differ from the Sr sialon red phosphor represented by 2), and for this reason, the emission intensity of the phosphor powder may be weakened.
  • the firing time is usually 0.5 hours to 20 hours, preferably 2 hours to 10 hours, more preferably 3 hours to 5 hours.
  • the composition of the obtained phosphor powder is represented by the Sr sialon green phosphor represented by the general formula (1) or the general formula (2). This is different from the Sr sialon red phosphor, and for this reason, the emission intensity of the phosphor powder may be weakened.
  • the firing time is preferably a short time within a range of 0.5 to 20 hours when the firing temperature is high, and a long time within a range of 0.5 to 20 hours when the firing temperature is low. It is preferable that
  • a fired body made of phosphor powder is generated.
  • the fired body is usually in the form of a weak and solid lump.
  • a phosphor powder is obtained.
  • the phosphor powder obtained by crushing becomes a powder of Sr sialon green phosphor represented by general formula (1) or Sr sialon red phosphor represented by general formula (2).
  • a phosphor having good temperature characteristics can be obtained.
  • the light emitting device is a light emitting device using the Sr sialon green phosphor represented by the general formula (1) or the Sr sialon red phosphor represented by the general formula (2). Specifically, the light-emitting device is formed on the substrate, the semiconductor light-emitting element disposed on the substrate and emitting ultraviolet light to blue light, and the light-emitting surface of the semiconductor light-emitting element.
  • a phosphor that emits visible light when excited by the emitted light, and the phosphor is a Sr sialon green phosphor represented by the general formula (1) or Sr represented by the general formula (2).
  • the light emitting device emits green light from the emission surface of the light emitting device if the phosphor contained in the light emitting portion is only Sr sialon green phosphor, and the phosphor contained in the light emitting portion is only Sr sialon red phosphor. If there is, red light is emitted from the emission surface of the light emitting device.
  • the light emitting unit includes a phosphor such as a blue phosphor and a red phosphor in addition to the Sr sialon green phosphor, or a blue phosphor and a green phosphor in addition to the Sr sialon red phosphor.
  • White light emitting device that emits white light from the emitting surface of the light emitting device by mixing the light of each color such as red light, blue light, and green light emitted from the phosphors of each color. It can also be.
  • the light emitting device may contain other green phosphors in addition to Sr sialon green phosphors, or may contain other red phosphors in addition to Sr sialon red phosphors.
  • the light emitting device may include a Sr sialon green phosphor represented by the general formula (1) and a Sr sialon red phosphor represented by the general formula (2) as phosphors.
  • a Sr sialon green phosphor represented by the general formula (1) and a Sr sialon red phosphor represented by the general formula (2) as phosphors.
  • both the Sr sialon green phosphor and the Sr sialon red phosphor represented by the general formula (2) are included as the phosphor, a light emitting device with good temperature characteristics can be obtained.
  • substrate for example, ceramics such as alumina and aluminum nitride (AlN), glass epoxy resin, and the like are used. It is preferable that the substrate is an alumina plate or an aluminum nitride plate because the thermal conductivity is high and the temperature rise of the LED light source can be suppressed.
  • AlN aluminum nitride
  • the substrate is an alumina plate or an aluminum nitride plate because the thermal conductivity is high and the temperature rise of the LED light source can be suppressed.
  • the semiconductor light emitting element is disposed on the substrate.
  • a semiconductor light emitting element that emits ultraviolet light to blue light is used.
  • ultraviolet light to blue light means light having a peak wavelength in the wavelength range of ultraviolet light to blue light.
  • the ultraviolet light to blue light is preferably light having a peak wavelength in the range of 370 nm to 470 nm.
  • Examples of semiconductor light emitting devices that emit ultraviolet light to blue light include ultraviolet light emitting diodes, purple light emitting diodes, blue light emitting diodes, ultraviolet laser diodes, purple laser diodes, and blue laser diodes.
  • the semiconductor light emitting element is a laser diode
  • the peak wavelength means a peak oscillation wavelength.
  • the light emitting section includes a phosphor that is excited by ultraviolet light to blue light, which is emitted light from the semiconductor light emitting element, and emits visible light in the transparent resin cured product, and covers the light emitting surface of the semiconductor light emitting element. Formed as follows.
  • the phosphor used in the light emitting unit includes at least the above-described Sr sialon green phosphor or Sr sialon red phosphor.
  • the phosphor may include both Sr sialon green phosphor and Sr sialon red phosphor.
  • the phosphor used in the light emitting unit may include a Sr sialon green phosphor or a Sr sialon red phosphor and a phosphor other than the Sr sialon green phosphor or the Sr sialon red phosphor.
  • a phosphor other than the Sr sialon green phosphor or the Sr sialon red phosphor for example, a red phosphor, a blue phosphor, a green phosphor, a yellow phosphor, a purple phosphor, an orange phosphor and the like can be used.
  • the phosphor a powdery one is usually used.
  • the phosphor is contained in the cured transparent resin. Usually, the phosphor is dispersed in a cured transparent resin.
  • the transparent resin cured product used for the light emitting part is obtained by curing a transparent resin, that is, a highly transparent resin.
  • a transparent resin for example, a silicone resin or an epoxy resin is used. Silicone resins are preferred because they have higher UV resistance than epoxy resins. Among silicone resins, dimethyl silicone resin is more preferable because of its high UV resistance.
  • the light emitting part is preferably composed of 20 to 1000 parts by mass of the transparent resin cured product with respect to 100 parts by mass of the phosphor. When the ratio of the transparent resin cured product to the phosphor is within this range, the light emission intensity of the light emitting part is high.
  • the film thickness of the light emitting part is usually 80 ⁇ m or more and 800 ⁇ m or less, preferably 150 ⁇ m or more and 600 ⁇ m or less.
  • the film thickness of the light emitting portion is 80 ⁇ m or more and 800 ⁇ m or less, practical brightness can be ensured with a small amount of leakage of ultraviolet light to blue light emitted from the semiconductor light emitting element.
  • the film thickness of the light emitting part is 150 ⁇ m or more and 600 ⁇ m or less, light emitted from the light emitting part can be brightened.
  • the light emitting unit first mixes a transparent resin and a phosphor to prepare a phosphor slurry in which the phosphor is dispersed in the transparent resin, and then applies the phosphor slurry to the semiconductor light emitting device and the inner surface of the globe. It is obtained by curing.
  • the light emitting portion When the phosphor slurry is applied to the semiconductor light emitting element, the light emitting portion is in contact with and covered with the semiconductor light emitting element. Further, when the phosphor slurry is applied to the inner surface of the globe, the light emitting portion is formed on the inner surface of the globe while being separated from the semiconductor light emitting element.
  • a light emitting device in which the light emitting portion is formed on the inner surface of the globe is referred to as a remote phosphor type LED light emitting device.
  • the phosphor slurry can be cured by heating to 100 ° C. to 160 ° C., for example.
  • FIG. 1 is an example of an emission spectrum of the light emitting device.
  • a violet LED that emits violet light having a peak wavelength of 400 nm is used as a semiconductor light emitting element, and Sr sialon represented by Sr 2.7 Eu 0.3 Si 13 Al 3 O 2 N 21 as a phosphor. It is an emission spectrum of a green light emitting device at 25 ° C. using only a green phosphor.
  • the purple LED has a forward voltage drop Vf of 3.195 V and a forward current If of 20 mA.
  • the green light emitting device using the Sr sialon green phosphor represented by the general formula (1) as the phosphor has a high emission intensity even when excitation light having a short wavelength such as violet light is used.
  • FIG. 2 is another example of an emission spectrum of the light emitting device.
  • a violet LED that emits violet light having a peak wavelength of 400 nm is used as a semiconductor light emitting device, and Sr sialon red fluorescence represented by Sr 1.6 Eu 0.4 Si 7 Al 3 ON 13 as a phosphor. It is an emission spectrum of a red light emitting device at 25 ° C. using only the body.
  • the purple LED has a forward voltage drop Vf of 3.190 V and a forward current If of 20 mA.
  • the red light emitting device using the Sr sialon red phosphor represented by the general formula (2) as the phosphor has a high emission intensity even when excitation light having a short wavelength such as violet light is used. .
  • a light emitting device with good temperature characteristics can be obtained.
  • Example 1 (Production of phosphor) First, 337 g of SrCO 3 , 104 g of AlN, 514 g of Si 3 N 4 , 45 g of Eu 2 O 3 , and 0.003 g of SiC are weighed, and an appropriate amount of a flux agent is added thereto, followed by dry mixing to obtain a phosphor raw material mixture Was prepared. Thereafter, the phosphor raw material mixture was filled in a boron nitride crucible. Table 1 shows the blending amounts of raw materials such as SrCO 3 . When a boron nitride crucible filled with the phosphor raw material mixture is baked in an electric furnace at 1800 ° C.
  • the calcined powder contained the amount of carbon shown in Table 2.
  • the carbon content is the ratio of the mass of carbon to the total mass of the calcined powder including carbon. A large amount of carbon was present in the vicinity of the surface of each particle constituting the phosphor powder (fired powder).
  • the obtained Sr sialon green light emitting phosphor was examined for average particle diameter, emission peak wavelength and luminance.
  • the average particle diameter is a value measured by the Coulter counter method, the value of the median D 50 of the cumulative volume distribution.
  • the luminance was measured at room temperature (25 ° C.) and 150 ° C.
  • the luminance at room temperature is shown as a relative value (%) (hereinafter referred to as relative luminance) where the luminance at room temperature of Example 1 is 100.
  • the luminance at room temperature is shown as a relative value (%) (relative luminance) where the luminance at room temperature in Example 1 is 100.
  • Example 2 Sr sialon green light emitting phosphor was examined in the same manner as in Example 1 for the average particle size, emission peak wavelength, and luminance.
  • the brightness of some examples (Examples 2 to 7) and comparative examples (Comparative Examples 1 to 3) were measured at room temperature (25 ° C.) and 150 ° C. as in Example 1.
  • the luminances of Examples 8 and 9 and Comparative Examples (Comparative Examples 4 to 6) were measured at room temperature (25 ° C.) and 100 ° C. The luminance measured at 100 ° C.
  • Example 10 (Production of phosphor)
  • Sr sialon red light emitting phosphors having the composition and carbon content shown in Table 5
  • the blending amounts of SrCO 3 , AlN, Si 3 N 4 , Eu 2 O 3 , and SiC in the phosphor raw material mixture are shown in Table 4.
  • a red powder was obtained in the same manner as in Example 1 except that the changes were made.
  • the red powder was analyzed, it was a single crystal Sr sialon red light emitting phosphor having the composition shown in Table 5.
  • the red powder contained carbon in the amount shown in Table 5. A large amount of carbon was present in the vicinity of the surface of each particle constituting the phosphor powder (red powder).
  • a phosphor and a light emitting device having good temperature characteristics can be obtained.
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KR20150045650A (ko) * 2013-10-21 2015-04-29 엘지전자 주식회사 녹색 발광 형광체, 그 제조 방법 및 이를 이용한 발광 소자 패키지
KR102171446B1 (ko) * 2013-10-21 2020-10-29 엘지전자 주식회사 적색 발광 형광체, 그 제조 방법 및 이를 이용한 발광 소자 패키지
CN105441078B (zh) * 2014-09-30 2017-07-14 中国科学院上海硅酸盐研究所 稀土离子Eu2+掺杂的Y5Si3O12N荧光粉及其制备方法
CN105462579A (zh) * 2015-12-04 2016-04-06 许昌学院 一种长余辉红色荧光材料及其制备方法
CN110513605B (zh) * 2019-08-20 2020-12-29 西安鸿钧睿泽新材料科技有限公司 一种具有自发光功能的园林景观灯及其制造方法

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