WO2017030030A1 - Corps fluorescent, son procédé de production, et dispositif électroluminescent - Google Patents

Corps fluorescent, son procédé de production, et dispositif électroluminescent Download PDF

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Publication number
WO2017030030A1
WO2017030030A1 PCT/JP2016/073243 JP2016073243W WO2017030030A1 WO 2017030030 A1 WO2017030030 A1 WO 2017030030A1 JP 2016073243 W JP2016073243 W JP 2016073243W WO 2017030030 A1 WO2017030030 A1 WO 2017030030A1
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Prior art keywords
phosphor
containing compound
range
boron
ppm
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PCT/JP2016/073243
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English (en)
Japanese (ja)
Inventor
拓馬 酒井
努 児玉
あき 植田
岩下　和樹
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宇部興産株式会社
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Priority to JP2017535492A priority Critical patent/JP6763387B2/ja
Publication of WO2017030030A1 publication Critical patent/WO2017030030A1/fr

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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
    • C09K11/08—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
    • C09K11/64—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 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the present invention relates to a phosphor, a manufacturing method thereof, and a light emitting device, and more particularly, to a phosphor exhibiting green light emission, a manufacturing method thereof, and a light emitting device.
  • a white light emitting diode (white LED) is widely used as a two-color mixed type that obtains white light by mixing blue and yellow by combining a semiconductor light emitting element that emits blue light and a yellow phosphor. ing.
  • the white light emitted from this two-color mixed type white LED has a problem that the color rendering is poor. Therefore, as another configuration, a combination of a semiconductor light emitting element that emits blue light and two types of phosphors, green and red, is used to excite each phosphor with light from the semiconductor light emitting element. Development of a white LED of a three-color mixed type that obtains white light with a mixed color of green and red is underway.
  • Green phosphors having various compositions have been developed as phosphors that emit green light.
  • Patent Document 1 and Non-Patent Document 1 as a green phosphor used for an LED or the like, Sr 5- yza My Si 23-x Al 3 + x O x + 2a N 37-x-2a : Eu z
  • a phosphor having a Ce z1 composition is described, and in particular, a phosphor having a Sr 4.9 Al 5 Si 21 O 2 N 35 : Eu 0.1 composition is described in the example of Patent Document 1.
  • Patent Document 2 includes Eu-activated Sr 3 Si 13 Al 3 O 2 N 21 group crystal that defines the ratio of the oxygen concentration in the outer region to the oxygen concentration in the inner region.
  • a phosphor that contains particles and emits light having an emission peak between wavelengths 490 and 580 nm when excited with light having a wavelength of 250 to 500 nm is described.
  • the green phosphors described in Patent Document 1 and Non-Patent Document 1 have a problem that the light emission characteristics are not sufficient and the light emission intensity is particularly low. Further, as described in Non-Patent Document 1, since orange to red phosphors such as SrAlSi 4 N 7 and Sr 2 Si 5 N 8 are generated as different phases, it is necessary to remove them mechanically. Have a problem. Furthermore, although the phosphor described in Patent Document 2 has high stability of emission intensity against heat, further improvement is expected in the emission characteristics of the phosphor itself.
  • the particle size of the white LED phosphor is too large, it is difficult to uniformly disperse in the resin and the color tone varies, and it is necessary to control the phosphor within a predetermined particle size range. Further, if pulverization and classification are performed in order to reduce the particle size, fine particles are generated and the luminance is reduced. Therefore, the pulverization step is not required and the particle size needs to be controlled.
  • the present invention has been made in view of the above-mentioned problems, and is controlled to a predetermined particle size and the generation of a heterogeneous phase is suppressed, and a phosphor excellent in light emission characteristics, in particular, light emission intensity, compared to the prior art, and its production It is an object to provide a method and a light emitting device.
  • the present inventors have conducted intensive research, and as a result, by adding a specific amount of boron to the green phosphor activated with europium and / or cerium, the predetermined particle size is reduced. It was found that the generation of heterogeneous phases was suppressed and the emission intensity could be greatly improved, and the present invention was achieved.
  • the present invention relates to a phosphor containing a crystal phase represented by the composition of the following formula (1), and further containing 100 to 2500 ppm of boron.
  • M1 is one or more metal elements selected from the group consisting of Ca, Ba and Mg, and 2 ⁇ a ⁇ 8, 0 ⁇ b ⁇ 3, 2 ⁇ c ⁇ 7, 10 ⁇ d ⁇ 25, (15 ⁇ e ⁇ 37, 0 ⁇ f ⁇ 3, 0 ⁇ x1 + y1 ⁇ 0.6)
  • the present invention includes at least a phosphor containing Sr 5 Al 5 Si 21 N 35 O 2 structure crystalline phase, of Sr 5 Al 5 Si 21 N 35 O 2 structure in X-ray diffraction pattern phosphor ( 021)
  • a phosphor containing Sr 5 Al 5 Si 21 N 35 O 2 structure crystalline phase of Sr 5 Al 5 Si 21 N 35 O 2 structure in X-ray diffraction pattern phosphor ( 021)
  • the present invention relates to a characteristic phosphor.
  • this invention relates to the fluorescent substance containing the crystal phase represented by a composition of following formula (2).
  • M2 is one or more metal elements selected from the group consisting of Ca, Ba and Mg, and 2 ⁇ g ⁇ 8, 0 ⁇ h ⁇ 3, 0.02 ⁇ i ⁇ 0.8, 2 ⁇ j ⁇ 7, 10 ⁇ k ⁇ 25, 15 ⁇ l ⁇ 37, 0 ⁇ m ⁇ 3, 0 ⁇ x2 + y2 ⁇ 0.6.
  • the present invention also includes a step of mixing a Sr-containing compound, an Al-containing compound, an Si-containing compound, an Eu-containing compound and / or a Ce-containing compound, and a B-containing compound to obtain a raw material mixture, and the raw material mixture as an inert gas.
  • a phosphor comprising a step of firing in an atmosphere or a reducing gas atmosphere, wherein the amount of the B-containing compound added is 250 to 10,000 ppm of the raw material mixture It relates to the manufacturing method.
  • the present invention relates to a light emitting device comprising the above phosphor and a light source that emits light by irradiating the phosphor with excitation light.
  • ADVANTAGE OF THE INVENTION while being controlled to a predetermined particle size, the production
  • the fluorescent substance which was excellent in luminescent characteristics, especially luminescence intensity compared with the past, its manufacturing method, and a light-emitting device can be provided. .
  • FIG. 5 It is a figure which shows the X-ray-diffraction (XRD) pattern of the fluorescent substance obtained in Example 5 and Comparative Example 1. It is a figure which shows the emission spectrum of the fluorescent substance obtained in Example 5 and Comparative Example 1. 2 is a scanning electron micrograph of the phosphors obtained in Example 5 and Comparative Example 1. FIG. It is a figure which shows the B density
  • XRD X-ray-diffraction
  • Phosphor The phosphor of the present invention includes a crystal phase represented by the composition of the following formula (1).
  • M1 is one or more metal elements selected from the group consisting of Ca, Ba and Mg, and 2 ⁇ a ⁇ 8, 0 ⁇ b ⁇ 3, 2 ⁇ c ⁇ 7, 10 ⁇ d ⁇ 25, (15 ⁇ e ⁇ 37, 0 ⁇ f ⁇ 3, 0 ⁇ x1 + y1 ⁇ 0.6)
  • the phosphor of the present invention is a phosphor activated with europium (Eu) and / or cerium (Ce), and has a peak between 500 and 560 nm when excited with light having a wavelength of 330 to 500 nm.
  • Eu europium
  • Ce cerium
  • europium (Eu) and / or cerium (Ce) is an activator and has a property of emitting light as a luminescent atom in the phosphor.
  • the molar ratio of europium in the phosphor that is, the value of x1 is in the range of 0 ⁇ x1 ⁇ 0.3, preferably in the range of 0.001 ⁇ x1 ⁇ 0.25, and 0.1 ⁇ x1 ⁇ . More preferably within the range of 0.15. If the value of x1 exceeds 0.3, the luminescent atoms become high in concentration and close to each other to cancel light emission, so that the light emission intensity tends to be weak.
  • the molar ratio of cerium in the phosphor that is, the value of y1 is in the range of 0 ⁇ y1 ⁇ 0.3, preferably in the range of 0 ⁇ y1 ⁇ 0.1, and 0 ⁇ y1 ⁇ 0. A range of 0001 is more preferable.
  • the value of x1 + y1 is in the range of 0 ⁇ x1 + y1 ⁇ 0.6, preferably in the range of 0.001 ⁇ x1 + y1 ⁇ 0.25, and more preferably in the range of 0.1 ⁇ x1 + y1 ⁇ 0.15.
  • the case where the composition does not contain Eu that is, the case where the value of x1 is 0, or the case where the composition does not contain Ce, that is, the case where the value of y1 is 0, is included. It is necessary that the composition contains any element of Ce, that is, a composition of x1 + y1> 0.
  • the molar ratio of strontium (Sr) in the phosphor is in the range of 2 ⁇ a ⁇ 8, preferably in the range of 4 ⁇ a ⁇ 8, and 4.5 ⁇ a ⁇ .
  • the range of 6 is more preferable, and the range of 4.75 ⁇ a ⁇ 5.25 is more preferable.
  • a is in the range of 2 ⁇ a ⁇ 8
  • a high-intensity green phosphor with a narrow half width is obtained.
  • M1 is one or more metal elements selected from the group consisting of calcium (Ca), barium (Ba), and magnesium (Mg), and the value of b is 0 ⁇ b Within the range of ⁇ 3 is preferable.
  • the case where the composition does not contain any of Ca, Ba and Mg, that is, the case where the value of b is 0 is also included.
  • the molar ratio of aluminum (Al) in the phosphor is in the range of 2 ⁇ c ⁇ 7, preferably in the range of 3 ⁇ c ⁇ 7, and in the range of 4 ⁇ c ⁇ 6. Within the range is preferable.
  • the value of c is in the range of 2 ⁇ c ⁇ 7, a high-intensity green phosphor with a narrow half width is obtained.
  • the molar ratio of silicon (Si) in the phosphor is in the range of 10 ⁇ d ⁇ 25, preferably in the range of 15 ⁇ d ⁇ 25, and 19.5 ⁇ d ⁇
  • the range of 22.5 is more preferable, and the range of 20.5 ⁇ d ⁇ 21.5 is more preferable.
  • d is in the range of 10 ⁇ d ⁇ 25
  • a high-brightness green phosphor with a narrow half-value width is obtained.
  • the molar ratio of nitrogen (N) in the phosphor is in the range of 15 ⁇ e ⁇ 37, preferably in the range of 32 ⁇ e ⁇ 37, and 34 ⁇ e ⁇ 36.
  • the range is more preferable, and the range of 34.5 ⁇ e ⁇ 35.5 is more preferable.
  • e is in the range of 15 ⁇ e ⁇ 37, a high-luminance green phosphor with a narrow half-value width is obtained.
  • the molar ratio of oxygen (O) in the phosphor is in the range of 0 ⁇ f ⁇ 3, and preferably in the range of 0.1 ⁇ f ⁇ 2.3.
  • O oxygen
  • the phosphor of the present invention is further characterized by containing boron.
  • the boron content with respect to the entire phosphor is 100 to 2500 ppm, preferably 200 to 1500 ppm, and more preferably 300 to 1500 ppm. If the boron content is less than 100 ppm, the emission intensity is not improved, and if it is more than 2500 ppm, the emission intensity is lowered.
  • the boron content can be measured using an inductively coupled plasma optical emission spectrometry (ICP-AES) apparatus.
  • ICP-AES inductively coupled plasma optical emission spectrometry
  • the elemental concentration of boron on the outermost surface of the phosphor is preferably 20000 to 100,000 ppm, more preferably 30000 to 60000 ppm.
  • the elemental concentration of boron on the outermost surface of the phosphor is defined as the elemental concentration of boron measured at a depth of several nm from the outside, from which photoelectrons can be extracted when the outermost surface of the phosphor is irradiated with X-rays. be able to.
  • the elemental concentration of boron on the outermost surface of the phosphor can be measured using an X-ray photoelectron spectroscopy (XPS) apparatus.
  • XPS X-ray photoelectron spectroscopy
  • Phosphor particles often have different compositions near the particle surface and inside the particle, and composition fluctuations are confirmed.
  • a depth region of 100 nm (outside to 100 nm) from the phosphor outermost surface is defined as the phosphor surface, and a depth region beyond the phosphor surface (over 100 nm from the outside) is defined as the inside of the phosphor. be able to. No composition variation is observed inside the phosphor.
  • the boron element concentration on the phosphor outermost surface is preferably higher than the boron element concentration inside the phosphor.
  • the boron element concentration on the outermost surface of the phosphor is higher than the boron element concentration inside the phosphor, a high-luminance green phosphor with a narrow half-value width is obtained.
  • the boron element concentration on the phosphor outermost surface preferably has a difference of about 5 to 8 times the boron element concentration present within 200 nm from the phosphor outermost surface.
  • the elemental concentration of boron existing 200 nm from the outermost surface of the phosphor is several times from the etched surface where photoelectrons can be extracted when X-rays are irradiated to the etched surface after etching from the phosphor outermost surface to 200 nm. It can be defined as the elemental concentration of boron measured at a depth of nm, and can be measured using an X-ray photoelectron spectroscopy (XPS) apparatus.
  • XPS X-ray photoelectron spectroscopy
  • the phosphor of the present invention preferably has a half width of the emission spectrum of 70 nm or less.
  • the half width is the wavelength width when the emission spectrum is measured when the vertical axis is the emission intensity and the horizontal axis is the wavelength, and the emission intensity at the peak is I, and the wavelength width is I / 2. means.
  • the full width at half maximum is relatively narrow as described above, high emission intensity can be obtained.
  • the phosphor of the present invention has a diffraction peak intensity derived from the (021) plane of the phosphor having the Sr 5 Al 5 Si 21 N 35 O 2 structure in the X-ray diffraction pattern measured with an X-ray diffraction (XRD) apparatus.
  • XRD X-ray diffraction
  • the Sr 5 Al 5 Si 21 N 35 O 2 structure is a crystal structure having the same shape as ICSD Coll Code: 420168, and a part of Sr is one or more metals selected from the group consisting of Ca, Ba and Mg.
  • the crystal structure of a phosphor substituted with an element is also included.
  • the SrAlSi 4 N 7 structure is a crystal structure having the same shape as ICSD Coll Code: 163667, and a part of Sr was substituted with one or more metal elements selected from the group consisting of Ca, Ba and Mg.
  • the crystal structure of the phosphor is also included.
  • B / A ⁇ 0.03 means that the amount of SrAlSi 4 N 7 structure crystals contained as a different phase (impurity) in the phosphor of the present invention is small.
  • a high-luminance green phosphor with a narrow half-value width of the emission spectrum can be obtained.
  • the phosphor of the present invention is preferably D 10 size measured by a laser diffraction / scattering particle size distribution analyzer is 20 ⁇ 30 [mu] m.
  • D 10 diameter is 20 ⁇ 30 [mu] m, fine less luminous intensity increases.
  • D 10 diameter exceeds 30 [mu] m, the light emitting device, when specifically to a white light emitting LED, becomes difficult to uniformly disperse in the resin, it tends to occur a variation in color tone.
  • the phosphor of the present invention preferably has an average value of Heywood diameter (equivalent circle diameter) of less than 32 ⁇ m measured by a scanning electron micrograph.
  • the Heywood diameter can be calculated by reading a powder image using image analysis type particle size distribution measurement software “Mac-View” manufactured by Mountec Co., Ltd.
  • the average value of the Heywood diameter is less than 32 ⁇ m, particularly when used as a light emitting element of a white LED, it is preferable because a desired particle size can be obtained without requiring pulverization.
  • the phosphor of the present invention includes a crystal phase represented by the composition of the following formula (2).
  • M2 is one or more metal elements selected from the group consisting of Ca, Ba and Mg, and 2 ⁇ g ⁇ 8, 0 ⁇ h ⁇ 3, 0.02 ⁇ i ⁇ 0.8, 2 ⁇ j ⁇ 7, 10 ⁇ k ⁇ 25, 15 ⁇ l ⁇ 37, 0 ⁇ m ⁇ 3, 0 ⁇ x2 + y2 ⁇ 0.6.
  • the value of x2 is in the range of 0 ⁇ x2 ⁇ 0.3, preferably in the range of 0.001 ⁇ x2 ⁇ 0.25, and more preferably in the range of 0.1 ⁇ x2 ⁇ 0.15. If the value of x2 exceeds 0.3, the luminescent atoms become high in concentration and cancel each other in close proximity to each other, so that the luminescence intensity tends to be weak.
  • the value of y2 is in the range of 0 ⁇ y2 ⁇ 0.3, preferably in the range of 0 ⁇ y2 ⁇ 0.1, and more preferably in the range of 0 ⁇ y2 ⁇ 0.0001.
  • the value of x2 + y2 is in the range of 0 ⁇ x2 + y2 ⁇ 0.6, preferably in the range of 0.001 ⁇ x2 + y2 ⁇ 0.25, and more preferably in the range of 0.1 ⁇ x2 + y2 ⁇ 0.15.
  • the case where the composition does not contain Eu that is, the case where the value of x2 is 0, or the case where the composition does not contain Ce, that is, the case where the value of y2 is 0, is included. It is necessary to have a composition containing any element of Ce, that is, a composition of x2 + y2> 0.
  • the molar ratio of strontium (Sr) in the phosphor is in the range of 2 ⁇ g ⁇ 8, preferably in the range of 4 ⁇ g ⁇ 8, and 4.5 ⁇ g ⁇ 6 is more preferable, and 4.75 ⁇ g ⁇ 5.25 is more preferable.
  • Sr strontium
  • M2 is one or more metal elements selected from the group consisting of calcium (Ca), barium (Ba), and magnesium (Mg), and the value of h is 0 ⁇ h. Within the range of ⁇ 3 is preferable. In the present invention, the case where the composition does not contain any of Ca, Ba and Mg, that is, the case where the value of h is 0 is included.
  • the molar ratio of boron (B) in the phosphor is in the range of 0.02 ⁇ i ⁇ 0.8, and in the range of 0.04 ⁇ i ⁇ 0.4. preferable.
  • the value of i is in the range of 0.04 ⁇ i ⁇ 0.4, a high-luminance green phosphor with a narrow half-value width is obtained.
  • the molar ratio of aluminum (Al) in the phosphor is in the range of 2 ⁇ j ⁇ 7, preferably in the range of 3 ⁇ j ⁇ 7, and 4 ⁇ j ⁇ 6. Within the range is more preferable.
  • the value of j is in the range of 2 ⁇ j ⁇ 7, a high-luminance green phosphor with a narrow half width is obtained.
  • the molar ratio of silicon (Si) in the phosphor is in the range of 10 ⁇ k ⁇ 25, preferably in the range of 15 ⁇ k ⁇ 25, and 19.5 ⁇ k ⁇
  • the range of 22.5 is more preferable, and the range of 20.5 ⁇ k ⁇ 21.5 is more preferable.
  • k is in the range of 10 ⁇ k ⁇ 25, a high-intensity green phosphor with a narrow half width is obtained.
  • the molar ratio of nitrogen (N) in the phosphor is in the range of 15 ⁇ l ⁇ 37, preferably in the range of 32 ⁇ l ⁇ 37, and 34 ⁇ l ⁇ 36.
  • the range is more preferable, and the range of 34.5 ⁇ l ⁇ 35.5 is more preferable.
  • the value of l is in the range of 15 ⁇ l ⁇ 37, a high-intensity green phosphor with a narrow half width is obtained.
  • the molar ratio of oxygen (O) in the phosphor is in the range of 0 ⁇ m ⁇ 3, and preferably in the range of 0.1 ⁇ m ⁇ 2.3.
  • O oxygen
  • the phosphor of the present invention includes, for example, an Sr-containing compound, an Al-containing compound, an Si-containing compound, an Eu-containing compound and / or a Ce-containing compound, and a B-containing compound.
  • Each raw material-containing compound of Sr-containing compound, Al-containing compound, Si-containing compound, Eu-containing compound, Ce-containing compound, B-containing compound and M-containing compound is nitride, oxynitride, oxide or It is selected from precursor materials that become oxides by thermal decomposition.
  • strontium (Sr) containing compounds for example, strontium nitride (Sr 3 N 2), strontium carbonate (SrCO 3), of one or more selected from the group consisting of strontium oxide (SrO)
  • SrO strontium oxide
  • a powder can be preferably used, and a strontium nitride (Sr 3 N 2 ) powder can be particularly preferably used.
  • Al aluminum
  • specific examples of containing compound include aluminum nitride (AlN), aluminum oxide (Al 2 O 3), is selected from the group consisting of aluminum carbonate (Al 2 (CO 3) 3 )
  • AlN aluminum nitride
  • AlN aluminum nitride
  • Si silicon containing compounds
  • Si 3 N 4 amorphous silicon nitride
  • Si 3 N 4 the crystalline silicon nitride
  • SiO 2 silicon dioxide
  • amorphous silicon nitride (Si 3 N 4 ) and crystalline silicon nitride (Si 3 N 4 ) powders can be preferably used.
  • europium (Eu) -containing compound examples are not particularly limited.
  • europium (III) oxide (Eu 2 O 3 ), europium (II) oxide (EuO), europium nitride (EuN), and europium metal (Eu) One or more kinds of powders selected from the group consisting of can be preferably used.
  • cerium (Ce) containing compounds for example, nitride, cerium (CeN), cerium oxide (CeO 2), one or more powder selected from the group consisting of metallic cerium (Ce) preferably Can be used.
  • the present invention is characterized in that in addition to the raw material-containing compound, a B-containing compound is added in a range of 250 to 10,000 ppm of the raw material mixture.
  • a B-containing compound is added in a range of 250 to 10,000 ppm of the raw material mixture.
  • 250 to 10,000 ppm of the B-containing compound 100 to 2500 ppm of boron can be contained in the obtained phosphor.
  • many crystals of the SrAlSi 4 N 7 structure are contained as a different phase (impurity) in the obtained phosphor.
  • SrAlSi 4 N 7 is added. It has been found that the amount of structural crystals can be reduced.
  • the amount of the B-containing compound added is preferably 750 to 10000 ppm, more preferably 1000 to 5000 ppm.
  • boron (B) containing compounds for example, boron nitride (BN), boron oxide (B 2 O 3), is selected from the group consisting of boron hydroxide (B (OH) 3)
  • B (OH) 3 boron hydroxide
  • an M-containing compound (wherein M is one or more metal elements selected from the group consisting of Ca, Ba and Mg) can be mixed as necessary.
  • Ca calcium nitride
  • CaCO 3 calcium carbonate
  • CaO calcium oxide
  • barium (Ba) containing compound in M-containing compound such as barium nitride (Ba 3 N 2), barium carbonate (BaCO 3), is selected from the group consisting of barium oxide (BaO)
  • barium oxide (BaO) One or more kinds of powders can be preferably used.
  • magnesium (Mg) containing compound in M-containing compound for example, magnesium nitride (Mg 3 N 2), magnesium carbonate (MgCO 3), is selected from the group consisting of magnesium oxide (MgO)
  • MgO magnesium oxide
  • raw material-containing compounds may be used alone or in combination of two or more.
  • Each raw material-containing compound preferably has a purity of 99% by mass or more. Since the mixing ratio of the raw material-containing compound is almost the same as that of the formula (1), the mixing ratio is adjusted so as to be a desired composition ratio. However, since the amount of oxygen and nitrogen are not always constant, considering the oxygen content and nitrogen content contained in the raw material, the mixing ratio of the raw material is set to achieve the target oxygen amount and nitrogen amount. Can be adjusted.
  • a Li-containing compound serving as a sintering aid can be added for the purpose of promoting sintering and generating at a lower temperature.
  • the Li-containing compound used include lithium oxide, lithium carbonate, metallic lithium, and lithium nitride. Each of these powders may be used alone or in combination.
  • the addition amount of the Li-containing compound is suitably 0.01 to 0.5 mol as a Li element with respect to 1 mol of the fired product obtained in the firing step described later. Li-containing compounds are easily volatilized in the firing step, and are hardly contained in the phosphor powder.
  • the mixing method of the raw material powder is not particularly limited, and a method known per se, for example, a dry mixing method, a method of removing the solvent after wet mixing in an inert solvent that does not substantially react with each component of the raw material, etc. Can be adopted.
  • a V-type mixer, a rocking mixer, a ball mill, a vibration mill, a medium stirring mill, or the like is preferably used.
  • the raw material mixture is fired.
  • the firing of the raw material mixture is preferably performed in an inert gas atmosphere or a reducing gas atmosphere.
  • the inert gas atmosphere can be composed of an inert gas such as a rare gas such as nitrogen or argon or a mixed gas thereof. Since it is an inert gas atmosphere, it is desirable not to contain oxygen, but oxygen may be contained as an impurity in an amount of less than 0.1 vol%, or even less than 0.01 vol%.
  • the reducing gas atmosphere can be composed of a mixed gas of a rare gas such as nitrogen or argon and hydrogen gas or carbon monoxide gas.
  • the firing temperature is in the range of 1500 to 2000 ° C., more preferably 1600 to 1800 ° C.
  • the firing time is generally in the range of 0.5 to 100 hours, and preferably in the range of 0.5 to 20 hours.
  • the firing pressure may be normal pressure or higher, and is preferably less than 0.92 MPa.
  • the phosphor obtained by firing does not need to be pulverized, and for example, when used as a light-emitting element of a white LED, a desired particle size can be obtained. Pulverized and optionally classified to a desired particle size range.
  • the pulverization method may be either a wet pulverization method or a dry pulverization method.
  • the classification method any operation method generally used for classification of powder, such as sieving operation, operation using fluid, etc. May be used.
  • the phosphor obtained by firing may be subjected to an acid cleaning treatment or a baking treatment with a mineral acid such as hydrochloric acid or nitric acid, if necessary.
  • the phosphor of the present invention can be used in various light-emitting devices.
  • the light-emitting device of the present invention includes at least a phosphor of the present invention that further contains 100 to 2500 ppm of boron in the composition represented by the above formula (1), and a light source that emits light by irradiating the phosphor with excitation light.
  • Specific examples of the light emitting device include a white light emitting diode (white LED), a fluorescent lamp, a fluorescent display tube (VFD), a cathode ray tube (CRT), a plasma display panel (PDP), and a field emission display (FED). it can.
  • the white LED includes a blue phosphor, a red phosphor, the phosphor of the present invention (green phosphor), and a semiconductor light emitting device that emits ultraviolet light having a wavelength of, for example, 350 to 430 nm, and ultraviolet light from the light emitting device.
  • a blue phosphor, a green phosphor and a red phosphor are excited to obtain a white color by mixing blue, red and green.
  • a red phosphor, the phosphor of the present invention (green phosphor), and a semiconductor element that emits blue light with a wavelength of 430 to 500 nm are provided.
  • the present invention can also be applied to a light emitting device that excites a phosphor and obtains white by mixing blue, red, and green.
  • blue light emitting phosphors examples include (Ba, Sr, Ca) 3 MgSi 2 O 8 : Eu, (Ba, Sr, Ca) MgAl 10 O 17 : Eu, (Ba, Sr, Mg, Ca) 10 (PO 4 ) 6 (Cl, F) 2 : Eu and the like.
  • red light emitting phosphor examples include (Ba, Sr, Ca) 3 MgSi 2 O 8 : Eu, Mn, Y 2 O 2 S: Eu, La 2 O 3 S: Eu, (Ca, Sr, Ba ) 2 Si 5 N 8 : Eu, CaAlSiN 3 : Eu, Eu 2 W 2 O 9 , (Ca, Sr, Ba) 2 Si 5 N 8 : Eu, Mn, CaTiO 3 : Pr, Bi, (La, Eu) 2 W 3 O 12 and the like can be mentioned.
  • the semiconductor light emitting device examples include an AlGaN semiconductor light emitting device.
  • the crystal phase was identified using an X-ray diffraction (XRD) apparatus (Ultima IV, manufactured by Rigaku Corporation).
  • the particle size distribution measurement was performed using a laser diffraction / scattering particle size distribution measuring apparatus (MT3300EX II manufactured by Nikkiso Co., Ltd.).
  • Fluorescence peak wavelength, emission intensity, half width of spectrum Using a spectrofluorimeter (manufactured by JASCO Corporation, FP-6500), the fluorescence spectrum at an excitation wavelength of 450 nm was measured, and the fluorescence peak wavelength, the emission intensity at that wavelength, and the half width of the spectrum were determined.
  • the light emission intensity is shown as 100% of the light emission intensity of Comparative Example 1 at the peak wavelength of 522.0 nm.
  • the boron content in the phosphor powder was quantitatively analyzed using an inductively coupled plasma emission spectroscopic analysis (ICP-AES) apparatus (manufactured by SII Nanotechnology Inc., SPS3250UV).
  • ICP-AES inductively coupled plasma emission spectroscopic analysis
  • FIG. 1 shows an XRD pattern
  • FIG. 2 shows an emission spectrum
  • FIG. 3 shows a scanning electron micrograph.
  • the synthetic powder was a mixed phase of Sr 5 Al 5 Si 21 N 35 O 2 structure and SrAlSi 4 N 7 structure.
  • the ratio (B / A) to the intensity (B) of the diffraction peak derived from the surface was 2.75.
  • D 10 diameter was 13.8Myuemu.
  • boron was not detected.
  • Comparative Example 1 When excited at a wavelength of 450 nm, the emission spectrum shown in FIG. 2 was obtained. The peak wavelength is 522.0 nm and green, but the half-value width is as wide as 111.1 nm, and light emission includes a red component. Further, from the scanning electron micrograph shown in FIG. 3, Comparative Example 1 has a large primary particle diameter before pulverization, the average value of Heywood diameter is 35.9 ⁇ m, and pulverization is performed when classifying with a sieve having an opening of 32 ⁇ m. There was an increase in crushed debris.
  • Example 1 Example 1 to 6 were carried out in the same manner as in Comparative Example 1 except that boron nitride (BN) powder (purity: 99%) was added as shown in Table 1.
  • the evaluation results of the synthetic powder are shown in Table 2.
  • the ratio (B / A) to the intensity (B) of the diffraction peak derived from the (221) plane in the vicinity is less than 0.03.
  • FIG. 1 shows an XRD pattern of Example 5.
  • the boron content increased according to the boron addition amount and was 110 to 2300 ppm.
  • the element concentration of boron on the outermost surface of the phosphor was 14000 to 92000 ppm.
  • the emission peak wavelength is 520.5 to 524.0 nm in green, and the relative emission intensity is 132.5 to 194.9% when Comparative Example 1 is taken as 100%. It was.
  • the full width at half maximum of the emission spectrum was 67.3 to 76.4 nm.
  • FIG. 2 shows an emission spectrum of Example 5
  • FIG. 3 shows a scanning electron micrograph of Example 5.
  • Example 5 since the boron content is in the range of 100 to 2500 ppm, the single phase of the Sr 5 Al 5 Si 21 N 35 O 2 structure has few fine particles, and the emission spectrum has a narrow half-value width and high brightness. A phosphor was obtained. Moreover, from the scanning electron micrograph before pulverization of Example 5 shown in FIG. 3, Example 5 has a smaller primary particle diameter than Comparative Example 1, and the average value of the Heywood diameter at this time is 26.8 ⁇ m. There was no need to grind when classifying with a sieve having an opening of 32 ⁇ m.
  • Example 5 Furthermore, about the sample of Example 5, using the X-ray photoelectron spectroscopy (XPS) apparatus (PHI5000 by ULVAC-PHI Co., Ltd.), the elemental concentration of boron on the surface after Ar etching to a depth of 200 nm in terms of SiO 2 was determined. , X-ray source: Al—K ⁇ , extraction angle: 45 ° from the surface. The results are shown in Table 3 and FIG.
  • the elemental concentration of boron on the outermost surface of the phosphor by XPS is 55000 ppm, and it decreases as it goes inside the particle, and the elemental concentration of boron at a depth of 100 nm or more from the outermost surface of the phosphor (measures the surface after etching). Then, it was asymptotic to about 9000 ppm.
  • XPS X-ray photoelectron spectroscopy
  • Comparative Examples 2 to 4 were carried out in the same manner as in Example 1 except that the amount of boron nitride (BN) powder (purity: 99%) was changed as shown in Table 1.
  • the evaluation results of the synthetic powder are shown in Table 2.
  • the intensity (A) of the diffraction peak derived from the (021) plane near 25.8 ° of the Sr 5 Al 5 Si 21 N 35 O 2 structure and 24.9 ° of the SrAlSi 4 N 7 structure.
  • the ratio (B / A) to the intensity (B) of the diffraction peak derived from the (221) plane in the vicinity is 0.04 to 0.21, and the Sr 5 Al 5 Si 21 N 35 O 2 structure and SrAlSi 4 It has been a mixed phase of N 7 structure.
  • D 10 diameter was 11.5 ⁇ 17.0 ⁇ m.
  • the boron content was 54 ppm in Comparative Example 2, 84 ppm in Comparative Example 3, and 3600 ppm in Comparative Example 4.
  • the element concentration at the outermost surface of the phosphor of Comparative Example 2 was 8000 ppm
  • the element concentration at the outermost surface of the phosphor of Comparative Example 3 was 12000 ppm
  • the boron at the outermost surface of the phosphor of Comparative Example 4 The element concentration was 120,000 ppm.
  • the emission peak wavelength was green of 523.0 to 524.0 nm, and the relative emission intensity was 113.4 to 120.1% when Comparative Example 1 was taken as 100%.
  • the full width at half maximum of the emission spectrum was 78.5-90.9 nm.

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Abstract

L'invention concerne un corps fluorescent qui comprend une phase cristalline représentée par une composition de formule (1), le corps fluorescent étant caractérisé en ce qu'il contient également 100 à 2 500 ppm de bore. SraM1bAlcSidNeOf : Eux1Cey1... (1) (dans laquelle : M1 est au moins un élément métallique choisi dans le groupe constitué par Ca, Ba et Mg ; 2 ≤ a ≤ 8 ; 0 ≤ b ≤ 3 ; 2 ≤ c ≤ 7 ; 10 ≤ d ≤ 25 ; 15 ≤ e ≤ 37 ; 0 ≤ f ≤ 3 ; et 0 < x1 + y1 ≤ 0,6.)
PCT/JP2016/073243 2015-08-19 2016-08-08 Corps fluorescent, son procédé de production, et dispositif électroluminescent WO2017030030A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP2006063214A (ja) * 2004-08-27 2006-03-09 Dowa Mining Co Ltd 蛍光体及びその製造方法並びに光源
WO2006093135A1 (fr) * 2005-02-28 2006-09-08 Denki Kagaku Kogyo Kabushiki Kaisha Substance fluorescente et procédé de fabrication idoine, et élément luminescent utilisant ladite substance
JP2009256558A (ja) * 2007-05-22 2009-11-05 Showa Denko Kk 蛍光体及びその製造方法、並びにそれを用いた発光装置
JP2009286995A (ja) * 2007-09-03 2009-12-10 Showa Denko Kk 蛍光体及びその製造方法、並びにそれを用いた発光装置
JP2010031201A (ja) * 2008-07-31 2010-02-12 Toshiba Corp 蛍光体およびそれを用いた発光装置
JP2011505451A (ja) * 2007-12-03 2011-02-24 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ 緑色光放出ＳｉＡｌＯＮをベースにする材料を含有する光放出デバイス
WO2012167517A1 (fr) * 2011-06-08 2012-12-13 中国科学院宁波材料技术与工程研究所 Procédé de préparation de poudre fluorescente de nitrure/oxynitrure utilisée par une del blanche
JP2013043937A (ja) * 2011-08-24 2013-03-04 Toshiba Corp 蛍光体、発光装置および蛍光体の製造方法
US20140110632A1 (en) * 2012-10-18 2014-04-24 Epistar Corporation Compound of phosphor and the manufacturing method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006063214A (ja) * 2004-08-27 2006-03-09 Dowa Mining Co Ltd 蛍光体及びその製造方法並びに光源
WO2006093135A1 (fr) * 2005-02-28 2006-09-08 Denki Kagaku Kogyo Kabushiki Kaisha Substance fluorescente et procédé de fabrication idoine, et élément luminescent utilisant ladite substance
JP2009256558A (ja) * 2007-05-22 2009-11-05 Showa Denko Kk 蛍光体及びその製造方法、並びにそれを用いた発光装置
JP2009286995A (ja) * 2007-09-03 2009-12-10 Showa Denko Kk 蛍光体及びその製造方法、並びにそれを用いた発光装置
JP2011505451A (ja) * 2007-12-03 2011-02-24 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ 緑色光放出ＳｉＡｌＯＮをベースにする材料を含有する光放出デバイス
JP2010031201A (ja) * 2008-07-31 2010-02-12 Toshiba Corp 蛍光体およびそれを用いた発光装置
WO2012167517A1 (fr) * 2011-06-08 2012-12-13 中国科学院宁波材料技术与工程研究所 Procédé de préparation de poudre fluorescente de nitrure/oxynitrure utilisée par une del blanche
JP2013043937A (ja) * 2011-08-24 2013-03-04 Toshiba Corp 蛍光体、発光装置および蛍光体の製造方法
US20140110632A1 (en) * 2012-10-18 2014-04-24 Epistar Corporation Compound of phosphor and the manufacturing method thereof

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