WO2010143618A1 - 蛍光体材料および発光装置 - Google Patents

蛍光体材料および発光装置 Download PDF

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Publication number
WO2010143618A1
WO2010143618A1 PCT/JP2010/059650 JP2010059650W WO2010143618A1 WO 2010143618 A1 WO2010143618 A1 WO 2010143618A1 JP 2010059650 W JP2010059650 W JP 2010059650W WO 2010143618 A1 WO2010143618 A1 WO 2010143618A1
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WO
WIPO (PCT)
Prior art keywords
coating layer
phosphor
oxide
aluminum
phosphor material
Prior art date
Application number
PCT/JP2010/059650
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English (en)
French (fr)
Japanese (ja)
Inventor
美史 傳井
敬輔 佐藤
佐藤　豊
井口　真仁
Original Assignee
株式会社日本セラテック
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Application filed by 株式会社日本セラテック filed Critical 株式会社日本セラテック
Priority to KR2020127000009U priority Critical patent/KR200475471Y1/ko
Publication of WO2010143618A1 publication Critical patent/WO2010143618A1/ja

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    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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

  • the present invention relates to a phosphor material having a coating layer on the surface of phosphor particles and a light emitting device using the same.
  • LED lamps are used in various display devices such as portable devices, PC peripheral devices, OA devices, various switches, and backlight light sources. Such LED lamps use phosphors to emit various colors, and various phosphors have been developed (see, for example, Patent Document 1).
  • the present invention has been made based on such problems, and an object of the present invention is to provide a phosphor material and a light emitting device capable of extending the life by improving water resistance, ultraviolet light resistance and the like. To do.
  • the phosphor material of the present invention has phosphor particles and a coating layer that covers the entire surface of the phosphor particles.
  • the coating layer includes rare earth oxide, aluminum oxide, a composite oxide of yttrium and aluminum, oxidation It contains at least one metal oxide selected from the group consisting of magnesium and composite oxides of aluminum and magnesium.
  • the light emitting device of the present invention includes the phosphor material of the present invention.
  • the entire surface of the phosphor particles is at least selected from the group consisting of rare earth oxide, aluminum oxide, yttrium and aluminum composite oxide, magnesium oxide, and aluminum and magnesium composite oxide. Since the coating layer made of one kind of metal oxide is formed, characteristics such as water resistance and ultraviolet light resistance can be improved. Therefore, according to the light emitting device using the phosphor material of the present invention, the lifetime can be extended.
  • the coating layer is formed of a rare earth oxide containing at least one element selected from the group consisting of yttrium (Y), gadolinium (Gd), and ytterbium (Yb), higher characteristics can be obtained. And cost can be reduced.
  • Y yttrium
  • Gd gadolinium
  • Yb ytterbium
  • the thickness of the coating layer is set to 5 nm or more and 1 ⁇ m or less, excellent water resistance can be obtained and high permeability can be obtained.
  • FIG. 2 It is a schematic diagram showing the structure of the phosphor material which concerns on one embodiment of this invention. It is a schematic diagram showing the structure of fluorescent substance materials other than one embodiment of this invention. It is a figure showing the structure of the light-emitting device using the fluorescent substance material of FIG. 2 is a TEM photograph of the phosphor material of Example 1. It is an enlarged photograph of the phosphor material of FIG. 4 is a TEM photograph of a phosphor material of Comparative Example 2. It is a characteristic view which shows the brightness
  • FIG. 1 schematically shows a phosphor material 10 according to an embodiment of the present invention.
  • the phosphor material 10 includes phosphor particles 11 and a coating layer 12.
  • Examples of the phosphor particles 11 include blue phosphors such as BaMgAl 10 O 17 : Eu or CaMgSi 2 O 6 : Eu, Zn 2 SiO 4 : Mn, (Y, Gd) BO 3 : Tb or (Ba, Sr). , Mg) O.aAl 2 O 3 : Mn green phosphors, and (Y, Gd) BO 3 : Eu or red phosphors such as YPVO 4 : Eu.
  • blue phosphors such as BaMgAl 10 O 17 : Eu or CaMgSi 2 O 6 : Eu, Zn 2 SiO 4 : Mn, (Y, Gd) BO 3 : Tb or (Ba, Sr).
  • Mg) O.aAl 2 O 3 Mn green phosphors
  • (Y, Gd) BO 3 Eu or red phosphors such as YPVO 4 : Eu.
  • the covering layer 12 is made of a rare earth oxide, aluminum oxide, a composite oxide of yttrium and aluminum such as yttrium / aluminum / garnet, magnesium oxide, and a composite oxide of aluminum and magnesium such as MgAl 2 O 4 . At least one kind is formed as a main component. This is because deterioration over time with respect to ultraviolet light can be suppressed and water resistance can be improved. Among these, rare earth oxides are preferred, rare earth oxides containing at least one element from the group consisting of yttrium, gadolinium and ytterbium are more preferred, and Y 2 O 3 is particularly desirable. This is because higher effects can be obtained and costs can be suppressed.
  • the coating layer 12 may be a single layer of these, or may be a stack of a plurality of layers.
  • the coating layer 12 may be mixed in the coating layer 12 in the process of manufacture, it is preferable to make the ratio of another component 0.1 mass% or less in that case. This is because deterioration over time with respect to ultraviolet light can be further suppressed, and water resistance can be further improved. Further, it is preferable that the other components do not adversely affect the characteristics of the coating layer 12. Specifically, silicon (Si), sodium (Na), iron (Fe), zinc (Zn), chromium ( Cr), nickel (Ni), copper (Cu), calcium (Ca), manganese (Mn), titanium (Ti) or potassium (K).
  • the green phosphor is greatly deteriorated by ultraviolet light, it is preferable to form the coating layer 12 with Y 2 O 3 because the deterioration can be remarkably suppressed.
  • the coating layer 12 covers the entire surface of the phosphor particles 11. Thereby, hydrolysis due to contact of the phosphor particles 11 with moisture can be suppressed, and water resistance can be improved. Further, since the phosphor particles 11 are irradiated with ultraviolet light through the coating layer 12, the effect of preventing deterioration can be improved.
  • FIG. 2 schematically shows the phosphor material 110 in which a part of the surface of the phosphor particle 111 is coated with the coating layer 112, but the phosphor particle 111 is exposed from between the coating layers 112. Therefore, sufficient effect cannot be obtained.
  • the fact that the coating layer 12 covers the entire surface of the phosphor particles 11 does not exclude even the presence of defects such as vacancies, and is substantially close to 100%. It means that it is coverage.
  • the thickness of the coating layer 12 is preferably 5 nm or more and 1 ⁇ m or less. If the thickness is small, it is difficult to form, and the effect of improving water resistance is reduced. If the thickness is thick, the permeability is lowered and the cost is increased.
  • the phosphor material 10 can form the coating layer 12 on the surface of the phosphor particles 11 by using a sol-gel method, for example. Specifically, for example, after the phosphor particles 11 are immersed in a solution in which a metal salt is dissolved in a solvent, the phosphor particles 11 to which the solution is attached are taken out, gelled by drying or the like, and then fired. 12 is preferably formed. This is because the coating layer 12 can be formed on the entire surface of the phosphor particles 11 by immersing the phosphor particles 11 in a solution in which a metal salt is dissolved in a solvent and attaching the solution to the surfaces of the phosphor particles 11. is there.
  • the solvent an organic solvent, water, or the like can be used.
  • the metal salt carbonate, nitrate, alkoxide, or the like can be used.
  • the firing temperature is preferably 300 ° C. or higher and 1000 ° C. or lower. This is because it is difficult to form the coating layer 12 when the temperature is lower than 300 ° C., and thermal deterioration may occur depending on the material of the phosphor particles 11 when the temperature exceeds 1000 ° C.
  • FIG. 3 shows a configuration example of the light emitting device 20 using the phosphor material 10.
  • a light emitting element 22 is mounted on a substrate 21, and the light emitting element 22 is electrically connected to a wiring 23 formed on the substrate 21 by a wire 24.
  • a reflector frame 25 is formed around the light emitting element 22, and a sealing layer 26 is formed on the light emitting element 22 so as to cover the light emitting element 22.
  • the sealing layer 26 is made of, for example, a resin in which the phosphor material 10 is dispersed.
  • the light emitting element 22 is, for example, one that emits ultraviolet light, blue light, or green light as excitation light.
  • Examples of the phosphor material 10 include one that absorbs excitation light emitted from the light emitting element 22 and emits red light, one that emits blue light, one that emits yellow light, and the like, or a mixture thereof as necessary. Used. Among these, when the light emitting element 22 that emits ultraviolet light is used, the phosphor material 10 of the present invention is preferably used. This is because the phosphor material 10 of the present invention has excellent ultraviolet light resistance.
  • the entire surface of the phosphor particles 11 is made of a rare earth oxide, aluminum oxide, a composite oxide of yttrium and aluminum, magnesium oxide, and a composite oxide of aluminum and magnesium. Since the coating layer 12 made of at least one metal oxide is formed, characteristics such as water resistance and ultraviolet light resistance can be improved. Therefore, according to the light emitting device 20 using the phosphor material 10, the lifetime can be extended.
  • the coating layer 12 is formed of a rare earth oxide containing at least one element selected from the group consisting of yttrium, gadolinium, and ytterbium, higher characteristics can be obtained, and costs can be reduced. be able to.
  • the thickness of the coating layer 12 is set to 5 nm or more and 1 ⁇ m or less, excellent water resistance can be obtained and high permeability can be obtained.
  • Example 1 As the phosphor particles 11, blue, green, and red particles were prepared, respectively, and immersed in a solution in which an yttrium salt was dissolved in a solvent. Next, the phosphor particles 11 with the solution attached were taken out, dried and gelled, and then baked at 500 ° C. for 2 hours.
  • FIG. 4 shows an example of a TEM (Transmission Electron Microscope) photograph near the surface of the obtained phosphor material 10
  • FIG. 5 is an enlarged view of a part of the TEM photograph of FIG. It is a thing. 4 and 5, the portion indicated by 11 is a phosphor particle, and the portion indicated by 12 is a coating layer.
  • the white part on the coating layer 12 is a carbon film used at the time of analysis.
  • the phosphor material 10 has the coating layer 12 formed on the entire surface of the phosphor particles 11.
  • a light emitting device 20 as shown in FIG. 3 was produced.
  • a light emitting element 22 that emits ultraviolet light is used, and a phosphor material 10 that emits blue, green, and red emits light to obtain white light emission. It was adjusted.
  • the green light-emitting device 20 was also produced by using only the thing which emits green as the fluorescent material 10.
  • Example 1 A light emitting device was fabricated in the same manner as in Example 1 except that the phosphor particles were used as they were without forming a coating layer on the phosphor particles.
  • FIG. 6 shows an example of a TEM photograph near the surface of the obtained phosphor material.
  • the portion indicated by 111 is a phosphor particle
  • the portion indicated by 112 is a coating layer.
  • the white part on the fluorescent substance particle 11 and the coating layer 112 is a carbon film used at the time of analysis.
  • the phosphor material 110 has particles of the coating layer 112 partially attached to a part of the surface of the phosphor particles 111.
  • FIG. 7 shows a comparison of the results of Example 1 and Comparative Example 1.
  • Example 1 in which the coating layer 12 was formed, a decrease in the luminance maintenance rate could be significantly suppressed as compared with Comparative Example 1 in which the coating layer was not formed.
  • Comparative Example 2 although the decrease in the luminance maintenance rate was slightly suppressed as compared with Comparative Example 1, it was not significantly improved as in Example 1. That is, it has been found that if the entire surface of the phosphor particles 11 is covered with the coating layer 12, the deterioration can be significantly improved.
  • Example 2 The phosphor material 10 is the same as that of Example 1 except that the concentration of the phosphor particles 11 in the solution in which the yttrium salt is dissolved is changed to change the thickness of the coating layer 12 in the range of 5 nm to 1 ⁇ m. And the light-emitting device 20 was produced. At that time, green particles were used as the phosphor particles 11.
  • Example 2 a deterioration test was conducted in the same manner as in Example 1. As a result, a good luminance maintenance rate was obtained when the thickness of the coating layer 12 was in the range of 5 nm to 1 ⁇ m. That is, it was found that the thickness of the coating layer 12 is preferably in the range of 5 nm to 1 ⁇ m.
  • the coating layer 12 is mainly made of at least one selected from the group consisting of rare earth oxides, aluminum oxides, yttrium and aluminum composite oxides, magnesium oxide, and aluminum and magnesium composite oxides.
  • the coating layer 12 is mainly made of at least one selected from the group consisting of rare earth oxides, aluminum oxides, yttrium and aluminum composite oxides, magnesium oxide, and aluminum and magnesium composite oxides.
  • It can be used for light emitting devices such as LEDs.
  • SYMBOLS 10 Phosphor material, 11 ... Phosphor particle, 12 ... Cover layer, 20 ... Light emitting device, 21 ... Substrate, 22 ... Light emitting element, 23 ... Wiring, 24 ... Wire, 25 ... Reflector frame, 26 ... Sealing layer, 110 ... phosphor material, 111 ... phosphor particle, 112 ... coating layer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Luminescent Compositions (AREA)
  • Led Device Packages (AREA)
PCT/JP2010/059650 2009-06-08 2010-06-08 蛍光体材料および発光装置 WO2010143618A1 (ja)

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JP2009137727A JP2010280877A (ja) 2009-06-08 2009-06-08 蛍光体材料および発光装置

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3004459A1 (fr) * 2013-04-16 2014-10-17 Commissariat Energie Atomique Particule inorganique coeur/coquille luminescente, procede de preparation et utilisation
US8907558B2 (en) 2012-03-15 2014-12-09 Kabushiki Kaisha Toshiba White light emitting device with red and green-yellow phosphor

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI594461B (zh) * 2011-08-04 2017-08-01 國家中山科學研究院 螢光粉包覆結構及其製造方法
JP7479006B2 (ja) 2020-03-26 2024-05-08 パナソニックＩｐマネジメント株式会社 セラミクス複合体

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006236961A (ja) * 2005-01-28 2006-09-07 Matsushita Electric Ind Co Ltd 蛍光ランプ、バックライト装置、及び蛍光ランプの製造方法
JP2008031429A (ja) * 2006-06-28 2008-02-14 Toray Ind Inc 蛍光体ペーストおよびディスプレイの製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69526423T2 (de) * 1994-08-08 2002-12-05 Koninklijke Philips Electronics N.V., Eindhoven Verfahren zur beschichtung eines lumineszenten materials
DE102007053770A1 (de) * 2007-11-12 2009-05-14 Merck Patent Gmbh Beschichtete Leuchtstoffpartikel mit Brechungsindex-Anpassung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006236961A (ja) * 2005-01-28 2006-09-07 Matsushita Electric Ind Co Ltd 蛍光ランプ、バックライト装置、及び蛍光ランプの製造方法
JP2008031429A (ja) * 2006-06-28 2008-02-14 Toray Ind Inc 蛍光体ペーストおよびディスプレイの製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8907558B2 (en) 2012-03-15 2014-12-09 Kabushiki Kaisha Toshiba White light emitting device with red and green-yellow phosphor
FR3004459A1 (fr) * 2013-04-16 2014-10-17 Commissariat Energie Atomique Particule inorganique coeur/coquille luminescente, procede de preparation et utilisation
WO2014170567A1 (fr) * 2013-04-16 2014-10-23 Commissariat A L'energie Atomique Et Aux Energies Alternatives Particule inorganique coeur/coquille luminescente, procede de preparation et utilisation

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TW201107452A (en) 2011-03-01
JP2010280877A (ja) 2010-12-16
KR20120002303U (ko) 2012-04-02
TWI544058B (zh) 2016-08-01
KR20110093950A (ko) 2011-08-18

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