WO2013108782A1 - Luminophore à base d'oxynitrure et dispositif électroluminescent l'utilisant - Google Patents

Luminophore à base d'oxynitrure et dispositif électroluminescent l'utilisant Download PDF

Info

Publication number
WO2013108782A1
WO2013108782A1 PCT/JP2013/050668 JP2013050668W WO2013108782A1 WO 2013108782 A1 WO2013108782 A1 WO 2013108782A1 JP 2013050668 W JP2013050668 W JP 2013050668W WO 2013108782 A1 WO2013108782 A1 WO 2013108782A1
Authority
WO
WIPO (PCT)
Prior art keywords
phosphor
light
less
emitting device
phosphors
Prior art date
Application number
PCT/JP2013/050668
Other languages
English (en)
Japanese (ja)
Inventor
文孝 吉村
岳史 田原
Original Assignee
三菱化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱化学株式会社 filed Critical 三菱化学株式会社
Publication of WO2013108782A1 publication Critical patent/WO2013108782A1/fr

Links

Images

Classifications

    • 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
    • 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
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144—Gold (Au) as principal constituent
    • 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
    • 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
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • 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

Definitions

  • the present invention relates to an oxynitride phosphor and a light-emitting device using the same.
  • Fluorescent substances are used in fluorescent display tubes (VFD), field emission displays (FED), plasma display panels (PDP), cold cathode tubes (CRT), light emitting devices (LEDs), and the like.
  • VFD fluorescent display tubes
  • FED field emission displays
  • PDP plasma display panels
  • CRT cold cathode tubes
  • LEDs light emitting devices
  • the phosphor is excited by an excitation source having high energy such as vacuum ultraviolet rays, ultraviolet rays, electron beams, blue light, and emits visible light.
  • Sr 2 Al 3 Si 7 ON 13 Eu
  • SrAl 1.25 Si 3.75 O 0.25 N 6.75 Eu
  • SrAlSi 4 N are one of the oxynitride phosphors that are attracting attention.
  • 7 Phosphors having a composition typified by Eu have been reported (Patent Documents 1 to 4).
  • JP 2010-106127 A International Publication No. 2007/037059 Pamphlet Special table 2010-518194 gazette JP 2011-195688 A
  • Patent Document 1 Although the crystal structure of the phosphor described in Patent Document 1 is disclosed, no study has been made on the size of the crystal lattice and the effect of element substitution, and high emission intensity can be obtained. Therefore, further improvement in emission intensity is required for practical use.
  • the phosphor described in Patent Document 2 discloses a specific example in which the Sr site is replaced with Ba, but the effect has not been sufficiently studied, and the relationship with the crystal structure has not been studied at all.
  • Patent Document 3 discloses that the emission wavelength can be lengthened by substituting the Sr site with Ca, there is no disclosure of specific examples of substituting with Ca, and the size of the crystal lattice due to Ca substitution. There is no suggestion of any change in light emission or improvement in emission intensity.
  • the phosphor described in Patent Document 4 described above has improved the emission intensity, it is still insufficient in practical use, and repeated firing is required to obtain a single phase. The manufacturing cost may be high.
  • the phosphors described in Patent Documents 1 to 4 that is, phosphors having a skeletal structure composed of Si, Al, N, and O and having a crystal structure in which Sr sites exist in the voids.
  • the improvement of the emission intensity was desired.
  • An object of the present invention is to improve the emission intensity of a phosphor having a skeleton structure composed of Si, Al, N, and O and having a crystal structure in which Sr sites exist in the voids.
  • the inventors of the present invention are excellent in terms of emission intensity of oxynitride phosphors whose unit cell volume of the crystal phase is in a specific range.
  • the general formula [1] it has been found that when Ca is essential among the alkaline earth metal elements, the emission intensity is further improved.
  • the present invention has been accomplished based on these findings.
  • the gist of the present invention includes the phosphor of the following first embodiment.
  • A represents an alkaline earth metal element essential for Sr and Ca
  • D represents a tetravalent metal element essential for Si
  • E represents a trivalent metal essential for Al.
  • x represents a number satisfying 0.0001 ⁇ x ⁇ 0.20
  • a, b, c, d, and e represent 0.7 ⁇ a ⁇ 1.3 and 2.8 ⁇ b ⁇ , respectively.
  • the crystal phase of the crystal phase is orthorhombic or monoclinic, and the emission peak is An oxynitride phosphor having a wavelength in the range of 581 nm to 650 nm.
  • the gist of the present invention includes the phosphor of the following third embodiment. [8] The following formula [2]: (A 1-x , Eu x ) a D b E c N d O e [2] (In the formula [2], A represents an alkaline earth metal element essential for Sr and Ca, D represents a tetravalent metal element essential for Si, and E represents a trivalent metal essential for Al.
  • x represents a number satisfying 0.0001 ⁇ x ⁇ 0.20
  • a, b, c, d, and e represent 0.7 ⁇ a ⁇ 1.3 and 2.8 ⁇ b ⁇ , respectively.
  • 3.6 1.0 ⁇ c ⁇ 3.0, 4.0 ⁇ (b + c) /a ⁇ 6.0, 5.0 ⁇ d ⁇ 7.0, 0 ⁇ e ⁇ 2.0, 6.5 ⁇ (D + e) /a ⁇ 7.3 is included.
  • the ratio of Ca to element A in the above [2] is 0.001 mol% or more and 80 mol% or less.
  • the crystal system of the crystal phase is orthorhombic or monoclinic.
  • the gist of the present invention includes the phosphor-containing composition, the light emitting device, the lighting device, and the image display device of the following embodiment.
  • a light-emitting device having a first light emitter (excitation light source) and a second light emitter capable of emitting visible light by converting light from the first light emitter,
  • the second light emitter contains at least one of the phosphors according to any one of [1] to [11] as the first phosphor, or the second light emitter according to [12]
  • a light emitting device comprising the phosphor-containing composition described above.
  • the second phosphor includes at least one phosphor having a light emission peak wavelength different from that of the first phosphor as the second phosphor. apparatus.
  • the present invention it is possible to improve the light emission intensity of a phosphor having a skeletal structure composed of Si, Al, N, and O and having a crystal structure in which Sr sites exist in the voids. Furthermore, the phosphor of the present invention hardly produces an impurity phase and can be easily manufactured. In addition, when the phosphor of the present invention is combined with an LED or the like, a light emitting device having excellent light emission characteristics can be provided.
  • FIG. 2A shows a bullet-type light emitting device
  • FIG. 2B shows a surface-mounted light-emitting device.
  • FIG. 2C shows typically the one aspect
  • 3 is an emission spectrum of the phosphors of Examples 2, 3, 6 to 9, 13 and Comparative Example 1.
  • 3 is an excitation spectrum of the phosphor of Example 2.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • each composition formula is delimited by a punctuation mark (,).
  • commas when a plurality of elements are listed separated by commas (,), one or two or more of the listed elements may be included in any combination and composition.
  • composition formula “(Ca, Sr, Ba) Al 2 O 4 : Eu” has “CaAl 2 O 4 : Eu”, “SrAl 2 O 4 : Eu”, and “BaAl 2 O 4 : Eu”. “Ca 1-x Sr x Al 2 O 4 : Eu”, “Sr 1-x Ba x Al 2 O 4 : Eu”, “Ca 1-x Ba x Al 2 O 4 : Eu”, “Ca 1-x-y Sr x Ba y Al 2 O 4: Eu " (. in the formula, 0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1,0 ⁇ a x + y ⁇ 1) all the comprehensive It shall be shown in the formula, 0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1,0 ⁇ a x + y ⁇ 1) all the comprehensive It shall be shown in
  • the phosphors of the first to third embodiments of the present invention have a skeletal structure composed of Si, Al, N, and O, and have a crystal structure in which Sr sites exist in the voids.
  • Crystal system The crystal system of the crystal phase contained in the phosphor according to the first to third embodiments of the present invention is orthorhombic or monoclinic, and is preferably orthorhombic.
  • the phosphors according to the first to third embodiments of the present invention preferably have a crystal structure similar to that of SrAlSi 4 N 7, and the crystal phase space group is “International Tables for Crystallography (Third, revised edition)”. No. 62 [Pnma], 33 [Pna2 1 ], 19 [P2 1 2 1 2 1 ], 7 [Pc], or 4 [P2 1 ] based on “Volume A Space-Group Symmetry” And those belonging to No. 33 [Pna2 1 ] are most preferred.
  • the space group can be uniquely determined by electron diffraction or convergent electron diffraction.
  • the phosphor according to the first embodiment of the present invention contains a crystal phase whose unit cell volume (V) calculated from the lattice constant is 1220 ⁇ 10 6 pm 3 or more and 1246 ⁇ 10 6 pm 3 or less.
  • V unit cell volume
  • the unit cell volume (10 6 pm 3 ) calculated from the lattice constant of the crystal phase contained in the phosphor of the first embodiment of the present invention is usually 1220 or more and 1246 or less, preferably It is 1224 or more, more preferably 1228 or more, further preferably 1232 or more, further preferably 1236 or more, particularly preferably 1240 or more, and preferably 1245 or less, more preferably 1244 or less.
  • the unit cell volume is too large, the emission intensity will decrease. Conversely, if the unit cell volume is too small, the skeletal structure will become unstable and impurities of another structure will be produced as a by-product. It tends to cause a decline.
  • the means for realizing the unit cell volume of the crystal phase contained in the phosphor according to the first embodiment of the present invention is that Sr and Ca are contained in the voids (Sr sites) formed by the open holes in the planar skeleton structure. It is preferable to introduce at a constant ratio, but other atoms having an ionic radius smaller than Sr, such as Mg and Li, may be introduced in addition to Sr and Ca. It is also preferable to adjust the unit cell volume by leaving defects at the Sr site. It is also possible to construct an appropriate skeleton structure by introducing both small atoms or defects such as Li that have a large effect on reducing the skeletal structure and large atoms such as Ba that have the effect of increasing the skeleton structure. is there.
  • the phosphors of the second to third embodiments of the present invention preferably satisfy the requirements for the unit cell volume (V).
  • the a-axis is usually 1162 or more, preferably 1164 or more, more preferably 1166 or more, and usually 1178. Hereinafter, it is preferably 1172 or less, more preferably 1168 or less. Further, the b-axis is usually 2115 or more, preferably 2125 or more, more preferably 2135 or more, particularly preferably 2137.5 or more, and usually 2165 or less, preferably 2155 or less, more preferably 2145 or less.
  • the phosphor according to the first to third embodiments of the present invention has a planar skeletal structure with a hole extending on a plane including the a-axis and the b-axis, and the planar skeletal structure is c-axis.
  • a skeletal structure is formed by stacking in the direction. Therefore, when the lattice constants of the a axis and the b axis are the above values, particularly the distortion of the planar skeleton structure can be suppressed, and the emission intensity is improved.
  • the c-axis is not particularly limited, but is usually 494 or more, preferably 494.5 or more, more preferably 495.5 or more, particularly preferably 496.5 or more, usually 499.5 or less, preferably 498.5 or more, More preferably, it is 497.5 or less.
  • the phosphors of the first to third embodiments of the present invention preferably contain a crystal phase exhibiting the following powder X-ray diffraction (XRD) pattern.
  • the crystal phase of the phosphor of the first to third embodiments of the present invention has a diffraction angle (2 ⁇ ) in the range of 31.0 ° to 31.9 ° (R0) in X-ray diffraction measurement using a CuK ⁇ X-ray source.
  • P0 reference diffraction peak
  • ⁇ 0 Bragg angle
  • the intensity of P0 is usually 20% or more, preferably 30% or more, more preferably 40% or more, particularly preferably 50% or more in terms of diffraction peak height ratio with respect to the height of the highest diffraction peak.
  • the diffraction peak height is the highest among the P1, P2, P3, P4, and P5.
  • a peak intensity of at least one or more is a diffraction peak height ratio, usually 5% or more, preferably 10% or more, more preferably 15% or more, and particularly preferably 20% or more of a crystal phase, P1, P2, P3 , P4 Is 5% or more crystalline phases at least one or more peak intensity diffraction peak height ratio of P5.
  • R1s, R2s, R3s, R4s, and R5s are the start angles of R1, R2, R3, R4, and R5, and R1e, R2e, R3e, R4e, and R5e are R1, R2, R3, R4, and R5, respectively.
  • the end angle is shown, and the following angles are shown.
  • R1s 2 ⁇ arcsin ⁇ sin ( ⁇ 0) / (1.268 ⁇ 1.015) ⁇
  • R1e 2 ⁇ arcsin ⁇ sin ( ⁇ 0) / (1.268 ⁇ 0.985) ⁇
  • R2s 2 ⁇ arcsin ⁇ sin ( ⁇ 0) / (1.037 ⁇ 1.015) ⁇
  • R2e 2 ⁇ arcsin ⁇ sin ( ⁇ 0) / (1.037 ⁇ 0.985) ⁇
  • R3s 2 ⁇ arcsin ⁇ sin ( ⁇ 0) / (1.023 ⁇ 1.015) ⁇
  • R3e 2 ⁇ arcsin ⁇ sin ( ⁇ 0) / (1.023 ⁇ 0.985) ⁇
  • R4s 2 ⁇ arcsin ⁇ sin ( ⁇ 0) / (0.882 ⁇ 1.015) ⁇
  • R4e 2 ⁇ arcsin ⁇ sin ( ⁇ 0) / (0.882 ⁇ 1.015) ⁇
  • the phosphor of the present invention includes a phosphor having a yellow to red emission color (first embodiment), a phosphor having an orange to red emission color (second embodiment), which will be described below. And a phosphor having a light emission color of yellow to orange (third embodiment).
  • the phosphor according to the first embodiment of the present invention has the following formula [1]: (A 1-x , Eu x ) a D b E c N d O e [1]
  • A represents an alkaline earth metal element essential for Sr and Ca
  • D represents a tetravalent metal element essential for Si
  • E represents a trivalent metal essential for Al.
  • x represents a number satisfying 0.0001 ⁇ x ⁇ 0.20
  • a, b, c, d, and e represent 0.7 ⁇ a ⁇ 1.3 and 2.8 ⁇ b ⁇ , respectively.
  • A represents an alkaline earth metal element in which Sr and Ca are essential.
  • the ratio of Sr and Ca to the entire A element is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more.
  • the element A may contain an alkaline earth metal element such as barium (Ba).
  • the ratio of Ca with respect to the entire element A is a number that usually satisfies 0.001 mol% or more and 80 mol% or less, preferably 0.01 mol% or more, more preferably 1 mol% or more, More preferably 5 mol% or more, particularly preferably 7 mol% or more, most preferably 9 mol% or more, preferably 65 mol% or less, more preferably 50 mol% or less, more preferably 35 mol% or less. Especially preferably, it is 20 mol% or less.
  • the proportion of Ca is in the above range, the lattice volume becomes a more appropriate size, and the skeletal structure can take a stable state without distortion.
  • Eu represents an activator element that requires europium.
  • Europium (Eu) which is an activator, includes chromium (Cr), manganese (Mn), iron (Fe), cerium (Ce), praseodymium (Pr), neodymium (Nd), and samarium (Sm) as other activators.
  • chromium (Cr) manganese (Mn), iron (Fe), cerium (Ce), praseodymium (Pr), neodymium (Nd), and samarium (Sm) as other activators.
  • Terbium (Tb) Dy
  • Dy dysprosium
  • Ho holmium
  • Er erbium
  • Tm thulium
  • Yb ytterbium
  • at least one metal element selected from the group consisting of Ce, Pr, Sm, Tb, and Yb is preferable, and Ce is more preferable in terms of emission quantum efficiency.
  • the ratio of europium (Eu) to the whole activator element is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more.
  • D represents a tetravalent metal element in which Si is essential.
  • the element D may contain germanium (Ge) or the like within a range that does not affect the properties of the obtained phosphor.
  • the proportion of Si with respect to the entire D element is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more. If the ratio of Si to the entire D element is too small, impurities are generated, and it tends to be difficult to obtain a phosphor having the target composition.
  • E represents a trivalent metal element in which Al is essential.
  • the element E may contain boron (B), gallium (Ga), or the like within a range that does not affect the properties of the obtained phosphor.
  • the proportion of Al to the entire E element is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more. If the ratio of Al to the entire E element is too small, impurities are generated, and it tends to be difficult to obtain a phosphor having the target composition.
  • N represents nitrogen.
  • the N element only needs to contain nitrogen as a main component, and may contain fluorine (F), chlorine (Cl), or the like within a range that does not affect the characteristics of the obtained phosphor.
  • O represents oxygen.
  • the O element only needs to contain oxygen as a main component, and may contain F, Cl, or the like within a range that does not affect the characteristics of the obtained phosphor.
  • the phosphor of the first embodiment of the present invention affects the effects of the first embodiment of the present invention in addition to the above-described constituent elements of A, Eu, D, E, N and O. It may contain an element inevitably mixed within a range, for example, an impurity element.
  • x represents the molar ratio of the activator element (Eu).
  • x is a number satisfying 0.0001 ⁇ x ⁇ 0.20, preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.01 or more, and preferably 0.19. In the following, it is more preferably 0.17 or less, further preferably 0.15 or less, particularly preferably 0.12 or less.
  • a represents the sum of molar ratios of the element A (an alkaline earth metal element essential for Sr and Ca) and the activator element (Eu).
  • a is usually a number satisfying 0.7 ⁇ a ⁇ 1.3, preferably 0.8 or more, more preferably 0.9 or more, particularly preferably 0.95 or more, and preferably 1. It is 2 or less, more preferably 1.1 or less, and particularly preferably 1.05 or less.
  • the molar ratio of “a” and the moles of “b” and “c” described below are within the scope of the first embodiment of the present invention, that is, the D element (a tetravalent metal element in which Si is essential) and By setting the ratio of element E (trivalent metal element essential for Al) within a specific range, element A (alkaline earth metal element essential for Sr and Ca) is surely solid-dissolved. A phosphor exhibiting the effect can be obtained.
  • b represents the molar ratio of the D element (a tetravalent metal element in which Si is essential).
  • b is a number satisfying 2.8 ⁇ b ⁇ 4.0, preferably 3.0 or more, more preferably 3.2 or more, more preferably 3.4 or more, more preferably 3.5 or more, particularly Preferably, it is 3.55 or more, preferably 3.9 or less, more preferably 3.8 or less, still more preferably 3.7 or less, and particularly preferably 3.65 or less.
  • c represents the molar ratio of the E element (a trivalent metal element in which Al is essential).
  • c is a number satisfying 1.0 ⁇ c ⁇ 3.0, preferably 1.1 or more, more preferably 1.2 or more, still more preferably 1.3 or more, and preferably 2.5 or more. Below, more preferably 2.0 or less, still more preferably 1.75 or less, particularly preferably 1.5 or less.
  • (b + c) / a is a ratio of the sum of the molar ratio of the D element and the E element to the sum of the molar ratio of the A element and the activator element, and is generally 4.0 ⁇ (b + c) / a ⁇ 6 It is a number satisfying .0. Further, (b + c) / a is preferably 4.25 or more, more preferably 4.5 or more, still more preferably 4.75 or more, and preferably 5.75 or less, more preferably 5.5. Hereinafter, it is more preferably 5.25 or less.
  • d represents the molar ratio of N element (nitrogen).
  • d is a number satisfying 5.0 ⁇ d ⁇ 7.0, preferably 5.5 or more, more preferably 6.0 or more, further preferably 6.25 or more, and particularly preferably 6.5 or more. Also, it is preferably 6.9 or less, more preferably 6.8 or less, and particularly preferably 6.7 or less.
  • e represents the molar ratio of O element (oxygen).
  • e is a number satisfying 0 ⁇ e ⁇ 2.0, preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, still more preferably 0.4 or more, More preferably 0.45 or more, further preferably 0.5 or more, particularly preferably 0.55 or more, preferably 1.5 or less, more preferably 1.0 or less, more preferably 0.8 or less. More preferably, it is 0.6 or less.
  • (d + e) / a is the ratio of the sum of the molar ratios of N element (nitrogen) and O element (oxygen) to the sum of the molar ratios of element A and activator element, and usually 6.5 ⁇ ( d + e) /a ⁇ 7.5.
  • (d + e) / a is preferably 6.7 or more, more preferably 6.9 or more, particularly preferably 6.95 or more, and preferably 7.3 or less, more preferably 7.1 or less. Particularly preferably, it is 7.05 or less.
  • the molar ratio of a, the molar ratio of d, and the molar ratio of e are within the above ranges, that is, a, b, c, (b + c) / a,
  • the A element can be reliably dissolved, and a phosphor exhibiting the above-described effects can be obtained.
  • Sr is 13.5 wt% or more and 25.4% or less
  • Ca is more than 0 and 6.3 wt% or less
  • Eu is more than 0 and 5.0 or less.
  • Wt% or less Si 25.0 wt% or more and 37.0 wt% or less, Al 8.1 wt% or more 17.7 wt% or less, N 25.0 wt% or more 33.0 wt% or less, O Is preferably more than 0 and 5.3% by weight or less.
  • the phosphor of the third embodiment of the present invention has the following formula [2]: (A 1-x , Eu x ) a D b E c N d O e [2]
  • A represents an alkaline earth metal element essential for Sr and Ca
  • D represents a tetravalent metal element essential for Si
  • E represents a trivalent metal essential for Al.
  • x represents a number satisfying 0.0001 ⁇ x ⁇ 0.20
  • a, b, c, d, and e represent 0.7 ⁇ a ⁇ 1.3 and 2.8 ⁇ b ⁇ , respectively.
  • a shows the sum of the molar ratio of A element (alkaline earth metal element which makes Sr and Ca essential) and activator element (Eu).
  • a is usually a number satisfying 0.7 ⁇ a ⁇ 1.3, preferably 0.95 or more, more preferably 0.97 or more, more preferably 0.99 or more, and preferably 1. 05 or less, more preferably 1.03 or less, more preferably 1.1 or less.
  • the molar ratio of “a” and the moles of “b” and “c” described below are included in the range of the third embodiment of the present invention, that is, D element (a tetravalent metal element in which Si is essential) and By setting the ratio of element E (trivalent metal element essential for Al) within a specific range, element A (alkaline earth metal element essential for Sr and Ca) is surely solid-dissolved. A phosphor exhibiting the effect can be obtained.
  • b represents the molar ratio of the D element (a tetravalent metal element in which Si is essential).
  • b is a number satisfying 2.8 ⁇ b ⁇ 3.6, preferably 2.9 or more, more preferably 3.0 or more, more preferably 3.1 or more, more preferably 3.2 or more. Also, it is preferably 3.55 or less, more preferably 3.50 or less, further preferably 3.45 or less, and particularly preferably 3.4 or less.
  • c represents the molar ratio of the E element (a trivalent metal element in which Al is essential).
  • c is a number satisfying 1.0 ⁇ c ⁇ 3.0, preferably 1.4 or more, more preferably 1.45 or more, more preferably 1.5 or more, and further preferably 1.55 or more. Also, it is preferably 2.2 or less, more preferably 2.1 or less, more preferably 2.0 or less, further preferably 1.9 or less, and particularly preferably 1.8 or less. Further, (b + c) / a is a ratio of the sum of the molar ratio of the D element and the E element to the sum of the molar ratio of the A element and the activator element, and is generally 4.0 ⁇ (b + c) / a ⁇ 6 It is a number satisfying .0.
  • (b + c) / a is preferably 4.7 or more, more preferably 4.75 or more, more preferably 4.8 or more, still more preferably 4.85 or more, and preferably 5.3.
  • it is more preferably 5.25 or less, more preferably 5.2 or less, further preferably 5.15 or less, and particularly preferably 5.1 or less.
  • "d" shows the molar ratio of N element (nitrogen).
  • d is a number satisfying 5.0 ⁇ d ⁇ 7.0, preferably 5.8 or more, more preferably 5.9 or more, more preferably 6.0 or more, still more preferably 6.1 or more, particularly Preferably, it is 6.2 or more, preferably 6.6 or less, more preferably 6.55 or less, more preferably 6.5 or less, further preferably 6.45 or less, and particularly preferably 6.4 or less. is there.
  • e represents the molar ratio of O element (oxygen).
  • e is a number satisfying 0 ⁇ e ⁇ 2.0, preferably 0.4 or more, more preferably 0.45 or more, more preferably 0.5 or more, still more preferably 0.55 or more, and particularly preferably It is 0.6 or more, preferably 1.2 or less, more preferably 1.1 or less, more preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.8 or less.
  • (d + e) / a is the ratio of the sum of the molar ratios of N element (nitrogen) and O element (oxygen) to the sum of the molar ratios of element A and activator element, and usually 6.5 ⁇ ( d + e) /a ⁇ 7.3.
  • (d + e) / a is preferably 6.7 or more, more preferably 6.75 or more, more preferably 6.8 or more, particularly preferably 6.85 or more, and preferably 7.3 or less. More preferably, it is 7.25 or less, More preferably, it is 7.2 or less, Most preferably, it is 7.15 or less.
  • the molar ratio of a, the molar ratio of d, and the molar ratio of e are within the above ranges, that is, a, b, c, (b + c) / a, d, e, (d + e ) / A in the above range makes it possible to obtain a phosphor exhibiting the effects described above by reliably dissolving the A element.
  • the phosphor of the first embodiment of the present invention is usually 550 nm or more, preferably 570 nm or more, more preferably 575 nm or more, more preferably 580 nm or more, more preferably 582 nm or more, more preferably 590 nm or more, particularly preferably 600 nm.
  • the emission peak is usually in the wavelength range of 650 nm or less, preferably 630 nm or less, more preferably 610 nm or less. That is, it has a yellow to red light emission color.
  • the phosphor of the second embodiment is usually 581 nm or more, preferably 582 nm or more, and usually has a light emission peak in a wavelength range of 650 nm or less, preferably 630 nm or less, more preferably 610 nm or less. That is, it has an emission color of orange to red.
  • the phosphor of the third embodiment is usually 550 nm or more, preferably 570 nm or more, more preferably 575 nm or more, particularly preferably 580 nm or more, and usually 650 nm or less, preferably 600 nm or less, more preferably 595 nm or less, More preferably, it has an emission peak in a wavelength range of 590 nm or less. That is, it has a yellow to orange emission color.
  • the phosphors of the first to third embodiments of the present invention have a wide half-value width of the emission peak, when used in combination with a blue LED, light emission with good color rendering can be obtained with only one type of phosphor. .
  • a light emitting device is formed by combining a blue to yellow-green phosphor, a red phosphor, or the like, a light emitting device that emits light of higher color rendering can be obtained. Obtainable.
  • the half width of the emission peak is usually 95 nm or more, preferably 97 nm or more, more preferably 100 nm or more, more preferably 103 nm or more, and particularly preferably 105 nm or more. . That is, it shows an emission spectrum with a wide half-value width.
  • the phosphor of the first to third embodiments of the present invention has a wide half-value width of the light emission peak, when used in combination with a blue LED, the first to third embodiments of the present invention are used as the second light emitter. Even when only the above phosphor is used, light emission with good color rendering can be obtained. In particular, when only the phosphor of the third embodiment is used as the second light emitter, a light emitter with particularly good color rendering properties can be obtained, and the effects of the present invention can be remarkably exhibited.
  • a light emitting device is formed by combining a blue to yellow-green phosphor, a red phosphor, or the like, a light emitting device that emits light of higher color rendering can be obtained. Obtainable.
  • the x value of the CIE chromaticity coordinate of the phosphor according to the first or second embodiment of the present invention is usually 0.400 or more, preferably 0.425 or more, more preferably 0.450 or more, more preferably 0.00. 50 or more, particularly preferably 0.520 or more, usually 0.66 or less, preferably 0.63 or less, more preferably 0.61 or less, more preferably 0.59 or less, more preferably 0.575 or less, Especially preferably, it is 0.56 or less.
  • the y value of the CIE chromaticity coordinates of the phosphor according to the first or second embodiment of the present invention is usually 0.30 or more, preferably 0.35 or more, more preferably 0.40 or more, and still more preferably.
  • the x value of CIE chromaticity coordinates of the phosphor according to the third embodiment of the present invention is usually 0.400 or more, preferably 0.425 or more, more preferably 0.450 or more, and usually 0.8. 575 or less, preferably 0.550 or less, more preferably 0.525 or less, more preferably 0.500 or less, and particularly preferably 0.475 or less.
  • the y value of the CIE chromaticity coordinates of the phosphor of the third embodiment of the present invention is usually 0.425 or more, preferably 0.450 or more, more preferably 0.475 or more, and particularly preferably 0.480.
  • the above is usually 0.550 or less, preferably 0.525 or less, more preferably 0.510 or less.
  • the phosphor according to the first to third embodiments of the present invention has a wavelength range of usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 500 nm or less, preferably 480 nm or less, more preferably 460 nm or less.
  • the phosphors according to the first to third embodiments of the present invention also have excellent temperature characteristics. Specifically, the ratio of the emission peak intensity value in the emission spectrum diagram at 100 ° C. to the emission peak intensity value in the emission spectrum diagram at 25 ° C. when light having a peak at a wavelength of 405 nm is usually 50 % Or more, preferably 60% or more, more preferably 70% or more. In addition, since the emission intensity of ordinary phosphors decreases with increasing temperature, it is unlikely that the ratio exceeds 100%, but it may exceed 100% for some reason. However, if it exceeds 150%, the color shift tends to occur due to a temperature change.
  • the external quantum efficiency ( ⁇ o ) of the phosphors of the first to third embodiments of the present invention is usually 40% or more, preferably 50 or more, more preferably 60% or more.
  • the internal quantum efficiency, external quantum efficiency, absorption efficiency, and the like can be measured by, for example, the methods described in paragraphs [0026] to [0038] of JP-A-2008-285562.
  • the phosphors of the first to third embodiments of the present invention are usually in the form of fine particles.
  • the mass median diameter D 50 is usually 2 ⁇ m or more, preferably 5 ⁇ m or more, and usually 30 ⁇ m or less, preferably fine particles of the range 20 [mu] m.
  • the mass median diameter D 50 is too large, for example, tend to dispersibility becomes poor in the resin which is used as a sealing material described later, they tend to be too small and the low luminance.
  • Mass median diameter D 50 is, for example, obtained by measuring particle size distribution by laser diffraction scattering method, is a value determined from the mass-standard particle size distribution curve.
  • the median diameter D 50 is in this mass-standard particle size distribution curve, the accumulated value refers to the particle size value when the 50%.
  • each phosphor raw material preferably has an elemental composition represented by the following formula [3] so as to have a crystal phase composition represented by the formula [1].
  • it can be produced by weighing a compound or metal as a raw material to prepare a phosphor raw material mixture and firing the obtained phosphor raw material mixture.
  • A represents an alkaline earth metal element essential for Sr and Ca
  • D represents a tetravalent metal element essential for Si
  • E represents a trivalent metal essential for Al.
  • X represents a number satisfying 0.0001 ⁇ x ⁇ 0.20
  • f, g, h, i and j represent 0.7 ⁇ f ⁇ 1.3 and 2.8 ⁇ g ⁇ , respectively.
  • each phosphor raw material preferably has the composition of the crystal phase represented by the formula [2], preferably the elemental composition is represented by the following formula [4].
  • the phosphor raw material mixture can be prepared by weighing the compound or metal used as the raw material, and the obtained phosphor raw material mixture can be fired.
  • A represents an alkaline earth metal element essential for Sr and Ca
  • D represents a tetravalent metal element essential for Si
  • E represents a trivalent metal essential for Al.
  • X represents a number satisfying 0.0001 ⁇ x ⁇ 0.20
  • f, g, h, i and j represent 0.7 ⁇ f ⁇ 1.3 and 2.8 ⁇ g ⁇ , respectively.
  • f, g, h, i, and j correspond to a, b, c, d, and e in the item of the composition of the phosphor of this embodiment, respectively, and explanations of preferred ranges thereof are incorporated.
  • phosphor raw material As the phosphor material, a metal compound, a metal, or the like is used. For example, when producing a phosphor having the composition of the crystal phase represented by the above formula [1] or [2], a raw material of A element (hereinafter referred to as “A source” as appropriate), a raw material of D element (hereinafter referred to as “D” as appropriate).
  • a source a raw material of A element
  • D element hereinafter referred to as “D” as appropriate
  • E source E element source
  • N source N element source
  • O source O element source
  • Eu element A necessary combination is mixed from raw materials (hereinafter referred to as “Eu source” as appropriate) (mixing step), the resulting mixture is fired (firing step), and the obtained fired product is crushed and pulverized as necessary. Or by washing (post-treatment process).
  • the raw material used as the alkaline earth metal source is preferably an alkaline earth metal oxide or an alkaline earth metal carbonate, particularly preferably an alkaline earth metal carbonate. This is because the raw material used as the alkaline earth metal source can be handled in the air, which eliminates the need for atmosphere control during mixing and is advantageous in terms of manufacturing costs.
  • an Sr source such as Sr 3 N 2 , SrO, SrCO 3 , or a Ca source such as Ca 3 N 2 , CaO, CaCO 3, etc.
  • Si source such as SiC, Si 3 N 4 , and SiO 2 as D source
  • Al source such as AlN, Al 2 O 3 , and Al 4 C 3 as E source
  • Eu metal, oxide, and carbonate as Eu source Eu compounds selected from chlorides, fluorides, nitrides or oxynitrides can be used.
  • the O source (oxygen) and N source (nitrogen) in the formula [3] or [4] are A source (Sr and Ca source), D source (Si source), E source (Al source), Eu source. May be supplied from a firing atmosphere. Each raw material may contain inevitable impurities.
  • the mixing of the phosphor raw material may be either the wet mixing method or the dry mixing method, but in order to avoid contamination of the phosphor raw material with moisture, a dry mixing method or a wet mixing method using a water-insoluble solvent is more preferable. .
  • the phosphor material mixture obtained in the mixing step is fired (firing step).
  • the above-mentioned phosphor raw material mixture is dried as necessary and then filled in a container such as a crucible and fired using a firing furnace, a pressure furnace or the like.
  • the pressure in the furnace is 0.2 MPa or more and 100 MPa or less as described above. It has been found that firing the phosphor raw material mixture is more preferable. Preferred conditions in the firing step are described below.
  • Examples of the material of the firing container (such as a crucible) used in the firing step include boron nitride and carbon.
  • Calcination temperature varies depending on other conditions such as pressure, but can be usually performed in a temperature range of 1300 ° C. or higher and 2100 ° C. or lower.
  • the highest temperature reached in the firing step is usually 1200 ° C. or higher, preferably 1400 ° C. or higher, more preferably 1600 ° C. or higher, particularly preferably 1800 ° C. or higher, and usually 2100 ° C. or lower, preferably 2000 ° C. or lower. Preferably it is 1900 degrees C or less. If the firing temperature is too high, nitrogen will fly, generating defects in the host crystal and coloring, and impurities tend to be generated. If it is too low, the progress of the solid phase reaction tends to be slow.
  • the heating rate in the firing step is usually 2 ° C./min or more, preferably 5 ° C./min or more, more preferably 10 ° C./min or more, and usually 30 ° C./min or less, preferably 25 ° C./min or less. It is. If the rate of temperature rise is below this range, the firing time may be long. In addition, if the rate of temperature rise exceeds this range, the firing device, container, etc. may be damaged.
  • the firing atmosphere in the firing step is arbitrary as long as the phosphors according to the first to third embodiments of the present invention are obtained, but a nitrogen-containing atmosphere is preferable. Specific examples include a nitrogen atmosphere and a hydrogen-containing nitrogen atmosphere, and a nitrogen atmosphere is particularly preferable.
  • the oxygen content in the firing atmosphere is usually 10 ppm or less, preferably 5 ppm or less.
  • the firing time varies depending on the temperature and pressure during firing, but is usually 10 minutes or longer, preferably 30 minutes or longer, and usually 24 hours or shorter, preferably 12 hours or shorter.
  • the pressure in the firing step varies depending on the firing temperature and the like, the pressure in the furnace can be set to atmospheric pressure (0.1013 MPa) or a pressurized state.
  • the pressure in the firing step is usually 0.1013 MPa or more, preferably 0.2 MPa or more, more preferably 0.4 MPa or more, and usually 100 MPa or less, preferably 50 MPa or less, more preferably 20 MPa or less, particularly preferably 10 MPa. It is as follows. If the pressure is too high, by-products tend to increase, and if the pressure is too low, the obtained phosphor may be decomposed or colored, so adjustment of the pressure is important.
  • the firing conditions may be the same or different between the first firing and the second firing. It is preferable to perform the second baking at a relatively high temperature after the first baking as a preliminary baking at a relatively low temperature in order to reduce the impurity phase and increase the luminous efficiency.
  • the obtained fired product is granular or massive. This is pulverized, pulverized and / or classified into a powder of a predetermined size.
  • D 50 is less than about 30 [mu] m.
  • the treatment include a method of subjecting the synthesized product to sieve classification with an opening of about 45 ⁇ m, and passing the powder that has passed through the sieve to the next step, or the synthesized product to a general method such as a ball mill, a vibration mill, or a jet mill.
  • a general method such as a ball mill, a vibration mill, or a jet mill.
  • pulverizing to a predetermined particle size using a grinder is mentioned. In the latter method, excessive pulverization not only generates fine particles that easily scatter light, but also generates crystal defects on the particle surface, which may cause a decrease in luminous efficiency.
  • a step of cleaning the phosphor may be provided. After the cleaning step, the phosphor is dried until it has no adhering moisture and is used. Further, if necessary, dispersion / classification treatment may be performed to loosen the aggregation.
  • the phosphor according to the first to third embodiments of the present invention can be used for any application using the phosphor.
  • the phosphors of the first to third embodiments of the present invention can be used alone, but two or more kinds of phosphors can be used together, or the phosphors of the first to third embodiments of the present invention can be used together. It can also be used as a phosphor mixture of any combination, such as in combination with other phosphors.
  • the phosphors of the first to third embodiments of the present invention can be used as a phosphor-containing composition by mixing with a known liquid medium (for example, a silicone compound).
  • a known liquid medium for example, a silicone compound.
  • the phosphor obtained by the first to third embodiments of the present invention can be used in various light emitting devices by combining with a light source that emits ultraviolet light, taking advantage of the fact that it can be excited by ultraviolet light. It can be used suitably.
  • the emission color of the light-emitting device is not limited to purple or white, but by appropriately selecting the combination and content of phosphors, light emission that emits light in any color, such as light bulb color (warm white) or pastel color
  • the device can be manufactured.
  • the light-emitting device thus obtained can be used as a light-emitting portion (particularly a liquid crystal backlight) or an illumination device of an image display device.
  • the phosphors of the first to third embodiments of the present invention can be used by mixing with a liquid medium.
  • the phosphor of the first to third embodiments of the present invention is used for a light emitting device or the like, it is preferably used in a form dispersed in a liquid medium.
  • the phosphor of the first to third embodiments of the present invention dispersed in a liquid medium is appropriately referred to as “the phosphor-containing composition of the present invention”, and the fourth embodiment of the present invention is A phosphor-containing composition obtained by dispersing at least one phosphor described above in a liquid medium.
  • or 3rd embodiment of this invention contained in a fluorescent substance containing composition may be only 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
  • the phosphor-containing composition may contain a phosphor other than the phosphors of the first to third embodiments of the present invention as long as the effects of the present embodiment are not significantly impaired.
  • the kind of liquid medium used for the phosphor-containing composition is not particularly limited, and a curable material that can be molded over the semiconductor light emitting element can be used.
  • the curable material is a fluid material that is cured by performing some kind of curing treatment.
  • the fluid state means, for example, a liquid state or a gel state.
  • the curable material is not particularly limited as long as it secures the role of guiding the light emitted from the solid light emitting element to the phosphor.
  • only 1 type may be used for a curable material and it may use 2 or more types together by arbitrary combinations and a ratio. Therefore, as the curable material, any of inorganic materials, organic materials, and mixtures thereof can be used.
  • the inorganic material for example, a solution obtained by hydrolytic polymerization of a solution containing a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or a combination thereof, an inorganic material (for example, a siloxane bond) Inorganic materials having
  • examples of the organic material include a thermosetting resin and a photocurable resin.
  • specific examples include (meth) acrylic resins such as methyl poly (meth) acrylate; styrene resins such as polystyrene and styrene-acrylonitrile copolymers; polycarbonate resins; polyester resins; phenoxy resins; butyral resins; Cellulose resins such as cellulose acetate and cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins and the like.
  • a silicon-containing compound is a compound having a silicon atom in the molecule, organic materials such as polyorganosiloxane (silicone compounds), inorganic materials such as silicon oxide, silicon nitride, and silicon oxynitride, and borosilicates and phosphosilicates. Examples thereof include glass materials such as salts and alkali silicates.
  • silicone materials are preferable from the viewpoints of transparency, adhesion, ease of handling, and excellent mechanical and thermal stress relaxation characteristics.
  • the silicone-based material usually refers to an organic polymer having a siloxane bond as a main chain, and for example, a silicone-based material such as a condensation type, an addition type, an improved sol-gel type, and a photocurable type can be used.
  • condensation type silicone material for example, semiconductor light-emitting device members described in JP-A No. 2007-129973 to No. 112975, JP-A No. 2007-19459, JP-A No. 2008-34833 and the like can be used.
  • Condensation-type silicone materials have excellent adhesion to packages, electrodes, and light-emitting elements used in semiconductor light-emitting devices, so the addition of adhesion-improving components can be minimized, and crosslinking is mainly due to siloxane bonds. There is an advantage of excellent heat resistance and light resistance.
  • addition-type silicone material examples include potting silicone materials described in JP-A No. 2004-186168, JP-A No. 2004-221308, JP-A No. 2005-327777, JP-A No. 2003-183881, Organically modified silicone materials for potting described in JP-A-2006-206919, silicone materials for injection molding described in JP-A-2006-324596, silicone materials for transfer molding described in JP-A-2007-231173, etc. Can be suitably used.
  • the addition-type silicone material has advantages such as a high degree of freedom in selection such as a curing speed and a hardness of a cured product, a component that does not desorb during curing, hardly shrinking due to curing, and excellent deep part curability.
  • an improved sol-gel type silicone material which is one of the condensation types
  • the silicone materials described in JP-A-2006-077234, JP-A-2006-291018, JP-A-2007-119569 and the like are used. It can be used suitably.
  • the improved sol-gel type silicone material has an advantage that it has a high degree of crosslinking, heat resistance, light resistance and durability, and is excellent in the protective function of a phosphor having low gas permeability and low moisture resistance.
  • the photocurable silicone-based material for example, silicone materials described in JP2007-131812A, JP2007-214543A, and the like can be suitably used.
  • the ultraviolet curable silicone material has advantages such as excellent productivity because it cures in a short time, and it is not necessary to apply a high temperature for curing, so that the light emitting element is hardly deteriorated.
  • silicone materials may be used alone, or a plurality of silicone materials may be mixed and used as long as they do not inhibit curing by mixing.
  • the content of the liquid medium is arbitrary as long as the effect of the present embodiment is not significantly impaired, but is usually 25% by mass or more, preferably 40% by mass or more with respect to the entire phosphor-containing composition of the present embodiment. Moreover, it is 99 mass% or less normally, Preferably it is 95 mass% or less, More preferably, it is 80 mass% or less.
  • the amount of the liquid medium is large, no particular problem occurs. However, in order to obtain a desired chromaticity coordinate, color rendering index, luminous efficiency, etc. in the case of a semiconductor light emitting device, it is usually at a blending ratio as described above. It is desirable to use a liquid medium. On the other hand, when there is too little liquid medium, fluidity
  • the liquid medium mainly has a role as a binder in the phosphor-containing composition of the present embodiment.
  • the liquid medium may be used alone or in combination of two or more in any combination and ratio.
  • other thermosetting resins such as an epoxy resin are contained so as not to impair the durability of the silicon-containing compound. Also good.
  • the content of the other thermosetting resin is usually 25% by mass or less, preferably 10% by mass or less, based on the total amount of the liquid medium as the binder.
  • the phosphor content in the phosphor-containing composition is arbitrary as long as the effect of the present embodiment is not significantly impaired, but is usually 1% by mass or more, preferably with respect to the entire phosphor-containing composition of the present embodiment. Is 5% by mass or more, more preferably 20% by mass or more, and usually 75% by mass or less, preferably 60% by mass or less.
  • the proportion of the phosphor of the first to third embodiments of the present invention in the phosphor in the phosphor-containing composition is also arbitrary, but is usually 30% by mass or more, preferably 50% by mass or more. Usually, it is 100 mass% or less.
  • the flowability of the phosphor-containing composition may be inferior and difficult to handle, and if the phosphor content is too low, the light emission efficiency of the light-emitting device decreases. There is a tendency.
  • the phosphor-containing composition has other components such as a metal oxide for adjusting the refractive index, a diffusing agent, a filler, and a viscosity, as long as the effects of the present embodiment are not significantly impaired.
  • You may contain additives, such as a regulator and a ultraviolet absorber. Only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.
  • a first light emitter excitation light source
  • a second light emitter that can emit visible light by converting light from the first light emitter into visible light.
  • the light emitting device of this embodiment includes a first phosphor as the second light emitter.
  • a first phosphor as the second light emitter.
  • the ratio of the first phosphor in the second phosphor is 95% by mass or more, preferably 98% by mass or more, and more preferably 99.9% by mass or more, different types of phosphors
  • By mixing the phosphors it is possible to avoid the problem of self-absorption that other phosphors absorb the light emission of the phosphors, so that a light-emitting device with high luminous efficiency can be provided.
  • phosphors of the first to third embodiments used in the light emitting device of the present embodiment include [1. Examples include phosphors according to the embodiments described in the “Phosphor” column, and phosphors used in each Example in the “Example” column described below. In addition, the phosphors of the first to third embodiments may be used alone or in combination of two or more in any combination and ratio.
  • the light emitting device of this embodiment has a first light emitter (excitation light source) and uses at least the phosphors of the first to third embodiments as the second light emitter.
  • the configuration is not limited, and a known device configuration can be arbitrarily employed. A specific example of the device configuration will be described later.
  • an excitation light source as described later is used as the first light emitter, and in addition to the phosphors of the first to third embodiments, the light source will be described later.
  • a phosphor that emits blue fluorescence hereinafter referred to as “blue phosphor” as appropriate
  • a phosphor that emits green fluorescence hereinafter referred to as “green phosphor” as appropriate
  • a phosphor that emits red fluorescence hereinafter referred to as “green phosphor”.
  • the white color of the white light emitting device is any of (yellowish) white, (greenish) white, (blueish) white, (purple) white and white as defined by JIS Z 8701. Of these, white is preferred.
  • the first light emitter in the light emitting device of this embodiment emits light that excites a second light emitter described later.
  • the emission peak wavelength of the first illuminant is not particularly limited as long as it overlaps with the absorption wavelength of the second illuminant described later, and an illuminant having a wide emission wavelength region can be used.
  • a light emitter having an emission wavelength from the ultraviolet region to the blue region is used.
  • the specific value of the emission peak wavelength of the first illuminant is usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 500 nm or less, preferably 480 nm or less, more preferably 460 nm or less. It is desirable to use a light emitter having a wavelength.
  • a semiconductor light emitting element is generally used, and specifically, a light emitting diode (LED), a laser diode (LD), or the like can be used.
  • a light-emitting body which can be used as a 1st light-emitting body an organic electroluminescent light emitting element, an inorganic electroluminescent light emitting element, etc. are mentioned, for example.
  • what can be used as a 1st light-emitting body is not restricted to what is illustrated by this specification.
  • a GaN LED or LD using a GaN compound semiconductor is preferable.
  • GaN-based LEDs and LDs have significantly higher emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and emit very bright light with low power when combined with the phosphor. It is because it is obtained.
  • GaN-based LEDs and LDs usually have a light emission intensity 100 times or more that of SiC-based.
  • the GaN-based LED and LD those having an Al X Ga Y N light emitting layer, a GaN light emitting layer, or an In X Ga Y N light emitting layer are preferable.
  • the GaN-based LED is particularly preferably one having an In X Ga Y N light emitting layer, and more preferably a multiple quantum well structure having an In X Ga Y N layer and a GaN layer. preferable.
  • the value of X + Y is usually in the range of 0.8 to 1.2.
  • those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.
  • a GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic components, and the light-emitting layer is an n-type and p-type Al X Ga Y N layer, GaN layer, or In X Those having a heterostructure sandwiched between Ga Y N layers and the like are preferable because of high light emission efficiency, and those having a heterostructure having a quantum well structure are more preferable because of high light emission efficiency. Note that only one first light emitter may be used, or two or more first light emitters may be used in any combination and ratio. Among the first light emitters described above, a blue LED is preferable as the first light emitter used in the light emitting device of the present invention.
  • the specific value of the emission peak wavelength of the first illuminant is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 500 nm or less, preferably 480 nm or less, more preferably 460 nm or less. It is desirable to use an illuminant having an emission peak wavelength in the above range.
  • a light emitting device with high color rendering can be obtained by including at least one blue LED and the phosphors of the first to third embodiments. In particular, the phosphor of the third embodiment. The use of is particularly preferred.
  • a blue LED and one or more phosphors of the first to third embodiments can be used to obtain a light emitting device with high color rendering, but as another embodiment, A light emitting device in which a near-ultraviolet LED, the phosphor of the first to third embodiments (first phosphor), and the blue phosphor (second phosphor) are combined can also be provided.
  • the specific value of the emission peak wavelength of the first illuminant at this time is usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 420 nm or less, preferably 415 nm or less, more preferably 410 nm or less.
  • the specific value of the emission peak wavelength of the second phosphor (blue phosphor) at this time is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 500 nm or less, preferably 480 nm or less, More preferably, it is desirable to use a phosphor having an emission peak wavelength in a range of 460 nm or less.
  • the second light emitter in the light emitting device of the present embodiment is a light emitter that emits visible light when irradiated with the light from the first light emitter described above, and the first to third embodiments are used as the first phosphor.
  • the second phosphor blue phosphor, green phosphor, yellow phosphor, orange phosphor, red phosphor, etc.
  • the second light emitter is configured by dispersing the first and second phosphors in a sealing material.
  • composition of the phosphor other than the phosphors of the first to third embodiments that is, the second phosphor used in the second luminous body, but it becomes a base crystal.
  • Y 2 O 3 , YVO 4 , Zn 2 SiO 4 metal oxides typified by Y 3 A 15 O 12 , Sr 2 SiO 4 , metal nitrides typified by Sr 2 Si 5 N 8 , Ca 5 Ce in phosphates typified by (PO 4 ) 3 Cl and the like, sulfides typified by ZnS, SrS, CaS and the like, oxysulfides typified by Y 2 O 2 S and La 2 O 2 S and the like , Ions of rare earth metals such as Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb and ions of metals such as Ag, Cu, Au, Al, Mn, Sb A combination of the coactiv
  • the matrix crystal and the activator element or coactivator element are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used. Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present embodiment are not limited to these. In the following examples, as described above, phosphors that differ only in part of the structure are omitted as appropriate.
  • the second light emitter in the light emitting device of this embodiment contains at least the first phosphor including the phosphors of the first to third embodiments described above. Any one of the phosphors of the first to third embodiments may be used alone, or two or more thereof may be used in any combination and ratio, so that a desired emission color is obtained. What is necessary is just to adjust suitably the composition of the fluorescent substance of the 1st thru
  • the second light emitter in the light emitting device of the present embodiment may contain a phosphor (that is, the second phosphor) in addition to the first phosphor described above, depending on the application.
  • the second phosphor emits fluorescence having a color different from that of the first phosphor.
  • phosphors are used. For example, when a green phosphor is used as the first phosphor, a phosphor other than a green phosphor such as a blue phosphor, a red phosphor, or a yellow phosphor may be used as the second phosphor.
  • a phosphor having the same color as the first phosphor can be used as the second phosphor.
  • Second phosphor mass median diameter D 50 that is used for the light emitting device of the present embodiment is generally 2 ⁇ m or more and preferably 5 ⁇ m or more, and usually 30 ⁇ m or less is preferably in a range of inter alia 20 ⁇ m or less.
  • the mass median diameter D 50 is too small, and the luminance decreases tends to phosphor particles tend to aggregate.
  • the mass median diameter is too large, there is a tendency for coating unevenness and blockage of a dispenser to occur.
  • the emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 480 nm or less, more preferably 470 nm or less, and further preferably 460 nm or less. It is preferable to be in the wavelength range.
  • the emission peak wavelength of the blue phosphor used is within this range, it overlaps with the excitation band of the phosphor of this embodiment, and the phosphor of this embodiment is efficiently excited by the blue light from the blue phosphor. Because you can. Table 2 shows phosphors that can be used as such blue phosphors.
  • (Ca, Sr, Ba) MgAl 10 O 17 : Eu, (Sr, Ca, Ba, Mg) 10 (PO 4 ) 6 (Cl, F) 2 : Eu, (Ba , Ca, Mg, Sr) 2 SiO 4 : Eu, (Ba, Ca, Sr) 3 MgSi 2 O 8: Eu are preferred, and (Ba, Sr) MgAl 10 O 17 : Eu, (Ca, Sr, Ba) 10 ( PO 4 ) 6 (Cl, F) 2 : Eu and Ba 3 MgSi 2 O 8 : Eu are more preferable, and Sr 10 (PO 4 ) 6 Cl 2 : Eu and BaMgAl 10 O 17 : Eu are particularly preferable.
  • the emission peak wavelength of the green phosphor is usually larger than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, especially 542 nm or less, and further preferably 535 nm or less. If this emission peak wavelength is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and the characteristics as green light may deteriorate. Table 3 shows phosphors that can be used as such green phosphors.
  • Y 3 (Al, Ga) 5 O 12 : Tb, CaSc 2 O 4 : CeCa 3 (Sc, Mg) 2 Si 3 O 12 : Ce, (Sr, Ba ) 2 SiO 4 : Eu, (Si, Al) 6 (O, N) 8 : Eu ( ⁇ -sialon), (Ba, Sr) 3 Si 6 O 12 N 2 : Eu are preferable.
  • the emission peak wavelength of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. Is preferred. Table 4 shows phosphors that can be used as such yellow phosphors.
  • Y 3 Al 5 O 12 Ce
  • a l5 O 12 Ce
  • (Ca, Sr) Si 2 N 2 O 2 : Eu is preferred.
  • any orange or red phosphor can be used as long as the effect of the present embodiment is not significantly impaired.
  • the emission peak wavelength of the orange to red phosphor is usually in the wavelength range of 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less. Is preferred. Table 5 shows phosphors that can be used as such orange to red phosphors.
  • red phosphors (Ca, Sr, Ba) 2 Si 5 (N, O) 8 : Eu, (Ca, Sr, Ba) Si (N, O) 2 : Eu, (Ca, Sr , Ba) AlSi (N, O) 3 : Eu, (Sr, Ba) 3 SiO 5 : Eu, (Ca, Sr) S: Eu, (La, Y) 2 O 2 S: Eu, Eu (dibenzoylmethane) ) ⁇ -diketone Eu complex such as 3,1,10-phenanthroline complex, carboxylic acid Eu complex, K 2 SiF 6 : Mn is preferred, (Ca, Sr, Ba) 2 Si 5 (N, O) 8 : Eu, (Sr, Ca) AlSi (N, O): Eu, (La, Y) 2 O 2 S: Eu, and K 2 SiF 6 : Mn are more preferable.
  • FIG. 1 denotes a phosphor-containing portion (second light emitter)
  • reference numeral 2 denotes a surface-emitting GaN-based LD as an excitation light source (first light emitter)
  • reference numeral 3 denotes a substrate.
  • the excitation light source (LD) 2 and the phosphor-containing portion 1 (second light emitter) are separately manufactured, and their surfaces are brought into contact with each other by an adhesive or other means.
  • the phosphor-containing portion 1 (second light emitter) may be formed (molded) on the light emitting surface of the excitation light source (LD) 2.
  • FIG. 2A is a typical example of a light emitting device of a form generally referred to as a shell type, and has a light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). It is typical sectional drawing which shows one Example of an apparatus.
  • reference numeral 5 is a mount lead
  • reference numeral 6 is an inner lead
  • reference numeral 7 is an excitation light source (first light emitter)
  • reference numeral 8 is a phosphor-containing portion
  • reference numeral 9 is a conductive wire
  • reference numeral 10 is a mold. Each member is indicated.
  • FIG. 2B is a representative example of a light-emitting device in a form called a surface-mount type, and light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter).
  • first light emitter an excitation light source
  • second light emitter a phosphor-containing portion
  • reference numeral 24 is a frame
  • reference numeral 25 is a conductive wire
  • reference numerals 26 and 27 are electrodes. Respectively.
  • the Ra of the emission color is usually 58 or more, preferably 60 or more, more preferably 62 or more, and particularly preferably 64 or more. As the value of Ra is larger, a light emitting device having better color rendering properties can be obtained.
  • the special color rendering index R9 of the emitted color is usually minus 75 or more, preferably minus 70 or more, more preferably minus 65 or more, particularly preferably minus 60 or more. When the special color rendering index R9 is in the above range, a light emitting device having good color rendering properties can be obtained.
  • the correlated color temperature of the emitted color is usually 2600 K or higher, preferably 2700 K or higher, particularly preferably 2800 K or higher, and usually 4500 K or lower, preferably 4300 K or lower, more preferably 4000 K or lower, Preferably it is 3700K or less, Especially preferably, it is 3400K or less.
  • the correlated color temperature is in the above-described range, a light emitting device that exhibits a warm emission color from a preferable white color to a light bulb color (a range in which the correlated color temperature is 2600K to 4500K) can be obtained.
  • the application of the light-emitting device of this embodiment is not particularly limited, and can be used in various fields where a normal light-emitting device is used. However, since the color rendering property is high and the color reproduction range is wide, illumination is particularly important. It is particularly preferably used as a light source for a device or an image display device.
  • a sixth embodiment of the present invention is an illumination device or an image display device including the above-described light emitting device.
  • FIG. 3 is a cross-sectional view schematically showing one embodiment of the illumination device of the present embodiment.
  • the surface-emitting illumination device has a large number of light-emitting devices 13 (on the light-emitting device 4 described above) on the bottom surface of a rectangular holding case 12 whose inner surface is light-opaque such as a white smooth surface.
  • the diffusion plate 14 is fixed for uniform light emission.
  • the surface-emitting illumination device 11 is driven to emit light by applying a voltage to the excitation light source (first light emitter) of the light-emitting device 13, and a part of the light emission is converted to the phosphor-containing portion (first The phosphor in the phosphor-containing resin portion as the second phosphor) absorbs and emits visible light, while light emission with high color rendering is obtained by mixing with blue light or the like that is not absorbed by the phosphor.
  • the light passes through the diffusion plate 14 and is emitted upward in the drawing, and illumination light with uniform brightness is obtained within the surface of the diffusion plate 14 of the holding case 12.
  • the specific configuration of the image display device is not limited, but it is preferably used together with a color filter.
  • the image display device is a color image display device using color liquid crystal display elements
  • the light emitting device is used as a backlight, a light shutter using liquid crystal, and a color filter having red, green, and blue pixels; By combining these, an image display device can be formed.
  • the present invention will be described more specifically with reference to examples.
  • the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
  • the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the value of the upper limit or the lower limit. It may be a range defined by a combination of values of the following examples or values of the examples.
  • the light from the excitation light source was passed through a diffraction grating spectrometer having a focal length of 10 cm, and only the excitation light having a wavelength of 455 nm was irradiated to the phosphor through the optical fiber.
  • the light generated from the phosphor by the irradiation of the excitation light is dispersed by a diffraction grating spectroscope having a focal length of 25 cm, the emission intensity of each wavelength is measured by a spectrum measuring device in a wavelength range of 300 nm to 800 nm, and a personal computer is used.
  • An emission spectrum was obtained through signal processing such as sensitivity correction.
  • the slit width of the light-receiving side spectroscope was set to 1 nm and the measurement was performed.
  • the emission peak wavelength (hereinafter sometimes referred to as “peak wavelength”) was read from the obtained emission spectrum.
  • the relative peak intensity was expressed as a relative value with the peak intensity of Comparative Example 1 as the reference value 100.
  • the relative emission luminance is a range obtained by excluding the excitation wavelength region from the emission spectrum in the visible region obtained by the above-described method, and the stimulus of Comparative Example 3 from the stimulus value Y in the XYZ color system calculated according to JIS Z8724.
  • the value Y was calculated as a relative value (hereinafter, sometimes simply referred to as “luminance”) with 100%.
  • ⁇ Chromaticity coordinates> The chromaticity coordinates of the x, y color system (CIE 1931 color system) are obtained from the data in the wavelength region of 360 nm to 800 nm of the emission spectrum obtained by the above method, according to JIS Z8724. The chromaticity coordinates x and y in the prescribed XYZ color system were calculated.
  • ⁇ Excitation spectrum> A fluorescence spectrophotometer F-4500 manufactured by Hitachi, Ltd. was used, and the wavelength was monitored according to the emission peak wavelength to obtain an excitation spectrum in the wavelength range of 250 nm to 500 nm.
  • the lattice constant has a skeletal structure composed of Si, Al, N, and O, and has a crystal structure in which Sr sites exist in the voids.
  • Examples 1 to 13, 17 and Comparative Examples 1 to 3 As phosphor raw materials, Sr 3 N 2 (manufactured by Shellac), Ca 3 N 2 (manufactured by Shellac), Si 3 N 4 (manufactured by Ube Industries), Al 2 O 3 (manufactured by Sumitomo Chemical), AlN (Tokuyama) The phosphor was prepared as follows using Eu 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the temperature was further increased to 1200 ° C. at a temperature increase rate of 20 ° C./min while maintaining 0.92 MPa. While maintaining at 1200 ° C. for 5 minutes, the thermocouple was changed to a radiation thermometer, and further heated to 1600 ° C. at a rate of temperature increase of 20 ° C./min. When the temperature reached 1600 ° C., the temperature was maintained for 2 hours, followed by heating to 1850 ° C. at 20 ° C./min, and the temperature was maintained for 6 hours. After firing, the mixture was cooled to 1200 ° C. at a temperature lowering rate of 20 ° C./min, and then allowed to cool. Thereafter, the product was crushed to obtain phosphors of Examples 1 to 13, 17 and Comparative Examples 1 to 3.
  • Example 14 to 16 Phosphors were prepared in the same manner as in Examples 1 to 13, 17 and Comparative Examples 1 to 3, except that the following preliminary firing was performed before firing.
  • BN crucible boron nitride crucible
  • This BN crucible was placed in a resistance heating type vacuum pressure atmosphere heat treatment furnace (manufactured by Fuji Denpa Kogyo Co., Ltd.). Subsequently, the pressure was reduced to 5 ⁇ 10 ⁇ 3 Pa or less, and then vacuum heating was performed from room temperature to 800 ° C. at a temperature rising rate of 20 ° C./min. When the temperature reached 800 ° C., high-purity nitrogen gas (99.9995%) was introduced for 30 minutes until the pressure in the furnace reached 0.92 MPa.
  • the temperature was further increased to 1200 ° C. at a temperature increase rate of 20 ° C./min while maintaining 0.92 MPa. While maintaining at 1200 ° C. for 5 minutes, the thermocouple was changed to a radiation thermometer and further heated to 1500 ° C. at a temperature rising rate of 20 ° C./min. When it reached 1500 ° C., it was maintained for 8 hours. After firing, the mixture was cooled to 1200 ° C. at a temperature lowering rate of 20 ° C./min, and then allowed to cool. Thereafter, the product was crushed to obtain pre-fired products of Examples 14 to 16.
  • Example 18 to 28 Examples 1 to 13 and 17 and Comparative Example except that Ba 3 N 2 (manufactured by Taiheiyo Cement Co., Ltd.) was used as the phosphor raw material, and the respective charge compositions of Examples 18 to 28 shown in Table 7 were used. Phosphors were obtained in the same manner as in Examples 1 to 3.
  • Comparative Examples 1 to 3 are phosphors in which Ca is not substituted at all, Examples 1 to 5 are phosphors in which Ca is substituted at a ratio of 10 mol% with respect to Sr, and Examples 6 to 12 and 17 are based on Sr.
  • Examples 13 to 15 and 18 to 21 were phosphors in which Ca was substituted at a ratio of 30 mol% to Sr
  • Examples 16 and 22 to 23 were Sr Phosphors in which Ca was substituted at a ratio of 40 mol% with respect to Example 24
  • Examples 24 to 28 were phosphors in which Ca was substituted at a ratio of 30 mol% and Ba at a ratio shown in Table 7.
  • Table 8 shows the results of refinement of the lattice constant based on the powder X-ray diffraction patterns of the phosphors of Examples 1 to 17 and Comparative Examples 1 to 3, and Patent Document 3 (Japanese Patent Publication No. 2010-518194).
  • V unit lattice volume
  • FIG. 4 is a powder X-ray pattern of the phosphors of Examples 2, 3, 6, 10 and Comparative Example 1.
  • FIG. The obtained powder X-ray diffraction pattern has a skeleton structure composed of Si, Al, N, and O, and SrAlSi 4 N, which is a kind of phosphor having a crystal structure in which Sr sites exist in the voids.
  • 7 shows a crystal phase having the same crystal structure as that of FIG. 7 , that is, a space group of a crystal structure in which the space group is classified as Pna2 1 , and the peak positions are slightly different. Moreover, it was confirmed that the difference in peak intensity ratio seen in FIG. 4 is the influence of selective orientation in the measurement.
  • FIG. 5 shows emission spectra of the phosphors obtained in Examples 2, 3, 6 to 9, 13 and Comparative Example 1. It was confirmed that the peak intensities of the phosphors of all the examples were increased from the peak intensity of Comparative Example 1. That is, the emission intensity was increased by adjusting the unit cell volume.
  • FIG. 6 is an excitation spectrum of the phosphor obtained in Example 2. It has been found that the phosphor of this example exhibits high-intensity orange light emission over a wide range of wavelengths from 300 nm to 550 nm, particularly from 400 nm to 500 nm.
  • FIG. 7 is a powder X-ray pattern of the phosphors of Examples 4 and 11 and Comparative Example 2, and FIG. 8 is an emission spectrum of those phosphors.
  • the ratio of Si and Al in the crystal structure is the same as that of the phosphor of Comparative Example 2, and only the amount of substitution of Ca is changed.
  • Comparative Example 2 a peak due to the impurity phase was confirmed, but in Example 4, the intensity decreased, and in Example 11, it was not confirmed. This suggests that by replacing the Sr site with Ca, the unit cell volume was adjusted and a phosphor having a more stable structure could be generated. Accordingly, the generation of the impurity phase is suppressed, and the target crystal phase is easily generated selectively, so that an increase in emission intensity is achieved.
  • FIG. 9 shows emission spectra of the phosphors of Examples 5 and 12 and Comparative Example 3.
  • the ratio of Si and Al in the crystal structure is the same as that of the phosphor of Comparative Example 3, and only the amount of substitution of Ca is changed.
  • the emission intensity increased in accordance with Example 5 and Example 12. This is because, as in the phosphors of Examples 4 and 11, and Comparative Example 2, the Sr site was replaced with Ca, whereby the unit cell volume was adjusted and a phosphor having a more stable structure could be generated. It is suggested.
  • FIG. 10 is a powder X-ray pattern of the phosphors of Examples 18 to 23.
  • the obtained powder X-ray diffraction pattern has a skeleton structure composed of Si, Al, N, and O, and SrAlSi 4 N, which is a kind of phosphor having a crystal structure in which Sr sites exist in the voids.
  • 7 shows a crystal phase having the same crystal structure as that of FIG. 7 , that is, a space group of a crystal structure in which the space group is classified as Pna2 1 , and the peak positions are slightly different. Moreover, it was confirmed that the difference in peak intensity ratio seen in FIG. 10 is the influence of selective orientation in the measurement.
  • FIG. 11 shows emission spectra of the phosphors of Examples 18 to 23. It can be seen that the emission peak wavelength can be controlled by adjusting the ratio of Si, Al, N, and O constituting the skeleton structure and the Ca substitution amount of the Sr site.
  • FIG. 12 is a powder X-ray pattern of the phosphors of Examples 18 and 24-28.
  • the obtained powder X-ray diffraction pattern has a skeleton structure composed of Si, Al, N, and O, and SrAlSi 4 N, which is a kind of phosphor having a crystal structure in which Sr sites exist in the voids.
  • 7 shows a crystal phase having the same crystal structure as that of FIG. 7 , that is, a space group of a crystal structure in which the space group is classified as Pna2 1 , and the peak positions are slightly different.
  • the difference in peak intensity ratio seen in FIG. 12 is the influence of the selective orientation in the measurement.
  • Ba could be solid solution-substituted at the ratio shown in Table 7 for the Sr sites in the crystal structure.
  • FIG. 13 shows the emission spectra of the phosphors of Examples 18 and 24-28.
  • the ratio of Si, Al, N, and O constituting the skeleton structure and the Ca substitution amount of the Sr site are made constant, and the Sr site is substituted with Ba, the full width at half maximum increases as the substitution amount increases.
  • the half-value width can be controlled by replacing the Sr site in the crystal structure of the phosphor of the present invention with Ba.
  • Table 9 shows the measurement results of the emission peak wavelength, CIE chromaticity coordinates, emission peak half width, and relative emission peak intensity of the phosphors of Examples 1 to 4, 6 to 11, and 13 and Comparative Examples 1 and 2. .
  • the peak intensity is increased from the peak intensity of Comparative Examples 1 and 2 while maintaining a wide half-value width, and the emission intensity is high in a wide range from yellow to red. It was confirmed that an excellent phosphor could be produced. This is considered to be because by replacing the Sr site with Ca together with the composition of the skeletal structure, the unit cell volume was adjusted and optimum stable structures could be constructed in various emission colors.
  • Table 10 shows the measurement results of the emission peak wavelength, CIE chromaticity coordinates, emission peak half-value width, and relative emission luminance of the phosphors of Examples 5, 12, 14 to 17 and Comparative Example 3.
  • the relative light emission luminance is higher than the relative light emission luminance of Comparative Example 3 while maintaining a wide half width.
  • Example 29 and 30 A phosphor was prepared in the same manner as in Example 9 in Example 29 and in the same manner as in Example 14 in Example 30. The obtained phosphor was subjected to composition analysis by the above method.
  • Table 11 shows the composition analysis results of the phosphors of Examples 29 and 30.
  • Example 29 is Sr 0.75 Ca 0.20 Eu 0.05 Si 3.57 Al 1.41 N 6.33 O 0.46
  • Example 30 is Sr 0. .67 Ca 0.28 Eu 0.05 Si 3.33 Al 1.73 N 6.13 O 0.74 , confirming that a phosphor having a substantially aimed composition (prepared composition) was obtained.
  • Sr 1.98 BaSiO 5 used in Comparative Example 5 Eu 0.02 is, Sr 1.98 BaSiO 5 by powder X-ray measurement: it was confirmed that Eu 0.02 is obtained.
  • the yttrium aluminum garnet phosphor used in Comparative Example 6 is P46-Y3 manufactured by Mitsubishi Chemical Corporation.
  • the phosphor of Example 18 is the phosphor of Example 14 described above
  • the phosphor of Example 19 is the phosphor of Example 15 described above
  • the phosphor of Example 22 is the fluorescence of Example 16 described above. It is the same as the body.
  • the simulation was performed by the following method.
  • Simulation method An emission spectrum obtained by subtracting the spectrum of the excitation light source from the actual measurement data of the blue LED (peak wavelength: 450 nm, half-value width: 21 nm) and the actual emission spectrum of the phosphor used at a wavelength of 455 nm was prepared. The emission peak intensity of each prepared spectrum is normalized to 1, and the spectrum obtained by multiplying the intensity of the blue LED and the emission peak intensity of the phosphor by an arbitrary ratio is added to obtain a white spectrum. As derived.
  • each optical characteristic evaluation item was as follows.
  • (I) The xy chromaticity coordinates on the CIE 1931 chromaticity diagram were calculated based on JIS Z8724: 1997 (title: color measurement method—light source color—).
  • (Ii) Based on the result of (i) above, after conversion to uv chromaticity coordinates on the CIE 1960 UCS chromaticity diagram, JIS Z8725: 1999 (title: measurement of light source distribution temperature and color temperature / correlated color temperature) Method) The correlated color temperature (Kelvin) and Duv were calculated.
  • (Iii) The color rendering index (Ra, R1 to R15) was calculated from the white spectrum based on JIS Z8726: 1990 (title: color rendering property evaluation method of light source).
  • Table 12 shows the chromaticity, correlated color temperature, and Duv values calculated from the white spectrum created by simulation for the light emitting devices using the phosphors of Examples 18 to 28 and Comparative Examples 4 to 6.
  • the light emitting device of Comparative Example 4 since the half-value width of the phosphor used was as narrow as 95 nm or less, the color rendering index Ra was as low as 57, and there was a problem in terms of color rendering properties. Since the full width at half maximum is 95 nm or more, the color rendering properties of the light emitting device are improved. In other words, the light emitting device of the present invention can provide a phosphor having a wide half-value width according to the present invention, so that it is possible to provide a light emitting device having good color rendering and white to light bulb color. .
  • Non-Patent Document 1 Proceedings of the IEICE General Conference, 2005, Electronics (2), 42, 2005-03-07.
  • the correlation color temperature of the light-emitting device described in 1 and the color rendering index Ra were almost the same, indicating the validity of the simulation used for creating the emission spectrum of the light-emitting device of the example.
  • the half width of the phosphor used is narrow, and the emission peak wavelength is too long as 594 nm, so the correlated color temperature is 1942K. It is not possible.
  • the emission peak wavelength of the phosphor to be used is on the short wavelength side, it is possible to provide a light emitting device with good color rendering and white to light bulb color.
  • the correlated color temperature of the phosphor used is about 5500K, and the blue LED and this phosphor alone cannot be a white to light bulb color (2600K to 4500K) light emitting device.
  • Examples 18 to 23 it was confirmed that a light emitting device having good color rendering properties and a light emitting color of white to light bulb color (4500K to 2600K) could be provided. This is because the emission peak wavelength can be adjusted while maintaining the feature that the phosphor of the present invention to be used has a wide half-value width of the emission spectrum.
  • the color rendering index Ra of the light emitting device of Example 18 is 7 points higher than that of Comparative Example 4, and the color rendering index Ra of Examples 19 to 23 is equivalent to that of Example 18. Or it increased within the range of plus 6 points.
  • the value of the color rendering index Ra is higher than that of Example 18 in Examples 24, 25, 26, It increased by 1 or 2 points in the order of 27 and 28. This is because the full width at half maximum of the emission spectrum can be widened by replacing the Sr site of the phosphor used in the light emitting device with Ba. As a result, it is possible to provide a light-emitting device having a light bulb color (2600K to 3250K) with good color rendering.
  • Example 31 Regarding the light emitting device simulated in Example 18 described above, a surface-mounted white light emitting device having the configuration shown in FIG. 2B was actually manufactured by the following procedure, and the light emission characteristics were measured. Of the constituent elements of the present embodiment, the constituent elements corresponding to those shown in FIG. 2B are indicated by parentheses as appropriate.
  • an InGaN light emitting diode manufactured by Showa Denko KK
  • Showa Denko KK which is a blue light emitting diode (hereinafter referred to as “blue LED” where appropriate) that emits light at a wavelength of 450 nm to 470 nm
  • This blue LED (22) was die-bonded to the electrode (27) at the bottom of the recess of the frame (24) using a silver paste as an adhesive.
  • the silver paste as the adhesive was thinly and uniformly applied in consideration of the heat dissipation of the heat generated in the blue LED (22).
  • the blue LED (22) and the electrode (26) of the frame (24) were wire-bonded.
  • a gold wire having a diameter of 25 ⁇ m was used as the wire (25).
  • the phosphor 18 described above was used as the luminescent material of the phosphor-containing part (23).
  • Phosphor slurry obtained by mixing the phosphor 18, the organically modified silicone resin (SCR 1011 manufactured by Shin-Etsu Silicone), and Aerosil (RX-200 manufactured by Nippon Aerosil Co., Ltd.) in a weight ratio of 15.5: 85.5: 2.
  • Aerosil RX-200 manufactured by Nippon Aerosil Co., Ltd.
  • the purpose of using Aerosil is to prevent sedimentation of the phosphor in the resin.
  • the obtained phosphor slurry is poured into the recesses of the frame (24) and cured by heating at 100 ° C. for 3 hours and further at 140 ° C. for 3 hours to form the phosphor-containing portion (23), and the surface A mounting type white light emitting device was produced. Further, the obtained light emitting device was driven to emit light at 25 ° C. by applying a current of 20 mA to the blue LED (22). All the light emission from the white light emitting device was received by an integrating sphere, and further introduced into a spectroscope by an optical fiber, the emission spectrum and the total luminous flux were measured, and the white chromaticity coordinates were measured.
  • the emission spectrum is measured by energizing 20 mA using Ocean Optics color / illuminance measurement software and USB2000 series spectroscope (integral sphere specification). , It was confirmed that it emitted light bulb color. From the obtained emission spectra, the correlated color temperature was calculated in the same manner as in Examples 18 to 28 and Comparative Examples 4 to 6, and it was 2773K.
  • the phosphor of the present invention can be used in any field where light is used.
  • image display of various electronic devices such as mobile phones, household appliances, and outdoor installation displays. It can be suitably used for an apparatus or the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Electroluminescent Light Sources (AREA)
  • Led Device Packages (AREA)

Abstract

L'invention porte sur un luminophore dont le squelette est constitué de Si, Al, N et O et dont l'intensité lumineuse est élevée. Le luminophore est un luminophore à base d'oxynitrure qui est caractérisé en ce qu'il contient une phase cristalline dont la composition est représentée par la formule (1) : (A1-x,Eux)aDbEcNdOe. (Dans la formule (1), A représente des éléments métalliques alcalinoterreux comprenant essentiellement Sr et Ca ; D représente des éléments métalliques tétravalents comprenant essentiellement Si ; E représente des éléments métalliques trivalents comprenant essentiellement Al ; x représente un nombre qui satisfait à la relation 0,0001 ≤ x ≤ 0,20 ; a, b, c, d et e représentent chacun respectivement des nombres qui satisfont aux relations 0,7 ≤ a ≤ 1,3, 2,8 ≤ b ≤ 4,0, 1,0 ≤ c ≤ 3,0, 4,0 ≤ (b + c)/a ≤ 6,0, 5,0 ≤ d ≤ 7,0, 0 < e ≤ 2,0 et 6,5 ≤ (d + e)/a ≤ 7,5). Le luminophore à base d'oxynitrure est également caractérisé en ce que le système cristallin de la phase cristalline est un système orthorhombique ou un système monoclinique, et en ce que le volume de la maille élémentaire (V) de la phase cristalline, calculé à partir du paramètre de maille, est de 1220 × 106 pm3 à 1246 × 106 pm3 (inclus).
PCT/JP2013/050668 2012-01-17 2013-01-16 Luminophore à base d'oxynitrure et dispositif électroluminescent l'utilisant WO2013108782A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2012-007128 2012-01-17
JP2012007128 2012-01-17
JP2012-049561 2012-03-06
JP2012049561 2012-03-06

Publications (1)

Publication Number Publication Date
WO2013108782A1 true WO2013108782A1 (fr) 2013-07-25

Family

ID=48799207

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/050668 WO2013108782A1 (fr) 2012-01-17 2013-01-16 Luminophore à base d'oxynitrure et dispositif électroluminescent l'utilisant

Country Status (3)

Country Link
JP (1) JP2013213191A (fr)
TW (1) TW201335338A (fr)
WO (1) WO2013108782A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103484110A (zh) * 2013-09-06 2014-01-01 北京科技大学 一种红色硅铝氧氮化物荧光材料及其制备方法
WO2019045106A1 (fr) * 2017-09-04 2019-03-07 三菱ケミカル株式会社 Luminophore, dispositif électroluminescent, dispositif d'affichage d'image et dispositif d'éclairage

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050230689A1 (en) * 2004-04-20 2005-10-20 Gelcore Llc Ce3+ and Eu2+ doped phosphors for light generation
WO2006061778A1 (fr) * 2004-12-06 2006-06-15 Philips Intellectual Property & Standards Gmbh Systeme d'eclairage comprenant une source de rayonnement et un phosphore a emission de bleu
JP2007137946A (ja) * 2005-11-15 2007-06-07 Mitsubishi Chemicals Corp 蛍光体、並びにそれを用いた発光装置、画像表示装置及び照明装置
JP2008527706A (ja) * 2005-01-10 2008-07-24 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 セラミック・ルミネッセンス変換器を有する照明システム
JP2010106127A (ja) * 2008-10-29 2010-05-13 Toshiba Corp 赤色蛍光体およびそれを用いた発光装置
JP2010268004A (ja) * 2010-08-18 2010-11-25 Toshiba Corp 赤色蛍光体およびそれを用いた発光装置
WO2011024296A1 (fr) * 2009-08-28 2011-03-03 株式会社 東芝 Procédé de fabrication d'une substance fluorescente et substance fluorescente obtenue par ce procédé
JP2011153320A (ja) * 2011-05-02 2011-08-11 Toshiba Corp 赤色蛍光体の製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050230689A1 (en) * 2004-04-20 2005-10-20 Gelcore Llc Ce3+ and Eu2+ doped phosphors for light generation
WO2006061778A1 (fr) * 2004-12-06 2006-06-15 Philips Intellectual Property & Standards Gmbh Systeme d'eclairage comprenant une source de rayonnement et un phosphore a emission de bleu
JP2008527706A (ja) * 2005-01-10 2008-07-24 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 セラミック・ルミネッセンス変換器を有する照明システム
JP2007137946A (ja) * 2005-11-15 2007-06-07 Mitsubishi Chemicals Corp 蛍光体、並びにそれを用いた発光装置、画像表示装置及び照明装置
JP2010106127A (ja) * 2008-10-29 2010-05-13 Toshiba Corp 赤色蛍光体およびそれを用いた発光装置
WO2011024296A1 (fr) * 2009-08-28 2011-03-03 株式会社 東芝 Procédé de fabrication d'une substance fluorescente et substance fluorescente obtenue par ce procédé
JP2010268004A (ja) * 2010-08-18 2010-11-25 Toshiba Corp 赤色蛍光体およびそれを用いた発光装置
JP2011153320A (ja) * 2011-05-02 2011-08-11 Toshiba Corp 赤色蛍光体の製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103484110A (zh) * 2013-09-06 2014-01-01 北京科技大学 一种红色硅铝氧氮化物荧光材料及其制备方法
WO2019045106A1 (fr) * 2017-09-04 2019-03-07 三菱ケミカル株式会社 Luminophore, dispositif électroluminescent, dispositif d'affichage d'image et dispositif d'éclairage
CN111051472A (zh) * 2017-09-04 2020-04-21 三菱化学株式会社 荧光体、发光装置、图像显示装置和照明装置
JPWO2019045106A1 (ja) * 2017-09-04 2020-08-20 三菱ケミカル株式会社 蛍光体、発光装置、画像表示装置及び照明装置
US11203713B2 (en) 2017-09-04 2021-12-21 Mitsubishi Chemical Corporation Phosphor, light-emitting device, image display device, and illumination device

Also Published As

Publication number Publication date
TW201335338A (zh) 2013-09-01
JP2013213191A (ja) 2013-10-17

Similar Documents

Publication Publication Date Title
US8709838B2 (en) Method for preparing a β-SiAlON phosphor
US7857994B2 (en) Green emitting phosphors and blends thereof
US20120212123A1 (en) Halophosphate phosphor and white light-emitting device
US20120267999A1 (en) Halophosphate phosphor and white light-emitting device
KR20120118469A (ko) 백색 발광 장치
US9657222B2 (en) Silicate phosphors
KR20110042122A (ko) 알파-사이알론 형광체
JP2009094231A (ja) 発光装置
JP2015113358A (ja) 蛍光体、蛍光体含有組成物、発光装置、照明装置、画像表示装置、及び蛍光体の製造方法
JP2010270196A (ja) 蛍光体及び蛍光体の製造方法、並びに、蛍光体含有組成物、発光装置、照明装置、画像表示装置及び蛍光塗料
US8414795B2 (en) Red light-emitting fluorescent substance and light-emitting device employing the same
JP2011256340A (ja) 蛍光体と、この蛍光体を用いた蛍光体含有組成物及び発光装置、並びに画像表示装置及び照明装置
JP6094377B2 (ja) 蛍光体、その蛍光体を用いた蛍光体含有組成物及び発光装置、並びに、その発光装置を用いた照明装置及び画像表示装置
KR101176212B1 (ko) 알카리 토류 포스포러스 나이트라이드계 형광체와 그 제조방법 및 이를 이용한 발광장치
WO2008065567A1 (fr) Systeme d&#39;eclairage comprenant un hétéropolyoxométalate
JP2013249466A (ja) 酸窒化物系蛍光体およびこれを用いた発光装置
WO2013108782A1 (fr) Luminophore à base d&#39;oxynitrure et dispositif électroluminescent l&#39;utilisant
JP2013144794A (ja) 酸窒化物系蛍光体およびこれを用いた発光装置
JP2013185011A (ja) 蛍光体の製造方法、およびその製造方法により得られる蛍光体
JP5471021B2 (ja) 蛍光体及び蛍光体の製造方法、並びに、蛍光体含有組成物、発光装置、照明装置及び画像表示装置
JP2013214718A (ja) 酸窒化物系蛍光体およびこれを用いた発光装置
JP2015000953A (ja) 酸窒化物系蛍光体およびこれを用いた発光装置
JP2015183084A (ja) 紫光励起用蛍光体、該蛍光体を用いた蛍光体含有組成物及び発光装置、並びに、該発光装置を用いた照明装置及び画像表示装置
JP2013227527A (ja) 蛍光体及びこれを用いた発光装置
US9475986B2 (en) Red phosphor and light-emitting device comprising the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13738331

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13738331

Country of ref document: EP

Kind code of ref document: A1