WO2014175385A1 - 蛍光体、その製造方法、発光装置および画像表示装置 - Google Patents
蛍光体、その製造方法、発光装置および画像表示装置 Download PDFInfo
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- WO2014175385A1 WO2014175385A1 PCT/JP2014/061578 JP2014061578W WO2014175385A1 WO 2014175385 A1 WO2014175385 A1 WO 2014175385A1 JP 2014061578 W JP2014061578 W JP 2014061578W WO 2014175385 A1 WO2014175385 A1 WO 2014175385A1
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Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H—ELECTRICITY
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- H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
- H01L2224/85909—Post-treatment of the connector or wire bonding area
- H01L2224/8592—Applying permanent coating, e.g. protective coating
-
- 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
Definitions
- the present invention provides at least an A element, a D element, and an X element (where A is one or more elements selected from Mg, Ca, Sr, and Ba, and D is Si, Ge, Sn, Ti, Zr) , Hf, one or more elements selected from Hf, X is one or more elements selected from O, N, and F), and E element (where E is B , Al, Ga, In, Sc, Y, La, or an inorganic crystal containing Li element and M element (where M is Mn, Ce, Pr, Nd, Sm, 1 or two or more elements selected from Eu, Tb, Dy, and Yb), and a method for producing the same, and a use thereof.
- A is one or more elements selected from Mg, Ca, Sr, and Ba, and D is Si, Ge, Sn, Ti, Zr
- Hf one or more elements selected from Hf
- X is one or more elements selected from O, N, and F
- E element where E is B , Al, Ga, In,
- Phosphors are fluorescent display tubes (VFD (Vacuum-Fluorescent Display)), field emission displays (FED (Field Emission Display) or SED (Surface-Conduction Electron Display) (Plasma Display) (PDP). ), Cathode ray tube (CRT (Cathode-Ray Tube)), liquid crystal display backlight (Liquid-Crystal Display Backlight), white light emitting diode (LED (Light-Emitting Diode)) and the like.
- VFD Voluum-Fluorescent Display
- FED Field Emission Display
- SED Surface-Conduction Electron Display
- Cathode ray tube CRT (Cathode-Ray Tube)
- liquid crystal display backlight Liquid-Crystal Display Backlight
- LED Light-Emitting Diode
- sialon phosphors can be used as phosphors with little reduction in luminance even when excited with high energy.
- phosphors based on inorganic crystals containing nitrogen in the crystal structure such as oxynitride phosphors and nitride phosphors.
- sialon phosphor is manufactured by a manufacturing process generally described below. First, silicon nitride (Si 3 N 4 ), aluminum nitride (AlN), and europium oxide (Eu 2 O 3 ) are mixed at a predetermined molar ratio, and the temperature is 1700 ° C. in nitrogen at 1 atm (0.1 MPa). It is manufactured by holding for 1 hour and firing by a hot press method (see, for example, Patent Document 1). It has been reported that ⁇ sialon activated by Eu 2+ ions obtained by this process becomes a phosphor that emits yellow light of 550 to 600 nm when excited by blue light of 450 to 500 nm. Further, it is known that the emission wavelength changes by changing the ratio of Si and Al and the ratio of oxygen and nitrogen while maintaining the crystal structure of ⁇ sialon (see, for example, Patent Document 2 and Patent Document 3). ).
- a green phosphor obtained by activating Eu 2+ to a ⁇ -type sialon is known (see Patent Document 4).
- this phosphor it is known that the emission wavelength changes to a short wavelength by changing the oxygen content while maintaining the crystal structure (see, for example, Patent Document 5). Further, it is known that when Ce 3+ is activated, a blue phosphor is obtained (for example, see Patent Document 6).
- a red phosphor in which Eu 2+ is activated using CaAlSiN 3 as a base crystal is known.
- this phosphor there is an effect of improving the color rendering properties of the white LED.
- a phosphor added with Ce as an optically active element has been reported as an orange phosphor.
- Non-Patent Documents 1 and 2 As a host crystal of another nitride phosphor, Ba 1 Si 7 N 10 or Sr 1 Si 7 N 10 is known (see Non-Patent Documents 1 and 2). It has been reported that a phosphor obtained by adding Eu 2+ using Ba 1 Si 7 N 10 as a base crystal emits blue light when excited by ultraviolet rays (Non-patent Document 3). Further, it has been reported that a phosphor obtained by adding Ce 3+ using Sr 1 Si 7 N 10 as a base crystal also emits blue light (Patent Document 10).
- the emission color of the phosphor is determined by the combination of the base crystal and the metal ion (activatable ion) to be dissolved therein. Furthermore, the combination of the base crystal and the activated ion determines the emission characteristics such as emission spectrum and excitation spectrum, chemical stability, and thermal stability, so when the base crystal is different or the activated ion is different, Considered as a different phosphor. In addition, even if the chemical composition is the same, materials having different crystal structures are regarded as different phosphors because their emission characteristics and stability differ due to different host crystals.
- Japanese Patent No. 3668770 Japanese Patent No. 3837551 Japanese Patent No. 4524368 Japanese Patent No. 3921545 International Publication No. 2007/066673 International Publication No. 2006/101096 International Publication No. 2005/019376 JP 2005-112922 A Japanese Patent No. 3837588 JP 2002-322474 A
- the present invention is intended to meet such a demand, and one of the objects is an LED having a light emission characteristic (emission color, excitation characteristic, emission spectrum) different from that of a conventional phosphor and having a wavelength of 410 nm or less.
- the object is to provide a chemically and thermally stable phosphor with high emission intensity even when combined with the above.
- Another object of the present invention is to provide a light emitting device with excellent durability and an image display device with excellent durability using such a phosphor.
- a element, D element and X element (where A is one or more elements selected from Mg, Ca, Sr and Ba, and D is selected from Si, Ge, Sn, Ti, Zr and Hf) 1 type or 2 types or more elements, X contains 1 type or 2 types or more elements chosen from O, N, and F), and E element (however, E is B, Al, Ga,
- An inorganic crystal containing one or more elements selected from In, Sc, Y, and La is an Li element and an M element (where M is Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy).
- One or more elements selected from Yb) Machine compound functions as a phosphor, the phosphor containing the inorganic compound as a main component were found to fluoresce high brightness. Moreover, it discovered that a specific composition showed
- this phosphor it is possible to obtain a white light emitting diode (light emitting device) having high luminous efficiency and small fluctuation due to temperature, a lighting apparatus using the same, and a brightly colored image display device. I found it.
- the present inventor has succeeded in providing a phosphor exhibiting a high luminance light emission phenomenon in a specific wavelength region by adopting the configuration described below. Moreover, it succeeded in manufacturing the fluorescent substance with the outstanding luminescent property using the following method. Furthermore, by using this phosphor, it has succeeded in providing a light emitting device, a lighting apparatus, an image display device, a pigment, and an ultraviolet absorber having excellent characteristics by adopting the configuration described below.
- the configuration is as described below.
- the phosphor of the present invention includes at least an A element, a D element, and an X element (where A is one or more elements selected from Mg, Ca, Sr, and Ba, and D is Si, Ge, Sn, 1 or 2 or more elements selected from Ti, Zr, and Hf, X contains 1 or 2 or more elements selected from O, N, and F), and an E element (provided that E Is an inorganic crystal containing one or more elements selected from B, Al, Ga, In, Sc, Y, and La, Li element and M element (where M is Mn, Ce, Pr, Nd) , Sm, Eu, Tb, Dy, Yb), and an inorganic compound containing the compound.
- A is one or more elements selected from Mg, Ca, Sr, and Ba
- D is Si, Ge, Sn, 1 or 2 or more elements selected from Ti, Zr, and Hf
- X contains 1 or 2 or more elements selected from O, N, and F
- E element provided that E Is an in
- the Li element and the M element may be dissolved in the inorganic crystal.
- the Li element may be interstitial solid solution in the inorganic crystal.
- (1) a crystal represented by A 1 (D, E) 7 X 10 , (2) a crystal having the same crystal structure as Sr 1 Si 7 N 10 crystal or Sr 1 Si 7 N 10 , ( 3) Either a Ba 1 Si 7 N 10 crystal or a crystal having the same crystal structure as Ba 1 Si 7 N 10 may be used.
- the element A is one or a mixture of two selected from Sr and Ba; the element D is Si; the element E is Al; the element X is N or a mixture of N and O;
- the M element may be Eu.
- the parameters f and g are 0.8 ⁇ f / (f + g) ⁇ 1.0 This condition may be satisfied.
- the ratio of h1 which is the number of N atoms contained in the inorganic compound and h2 which is the number of O atoms (where h1 + h2 h) is 0/10 ⁇ h2 / (h2 + h1) ⁇ 2/10 This condition may be satisfied.
- the element E contains at least boron, and the value of boron in the parameter g is 0.00001 ⁇ g ⁇ 0.01 This condition may be satisfied.
- the composition formula of the inorganic compound is Li w (Sr, Ba, Eu) p Si q Al z N s O t using parameters w, p, q, z, s, and t.
- the inorganic compound may be a single crystal particle having an average particle size of 0.1 ⁇ m or more and 100 ⁇ m or less, or an aggregate of the single crystal particles.
- the total of Fe, Co, and Ni impurity elements contained in the inorganic compound may be 500 ppm or less.
- the phosphor may further include another crystal phase or an amorphous phase in addition to the inorganic compound, and the content of the inorganic compound may be 20% by mass or more.
- the other crystal phase or amorphous phase may be an inorganic substance having conductivity.
- the conductive inorganic substance may be an oxide, oxynitride, or nitride containing one or more elements selected from Zn, Al, Ga, In, and Sn, or a mixture thereof.
- the other crystalline phase or amorphous phase may be an inorganic phosphor made of an inorganic compound of a different type from the inorganic compound. Fluorescence having a peak at a wavelength in the range of 470 nm to 620 nm may be emitted by irradiating the excitation source.
- the excitation source may be vacuum ultraviolet light, ultraviolet light, visible light, electron beam, or X-ray having a wavelength of 100 nm to 410 nm.
- the color emitted when the excitation source is irradiated is the value of (x, y) on the CIE 1931 chromaticity coordinates, 0.25 ⁇ x ⁇ 0.45 0.25 ⁇ y ⁇ 0.45 This condition may be satisfied.
- the value of (x, y) on the CIE1931 chromaticity coordinates is 0.25 ⁇ x ⁇ 0.45 0.25 ⁇ y ⁇ 0.45 You may emit the light with the chromaticity of the range.
- the production method of the present invention is a mixture of metal compounds that is baked to produce a raw material mixture that can constitute the above-described phosphor in a nitrogen-containing inert atmosphere at a temperature range of 1200 ° C. to 2200 ° C. By firing, the above-mentioned problems are solved.
- the mixture of metal compounds contains a compound containing Li, a compound containing M, a compound containing A, a compound containing D, a compound containing E as required, and X.
- M is one or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb, and A is selected from Mg, Ca, Sr, Ba
- D is one or more elements selected from Si, Ge, Sn, Ti, Zr, Hf
- E is B, Al, Ga, In, Sc, Y, La Or one or more elements selected from X
- X may be one or more elements selected from O, N, and F).
- the compound containing M is a single substance or a mixture of two or more selected from metals, silicides, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, or oxyfluorides containing M
- the compound containing A is a simple substance or two kinds selected from metals containing A, silicides, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, or oxyfluorides
- the above-mentioned mixture, wherein the compound containing D is a simple substance selected from metals, silicides, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, or oxyfluorides containing D Or it may be a mixture of two or more.
- the compound containing Li may be selected from a metal containing Li, a nitride of Li, an oxide of Li, a chloride of Li, and a fluoride of Li.
- the mixture of metal compounds may contain at least a nitride or oxide of europium, a nitride or oxide or carbonate of strontium, silicon oxide or silicon nitride, and a nitride of Li.
- the nitrogen-containing inert atmosphere may be a nitrogen gas atmosphere in a pressure range of 0.1 MPa to 100 MPa.
- Graphite may be used for the heating element and heat insulator of the firing furnace, and graphite or boron nitride may be used for the sample container.
- the metal compound in the form of powder or aggregate may be fired after filling the container in a state where the bulk density is kept at 40% or less.
- the average particle size of the powder particles or aggregates of the metal compound may be 500 ⁇ m or less. You may control the average particle diameter of the aggregate of a metal compound to 500 micrometers or less by spray dryer, sieving, or an air classification.
- the average particle size of the phosphor powder synthesized by firing may be adjusted to 50 nm or more and 20 ⁇ m or less by one or more methods selected from pulverization, classification, and acid treatment.
- the phosphor powder after firing, the phosphor powder after pulverization, or the phosphor powder after particle size adjustment may be heat-treated at a temperature of 1000 ° C.
- An inorganic compound that generates a liquid phase at a temperature not higher than the firing temperature is added to the mixture of the metal compounds and fired. If necessary, a liquid phase is generated at a temperature lower than the firing temperature by washing with a solvent after firing. You may reduce content of an inorganic compound.
- An inorganic compound that generates a liquid phase at a temperature not higher than the firing temperature is a fluoride, chloride, or iodide of one or more elements selected from Li, Na, K, Mg, Ca, Sr, and Ba, It may be a bromide or a mixture of one or more of phosphates.
- the light-emitting device of the present invention is composed of at least an excitation luminescent material and a phosphor, and is characterized by using at least the above-mentioned phosphor, thereby solving the above-described problems.
- the excitation light emitter may be a light emitting diode (LED), a laser diode (LD), a semiconductor laser, or an organic EL light emitter (OLED) that emits light having a wavelength of 330 to 410 nm.
- the light emitting device may be a white light emitting diode, a lighting fixture including a plurality of white light emitting diodes, or a backlight for a liquid crystal panel.
- the excitation illuminant emits ultraviolet or visible light having a peak wavelength of 300 to 410 nm, and the above-described phosphor has a value of (x, y) on the CIE1931 chromaticity coordinates, 0.25 ⁇ x ⁇ 0.45 0.25 ⁇ y ⁇ 0.45 You may emit the light which is the chromaticity of the range.
- the light emitting device may further include a blue phosphor that emits light having a peak wavelength of 450 nm to 500 nm or less by the excitation light emitter.
- the blue phosphor is selected from AlN: (Eu, Si), BaMgAl 10 O 17 : Eu, SrSi 9 Al 19 ON 31 : Eu, LaSi 9 Al 19 N 32 : Eu, ⁇ -sialon: Ce, JEM: Ce May be.
- the light emitting device may further include a green phosphor that emits light having a peak wavelength of 500 nm or more and 550 nm or less by the excitation light emitter.
- the green phosphor is ⁇ -sialon: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4 : Eu, (Ca, Sr, Ba) Si 2 O 2 N 2 : Eu, La 3 Si 6 N 11 : You may choose from Ce.
- the light emitting device may further include a yellow phosphor that emits light having a peak wavelength of 550 nm or more and 600 nm or less by the excitation light emitter.
- the yellow phosphor may be selected from YAG: Ce, ⁇ -sialon: Eu, CaAlSiN 3 : Ce, and La 3 Si 6 N 11 : Ce.
- the light emitting device may further include a red phosphor that emits light having a peak wavelength of 600 nm to 700 nm by the light emitter.
- the red phosphor may be selected from CaAlSiN 3 : Eu, (Ca, Sr) AlSiN 3 : Eu, Ca 2 Si 5 N 8 : Eu, and Sr 2 Si 5 N 8 : Eu.
- the excitation light emitter may be an LED that emits light having a wavelength of 300 to 410 nm.
- the light emitting device may further include a short wavelength light absorbing member that absorbs light of 410 nm or less and transmits light of 420 nm or more.
- An image display apparatus includes an excitation source and a phosphor, and is characterized by using at least the above-described phosphor, thereby solving the above-described problems.
- the image display device may be any one of a fluorescent display tube (VFD), a field emission display (FED), a plasma display panel (PDP), a cathode ray tube (CRT), and a liquid crystal display (LCD).
- the pigment or ultraviolet absorber of the present invention contains the above-described inorganic compound.
- the phosphor of the present invention contains at least an A element, a D element, an X element, a Li element, and an M element, and an inorganic compound containing an E element as a main component. It emits light with higher luminance than phosphors and oxynitride phosphors, and is excellent as a white phosphor in a specific crystal structure and composition. Even when exposed to an excitation source, the phosphor of the present invention does not decrease in luminance, so it is suitable for light emitting devices such as white light emitting diodes, lighting fixtures, backlight sources for liquid crystals, VFD, FED, PDP, CRT, etc. It provides a useful phosphor to be used. Moreover, the phosphor of the present invention absorbs ultraviolet rays and is therefore suitable for pigments and ultraviolet absorbers.
- FIG. 15 is a diagram illustrating the object color of the phosphor synthesized in Example 14.
- the phosphor of the present invention includes at least an A element, a D element, and an X element (where A is one or more elements selected from Mg, Ca, Sr, and Ba, and D is Si, Ge, Sn, 1 or 2 or more elements selected from Ti, Zr, and Hf, X contains 1 or 2 or more elements selected from O, N, and F), and an E element (provided that E Is an inorganic crystal containing one or more elements selected from B, Al, Ga, In, Sc, Y, and La, further Li element and M element (where M is Mn, Ce, Pr) , Nd, Sm, Eu, Tb, Dy, and Yb).
- the solid solution of Li can take the form of an interstitial solid solution or a substitutional solid solution, and the interstitial solid solution exhibits white light emission because the interaction between the light-emitting ions and the Li ions is strong.
- a phosphor that is either a Ba 1 Si 7 N 10 crystal or a crystal having the same crystal structure as Ba 1 Si 7 N 10 exhibits particularly high luminance.
- the inventors have (1) a crystal represented by A 1 (D, E) 7 X 10 , (2) a Sr 1 Si 7 N 10 crystal, or Sr 1 Si, such as SrSi 7 N 10 or BaSi 7 N 10.
- a crystal having the same crystal structure as 7 N 10 (3) a Ba 1 Si 7 N 10 crystal or a crystal having the same crystal structure as Ba 1 Si 7 N 10, and at least Li and an M element that is a luminescent center element; It was found that white luminescence was obtained by adding. More preferably, a phosphor that emits white light can be provided by adding Eu as the Li and M elements and / or Al as the Ce and E elements to the inorganic crystal.
- SrSi 7 N 10 and BaSi 7 N 10 are synonymous with Sr 1 Si 7 N 10 and Ba 1 Si 7 N 10 , but the latter clearly shows that Sr and Ba are 1, the former is This is a general description.
- the added M element typified by Eu, Al, and Li are taken into the crystal without greatly changing the crystal structure by being dissolved in the A 1 (D, E) 7 X 10 crystal.
- the M element is considered to be a substitutional solid solution with the A element position.
- Al is considered to be a substitutional solid solution at the D element position.
- Li is considered to be an interstitial solid solution in a place other than the element positions of A, D, and E.
- FIG. 1 is a diagram showing a crystal structure of a Ba 1 Si 7 N 10 crystal.
- (Ba, Sr) 1 (Si, Al) 7 (O, N) 10 Li + synthesized by the present inventors is one of crystals having the same crystal structure as that of the Ba 1 Si 7 N 10 crystal.
- the single-crystal structure analysis performed on the (Ba, Sr) 1 (Si, Al) 7 (O, N) 10 Li + crystal, it is a (Ba, Sr) 1 (Si, Al) ) 7 (O, N) 10 : Li + crystal belongs to the monoclinic system, belongs to the Pc space group (the 7th space group of International Tables for Crystallography), and occupies the crystal parameters and atomic coordinate positions shown in Table 1. .
- inorganic crystal metal element
- inorganic crystal metal element
- (Ba, Sr) 1 (Si, Al) 7 (O, N) 10 Li + is used. Indicates a material in which monovalent Li is dissolved in (Ba, Sr) 1 (Si, Al) 7 (O, N) 10 crystal.
- Li + was synthesized as follows. A mixed composition of silicon nitride (Si 3 N 4 ), aluminum nitride (AlN), lithium nitride (Li 3 N), strontium nitride (Sr 3 N 2 ) and barium nitride (Ba 3 N 2 ) in a molar ratio of 2: 1 : 0.667: 0.0667: 0.2667, and the mixed powder weighed and mixed to satisfy this mixed composition was fired in the same procedure as in Example 1 described later.
- lattice constants a, b, and c indicate the lengths of the unit cell axes, and ⁇ , ⁇ , and ⁇ indicate the angles between the unit cell axes.
- the atomic coordinates indicate the position of each atom in the unit cell as a value between 0 and 1 with the unit cell as a unit.
- the analysis result was obtained.
- Si and Al obtained the analysis result which exists in seven types of seats (Si, Al (1) to Si, Al (7)) without distinguishing the seats.
- N and O obtained the analysis result which exists in ten types of seats (N, O (1) to N, O (10)), without distinguishing a seat. Further, Li was detected by an ICP mass spectrometer, but the coordinate position could not be specified, suggesting that it is an interstitial solid solution.
- (Ba, Sr) 1 (Si, Al) 7 (O, N) 10 Li + crystal as a result of considering the Li: Si: Al ratio and Ba: Sr ratio by the ICP mass spectrometer and the neutrality of the charge The composition was Ba 0.8 Sr 0.2 Si 6.7 Al 0.3 Li 0.1 O 0.2 N 9.8 .
- Li + crystal has the structure shown in FIG. It has been found that the structure has a structure in which a Ba element, a Sr element, and a Li element are contained in a skeleton in which tetrahedrons formed by bonding with N are connected. In this crystal, the M element that becomes an activating ion such as Eu is incorporated into the crystal in a form that replaces part of the Ba element or Sr element.
- the ratio of the number of atoms of A element to 1, D and E can be 7 in total, and X can be 10 in total.
- the ratio of the cation of A, D, E and the anion of X satisfies the condition that the electrical neutrality in the crystal is maintained.
- the ratio of the number of atoms of A element to 1 and Si and Al in total 7 and O and N in total 10 can be made.
- the Si / Al ratio and the O / N ratio satisfy the condition that the electrical neutrality in the crystal is maintained.
- the Ba 1 Si 7 N 10- based crystal of the present invention can be identified by X-ray diffraction or neutron diffraction.
- a substance exhibiting the same diffraction as the X-ray diffraction result of the Ba 1 Si 7 N 10 based crystal shown in the present invention there is a crystal represented by A 1 (D, E) 7 X 10 .
- a crystal whose lattice constant or atomic position is changed by replacing a constituent element with another element in a Ba 1 Si 7 N 10 crystal.
- the constituent element is replaced by another element, for example, a part or all of Ba in the Ba 1 Si 7 N 10 crystal is an A element other than Ba (where A is Mg, Ca, Sr).
- One or more elements selected from Ba) or M element (where M is one or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb) Element).
- M element one or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb
- D element other than Si where D is one or more elements selected from Si, Ge, Sn, Ti, Zr, and Hf.
- D is one or more elements selected from Si, Ge, Sn, Ti, Zr, and Hf.
- E element is one or more elements selected from B, Al, Ga, In, Sc, Y, and La.
- Those whose crystal structure does not change as a result of element substitution are Ba 1 Si 7 N 10 based crystals. Substitution of elements changes the light emission characteristics, chemical stability, and thermal stability of the phosphor. Therefore, it is preferable that the phosphor is selected in a timely manner according to the application within a range in which the crystal structure is maintained.
- the Ba 1 Si 7 N 10- based crystal changes its lattice constant when its constituent components are replaced by other elements or when an activating element such as Eu is dissolved, but the crystal structure and the sites occupied by atoms and its coordinates The atomic position given by does not change so much that the chemical bond between the skeletal atoms is broken.
- the lengths of chemical bonds of Al—N and Si—N (proximity) calculated from lattice constants and atomic coordinates obtained by Rietveld analysis of the results of X-ray diffraction and neutron diffraction in the Pc space group.
- the interatomic distance When the interatomic distance) is within ⁇ 5% of the length of the chemical bond calculated from the lattice constant and atomic coordinates of the Ba 1 Si 7 N 10 crystal shown in Table 1, it is defined as the same crystal structure. It is determined whether it is a 1 Si 7 N 10 series crystal. This criterion is because, according to experiments, when the length of the chemical bond in the Ba 1 Si 7 N 10- based crystal changes beyond ⁇ 5%, the chemical bond is broken and another crystal is formed.
- FIG. 2 is a diagram showing powder X-ray diffraction using CuK ⁇ rays calculated from the crystal structure of (Ba, Sr) 1 (Si, Al) 7 (O, N) 10 : Li + crystal.
- the crystal is a Ba 1 Si 7 N 10- based crystal.
- the main peak of the Ba 1 Si 7 N 10- based crystal may be determined by about 10 having strong diffraction intensity.
- Table 1 is important because it serves as a reference in specifying the Ba 1 Si 7 N 10- based crystal in that sense.
- an approximate structure can be defined by using another monoclinic crystal system for the crystal structure of the Ba 1 Si 7 N 10 system crystal. In that case, different space groups, lattice constants, and plane indices can be obtained. Although it is the expression used, there is no change in the X-ray diffraction result (for example, FIG. 2) and the crystal structure (for example, FIG.
- One or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb are added to the Ba 1 Si 7 N 10- based crystal as M elements. When activated, a phosphor is obtained. Since emission characteristics such as excitation wavelength, emission wavelength, emission intensity, and the like vary depending on the composition of the Ba 1 Si 7 N 10- based crystal and the type and amount of the activation element, it may be selected according to the application.
- the A element is a mixture of one or two selected from Sr and Ba, the D element is Si, the E element is Al, and X A phosphor in which the element is N or a mixture of N and O and the M element is Eu has high emission intensity.
- an inorganic crystal having the same crystal structure as the crystal represented by A 1 (D, E) 7 X 10 or the crystal represented by Ba 1 Si 7 N 10 is a monoclinic crystal and has a space group Pc.
- the parameter c is a parameter representing the composition of L element such as Li, and if it is less than 0.001 or higher than 0.7, the crystal structure becomes unstable and the emission intensity decreases.
- the parameter d is the addition amount of the activating element, and if it is less than 0.00001, the amount of luminescent ions is insufficient and the luminance is lowered. If it exceeds 0.05, the emission intensity may decrease due to concentration quenching due to the interaction between luminescent ions.
- the parameter e is a parameter representing the composition of an alkaline earth element such as Ba. When the parameter e is less than 0.01 or higher than 0.1, the crystal structure becomes unstable and the emission intensity decreases.
- the parameter f is a parameter representing the composition of the D element such as Si, and if it is less than 0.1 or higher than 0.4, the crystal structure becomes unstable and the emission intensity decreases.
- the parameter g is a parameter representing the composition of an E element such as Al, and if it is higher than 0.1, the crystal structure becomes unstable and the emission intensity decreases. Preferably, parameter g is greater than zero. Thereby, high-luminance white light emission is enabled.
- the parameter h is a parameter representing the composition of the X element such as O, N, F, etc. If it is less than 0.15 or higher than 0.65, the crystal structure becomes unstable and the emission intensity decreases.
- the X element is an anion, and the composition of the O, N, and F ratio is determined so that the cation of the A, M, D, and E elements and the neutral charge are maintained.
- a crystal having a value in a range that satisfies all of the above conditions has a stable crystal structure and particularly high emission intensity.
- (D + e) / (d + e + f + g) 1/8 A crystal having a value satisfying all of the above conditions, that is, a crystal having a composition of (M, A) 1 (D, E) 7 X 10 has a particularly stable crystal structure and particularly high emission intensity.
- parameters f and g are 0.8 ⁇ f / (f + g) ⁇ 1.0
- a composition satisfying the above condition has a stable crystal structure and high emission intensity.
- a composition satisfying the above condition has a stable crystal structure and high emission intensity.
- a composition satisfying the above condition has a particularly stable crystal structure and particularly high emission intensity.
- the element E contains at least boron, and the value of boron in the parameter g is 0.00001 ⁇ g ⁇ 0.01
- the composition satisfying the above condition has a stable crystal structure and high emission intensity.
- the composition formula of the inorganic compound is Li w (Sr, Ba, Eu) p Si q Al z N s O t using the parameters w, p, q, z, s, and t.
- the inorganic compound is a single crystal particle having an average particle size of 0.1 ⁇ m or more and 100 ⁇ m or less, or a phosphor that is an aggregate of these single crystal particles has high luminous efficiency and good operability when mounted on an LED, It is better to control the particle size within the range.
- the Fe, Co, and Ni impurity elements contained in the inorganic compound may reduce the emission intensity.
- the total of these elements in the phosphor is 500 ppm or less, the influence of the decrease in emission intensity is reduced.
- the phosphor of the present invention uses the above Ba 1 Si 7 N 10- based crystal as a base crystal, in addition to an inorganic compound in which a Li element and an M element are dissolved, Other crystal phases or amorphous phases may be contained, and the content of the inorganic compound is 20% by mass or more.
- the embodiment of the present invention may be used when the phosphor of the present invention cannot obtain the desired characteristics with the above inorganic compound alone or when a function such as conductivity is added.
- the content of the inorganic compound may be adjusted according to the intended characteristics, but if it is less than 20% by mass, the emission intensity may be lowered. From such a viewpoint, in the phosphor mainly composed of the inorganic compound having the Ba 1 Si 7 N 10 based crystal of the present invention as a base crystal, the amount of the main component is 20% by mass or more.
- an inorganic substance having conductivity as another crystal phase or amorphous phase may be added.
- Examples of the inorganic substance having conductivity include an oxide, an oxynitride, a nitride, or a mixture thereof containing one or more elements selected from Zn, Al, Ga, In, and Sn.
- Examples thereof include zinc oxide, aluminum nitride, indium nitride, and tin oxide.
- Ba 1 Si 7 N 10 system crystal is used as a base crystal, and an inorganic compound in which Li element and M element are dissolved in the base crystal (hereinafter referred to as Ba 1 Si 7 N 10 system crystal phosphor for simplicity). Then, if the target emission spectrum cannot be obtained, a second phosphor may be added.
- An inorganic phosphor such as a body can be mentioned. These inorganic phosphors may be used as the other crystalline phase or amorphous phase described above.
- a phosphor having a peak at a wavelength in the range of 470 nm to 620 nm when irradiated with an excitation source there is a phosphor having a peak at a wavelength in the range of 470 nm to 620 nm when irradiated with an excitation source.
- a phosphor of Ba 1 Si 7 N 10- based crystal activated with Eu has a light emission peak in this range by adjusting the composition.
- a phosphor that emits light using vacuum ultraviolet rays, ultraviolet rays, visible light, electron beams, or X-rays having an excitation source with a wavelength of 100 nm to 410 nm. By using these excitation sources, light can be emitted efficiently.
- Li and Eu are added to an inorganic crystal having the same crystal structure as that of a crystal represented by A 1 (D, E) 7 X 10 or a crystal represented by Ba 1 Si 7 N 10.
- a phosphor whose main component is an inorganic compound in which is dissolved.
- the composition By adjusting the composition, it emits white fluorescence of 470 nm to 620 nm when irradiated with light of 100 nm to 410 nm. Therefore, the composition is preferably used for white light emission such as a white LED.
- the color emitted when the excitation source is irradiated is a value of (x, y) on the CIE1931 chromaticity coordinates, 0.25 ⁇ x ⁇ 0.45 0.25 ⁇ y ⁇ 0.45
- phosphors Li w (Sr, Ba, Eu) p Si q Al z N s O t
- a phosphor that develops a color having a chromaticity coordinate in this range can be obtained. It may be used for white light emitting applications such as white LEDs.
- the phosphor of the present invention has a broad excitation range from electron beam, X-ray, and ultraviolet to visible light, and emits white light, compared with normal oxide phosphors and existing sialon phosphors.
- the specific composition is characterized in that it exhibits a white color of 470 nm to 620 nm and the emission wavelength and emission peak width can be adjusted.
- the phosphor of the present invention is suitable for lighting fixtures, image display devices, pigments, and ultraviolet absorbers due to such light emission characteristics.
- the phosphor of the present invention is also excellent in heat resistance because it does not deteriorate even when exposed to high temperatures, and also has the advantage of excellent long-term stability in an oxidizing atmosphere and moisture environment, and is durable. Products with excellent properties can be provided.
- the method for producing the phosphor of the present invention is not particularly defined.
- a raw material mixture that is a mixture of metal compounds and can form a phosphor of Ba 1 Si 7 N 10 crystal by firing is used. It can be obtained by firing in a temperature range of 1200 ° C. to 2200 ° C. in an inert atmosphere containing nitrogen.
- the main crystal of the present invention is monoclinic and belongs to the space group Pc, crystals having a different crystal system or space group may be mixed depending on the synthesis conditions such as the firing temperature. Since the change in the light emission characteristics is slight, the phosphor of the present invention enables high luminance light emission.
- a mixture of metal compounds is a compound containing Li, a compound containing M, a compound containing A, a compound containing D, and a compound containing E as necessary.
- a compound containing X (where M is one or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb, A is Mg, Ca, Sr) 1 or 2 or more elements selected from Ba, D is one or more elements selected from Si, Ge, Sn, Ti, Zr, or Hf, E is B, Al, Ga, In , Sc, Y, La or one or more elements selected from X, and X may be one or more elements selected from O, N, or F).
- the compound containing M is a simple substance or two kinds selected from metals containing M, silicides, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, or oxyfluorides A mixture of the above, wherein the compound containing A is a simple substance selected from metals containing A, silicides, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, or oxyfluorides, or A compound containing two or more kinds and containing D is selected from metals containing D, silicides, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, or oxyfluorides A simple substance or a mixture of two or more kinds is preferred because the raw materials are easily available and have excellent stability.
- the compound containing X is a simple substance or a mixture of two or more selected from oxides, nitrides, oxynitrides, fluorides, and oxyfluorides containing X
- the raw materials are easily available and stable. It is preferable because it is excellent.
- the compound containing E is a simple substance or a mixture of two or more selected from metals, silicides, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, or oxyfluorides containing E Some are preferred because the raw materials are readily available and have excellent stability.
- a compound containing Li is a simple substance or a mixture of two or more selected from a metal containing Li, a nitride of Li, an oxide of Li, a chloride of Li, and a fluoride of Li It is preferable because the raw material is easily available and excellent in stability.
- a phosphor of Ba 1 Si 7 N 10- based crystal activated with Eu at least a nitride or oxide of europium, a nitride or oxide or carbonate of barium, silicon oxide or silicon nitride And a starting material containing a nitride of Li is preferable because the reaction easily proceeds during firing.
- the furnace used for firing has a high firing temperature, and the firing atmosphere is an inert atmosphere containing nitrogen. Therefore, carbon is used as a material for the high-temperature part of the furnace in a metal resistance heating method or a graphite resistance heating method.
- a suitable electric furnace is preferred.
- the inert atmosphere containing nitrogen is preferably in the pressure range of 0.1 MPa or more and 100 MPa or less because thermal decomposition of nitrides and oxynitrides which are starting materials and products is suppressed.
- the oxygen partial pressure in the firing atmosphere is preferably 0.0001% or less in order to suppress the oxidation reaction of nitrides and oxynitrides as starting materials and products.
- the firing time varies depending on the firing temperature, but is usually about 1 to 10 hours.
- boron or boron nitride components are mixed from the container into the product, but if the amount is small, the light emission characteristics are not deteriorated, so the influence is small. Furthermore, the addition of a small amount of boron nitride may improve the durability of the product, which is preferable in some cases.
- the relative bulk density is a ratio of a value (bulk density) obtained by dividing the mass of the powder filled in the container by the volume of the container and the true density of the substance of the powder.
- the relative bulk density is simply referred to as bulk density unless otherwise specified.
- the average particle diameter of the raw material powder particles or aggregate is 500 ⁇ m or less because of excellent reactivity and operability.
- a spray dryer, sieving, or air classification as a method for setting the particle size of the particles or aggregates to 500 ⁇ m or less because the work efficiency and operability are excellent.
- the firing method is not a hot press, but a sintering method that does not apply mechanical pressure from the outside, such as an atmospheric pressure sintering method or a gas pressure sintering method, is a method for obtaining a powder or aggregate product. preferable.
- the average particle diameter is 50 nm to 200 ⁇ m in terms of volume-based median diameter (d50), and the emission intensity is high. Therefore, it is preferable.
- the volume-based average particle diameter can be measured by, for example, a microtrack or a laser scattering method.
- the average particle size of the phosphor powder synthesized by firing may be adjusted to 50 nm to 200 ⁇ m.
- Defects in the powder or damage due to pulverization by heat-treating the phosphor powder after firing, phosphor powder after pulverization treatment, or phosphor powder after particle size adjustment at a temperature of 1000 ° C. or more and below the firing temperature May recover.
- Defects and damage may cause a decrease in emission intensity. In this case, the emission intensity is recovered by heat treatment.
- an inorganic compound that generates a liquid phase at a temperature lower than the firing temperature is added and fired to act as a flux, which promotes reaction and grain growth to produce stable crystals. May be obtained, which may improve the emission intensity.
- Fluoride chloride, iodide, bromide of one or more elements selected from Li, Na, K, Mg, Ca, Sr, Ba as an inorganic compound that generates a liquid phase at a temperature lower than the firing temperature Or a mixture of one or more phosphates. Since these inorganic compounds have different melting points, they may be used properly depending on the synthesis temperature.
- the emission intensity of the phosphor of the present invention may be increased by reducing the content of an inorganic compound that generates a liquid phase at a temperature lower than the firing temperature.
- the phosphor of the present invention When the phosphor of the present invention is used for a light emitting device or the like, it is preferable to use the phosphor in a form dispersed in a liquid medium. Moreover, it can also be used as a phosphor mixture containing the phosphor of the present invention.
- the phosphor of the present invention dispersed in a liquid medium is called a phosphor-containing composition.
- the liquid medium that can be used in the phosphor-containing composition of the present invention is a liquid medium that exhibits liquid properties under the desired use conditions, suitably disperses the phosphor of the present invention, and does not cause undesirable reactions. If there is, it is possible to select an arbitrary one according to the purpose.
- the liquid medium include addition-reactive silicone resins, condensation-reactive silicone resins, modified silicone resins, epoxy resins, polyvinyl resins, polyethylene resins, polypropylene resins, and polyester resins before curing. These liquid media may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
- the amount of the liquid medium used may be appropriately adjusted according to the application, etc., but in general, the weight ratio of the liquid medium to the phosphor of the present invention is usually 3% by weight or more, preferably 5% by weight or more, Moreover, it is 30 weight% or less normally, Preferably it is the range of 15 weight% or less.
- the phosphor-containing composition of the present invention may contain other optional components in addition to the phosphor of the present invention and the liquid medium, depending on its use and the like.
- other components include a diffusing agent, a thickener, a bulking agent, and an interference agent.
- silica-based fine powder such as Aerosil, alumina and the like can be mentioned.
- the light emitting device of the present invention is configured using at least an excitation light emitter or a light source and the phosphor of the present invention.
- excitation light emitters or light sources include LED light emitting devices, laser diode light emitting devices, EL light emitting devices, and fluorescent lamps.
- An LED light emitting device can be manufactured by using the phosphor of the present invention by a known method as described in JP-A-5-152609, JP-A-7-99345, JP-A-2927279, and the like. In this case, it is desirable that the light emitter or the light source emits light having a wavelength of 330 to 500 nm, and among these, an ultraviolet (or purple) LED light emitting element of 330 to 420 nm or a blue LED light emitting element of 420 to 500 nm is preferable.
- the LED light-emitting elements are made of a nitride semiconductor such as GaN or InGaN.
- the LED light-emitting element can be a light-emitting light source that emits light of a predetermined wavelength.
- Examples of the light emitting device of the present invention include a white light emitting diode including the phosphor of the present invention, a lighting fixture including a plurality of white light emitting diodes, or a backlight for a liquid crystal panel.
- Eu-activated ⁇ sialon phosphor in addition to the phosphor of the present invention, Eu-activated ⁇ sialon phosphor, Eu-activated ⁇ sialon yellow phosphor, Eu-activated Sr 2 Si 5 N 8 orange fluorescence body, Eu was activated (Ca, Sr) AlSiN 3 orange phosphor, and may further contain one or more phosphors selected from the CaAlSiN 3 red phosphor activated by Eu.
- yellow phosphors other than the above, for example, YAG: Ce, (Ca, Sr, Ba) Si 2 O 2 N 2 : Eu, or the like may be used.
- the value of (x, y) on the CIE1931 chromaticity coordinates that the excitation light-emitting body or light-emitting light source emits ultraviolet or visible light having a peak wavelength of 300 to 410 nm and the phosphor of the present invention emits so 0.25 ⁇ x ⁇ 0.45 0.25 ⁇ y ⁇ 0.45
- a light emitting device that emits light having a chromaticity in the range.
- a blue phosphor that emits light having a peak wavelength of 450 nm to 500 nm or less by an excitation light emitter or a light source can be included.
- Such blue phosphors include AlN: (Eu, Si), BaMgAl 10 O 17 : Eu, SrSi 9 Al 19 ON 31 : Eu, LaSi 9 Al 19 N 32 : Eu, ⁇ -sialon: Ce, JEM : Ce and the like.
- the expression “inorganic crystal: metal element” is a notation indicating a material in which a metal element is dissolved in an inorganic crystal.
- AlN: (Eu, Si) indicates that Eu and Si are solid in an AlN crystal. The melted material is shown.
- a green phosphor that emits light having a peak wavelength of 500 nm or more and 550 nm or less by a light emitting body or a light emitting light source can be included.
- examples of such green phosphors include ⁇ -sialon: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4 : Eu, (Ca, Sr, Ba) Si 2 O 2 N 2 : Eu, and the like. is there.
- a yellow phosphor that emits light having a peak wavelength of 550 nm or more and 600 nm or less by a light emitter or a light source can be included.
- Examples of such a yellow phosphor include YAG: Ce, ⁇ -sialon: Eu, CaAlSiN 3 : Ce, La 3 Si 6 N 11 : Ce.
- a red phosphor that emits light having a peak wavelength of 600 nm or more and 700 nm or less by a light emitter or a light source can be included.
- red phosphor include CaAlSiN 3 : Eu, (Ca, Sr) AlSiN 3 : Eu, Ca 2 Si 5 N 8 : Eu, and Sr 2 Si 5 N 8 : Eu.
- the light-emitting device of the present invention when an LED that emits light having a wavelength of 300 to 410 nm is used as a light emitter or light-emitting light source, the light-emitting efficiency is high, so that a highly efficient light-emitting device can be configured.
- the light emitting device of the present invention there is a light emitting device having a short wavelength light absorbing member that absorbs light of 410 nm or less and transmits light of 420 nm or more.
- the image display device of the present invention is composed of at least an excitation source and the phosphor of the present invention, and includes a fluorescent display tube (VFD), a field emission display (FED), a plasma display panel (PDP), a cathode ray tube (CRT) and the like. is there.
- the phosphor of the present invention has been confirmed to emit light by excitation of vacuum ultraviolet rays of 100 to 190 nm, ultraviolet rays of 190 to 380 nm, electron beams, etc., and in combination of these excitation sources and the phosphor of the present invention, An image display apparatus as described above can be configured.
- the phosphor of the present invention comprising an inorganic compound crystal phase having a specific chemical composition has a white object color, it can be used as a pigment or a fluorescent pigment. That is, when the phosphor of the present invention is irradiated with illumination such as sunlight or a fluorescent lamp, a white object color is observed, but the color development is good and the phosphor of the present invention does not deteriorate for a long time. Is suitable for inorganic pigments. For this reason, when used for paints, inks, paints, glazes, colorants added to plastic products, etc., good color development can be maintained high over a long period of time.
- the phosphor of the present invention absorbs ultraviolet rays and is therefore suitable as an ultraviolet absorber. For this reason, when used as a paint, applied to the surface of a plastic product, or kneaded into a plastic product, the effect of blocking ultraviolet rays is high, and the product can be effectively protected from ultraviolet degradation.
- the raw material powder used in the synthesis was a silicon nitride powder having a specific surface area of 11.2 m 2 / g, an oxygen content of 1.29 wt%, and an ⁇ -type content of 95% (SN-E10 manufactured by Ube Industries, Ltd.).
- Example 1 [Synthesis and structural analysis of single crystals] Moles of silicon nitride (Si 3 N 4 ), aluminum nitride (AlN), lithium nitride (Li 3 N), strontium nitride (Sr 3 N 2 ), barium nitride (Ba 3 N 2 ), and europium nitride (EuN) The mixture composition was designed in a ratio of 2.33: 1: 0.667: 0.5: 0.133: 0.1.
- the crucible containing the mixed powder was set in a graphite resistance heating type electric furnace.
- the firing operation is as follows. First, the firing atmosphere is set to a vacuum of 1 ⁇ 10 ⁇ 1 Pa or less with a diffusion pump, heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity is 99.999 vol% at 800 ° C. Nitrogen was introduced to bring the pressure in the furnace to 1 MPa, and the temperature was raised to 1900 ° C. at 500 ° C. per hour and held at that temperature for 2 hours.
- the synthesized product When the synthesized product was observed with an optical microscope, the synthesized product was a mixture composed of a single crystal and other phases. Single crystal particles having a size of 49 ⁇ m ⁇ 65 ⁇ m ⁇ 97 ⁇ m were collected from the synthesized product. Elements contained in crystal particles using a scanning electron microscope (SEM; SU1510 manufactured by Hitachi High-Technologies Corporation) equipped with an energy dispersive element analyzer (EDS; QUANTAX manufactured by Bruker AXS). was analyzed. As a result, the presence of Ba, Sr, Si, Al, Eu, O, and N elements was confirmed. In addition, it is thought that O element originates in the trace amount oxygen contained in raw material powder.
- SEM scanning electron microscope
- EDS energy dispersive element analyzer
- this crystal was fixed to the tip of the glass fiber with an organic adhesive.
- a single crystal X-ray diffractometer with a rotating counter cathode of MoK ⁇ rays (SMART APEXII Ultra manufactured by Bruker AXS Co., Ltd.) was used to perform X-ray diffraction measurement under the condition that the output of the X-ray source was 50 kV 50 mA. .
- the crystal particles were a single crystal.
- the crystal structure was determined from the X-ray diffraction measurement result using single crystal structure analysis software (APEX2 manufactured by Bruker AXS).
- APEX2 manufactured by Bruker AXS
- the obtained crystal structure data and crystal structure were the same as those in Table 1 and FIG. 1, respectively.
- the atomic positions are as shown in Table 1.
- oxygen and nitrogen can enter the seat where X enters in sialon-based crystals, but Ba is +2 valent, Sr is +2 valent, Si is +4 valent, Al is +3 valent, Eu is +2 valent. Therefore, if the atomic position and the ratio of Ba, Sr, Si, Al, and Eu are known, the ratio of O and N occupying the (O, N) position can be obtained from the electrical neutrality condition of the crystal.
- the ICP mass spectrum attached to laser ablation was used to analyze Li in the crystal.
- the sample was irradiated with a laser beam having a beam diameter of 30 ⁇ m and a wavelength of 213 nm from an Nd: YAG laser manufactured by New Wave Research, and the Li element volatilized from the sample was analyzed by an ICP mass spectrometer. As a result, it was confirmed that the sample contained Li.
- the crystal obtained from the Li: Ba: Sr: Si: Al: Eu ratio of the measured values of EDS and ICP and the crystal structure data is (Ba, Sr, Eu) 1 Si 6.7 Al 0.3 Li 0.1 (Ba, Sr, Eu) 1 (Si, Al) 7 (O, N) 10 as one of the crystals having the same crystal structure as the Ba 1 Si 7 N 10 crystal, which is O 0.2 N 9.8. It was a single crystal in which Li was dissolved. Note that the starting material composition and the crystal composition are different from each other in a composition other than (Ba, Sr, Eu) 1 Si 6.7 Al 0.3 Li 0.1 O 0.2 N 9.8 as a small amount of second phase. Depending on the generation of the product, since this measurement uses a single crystal, the analysis result is pure (Ba, Sr, Eu) 1 Si 6.7 Al 0.3 Li 0.1 O 0.2 N 9. 8 structures are shown.
- FIG. 3 is a diagram showing an emission spectrum of (Ba, Sr, Eu) 1 (Si, Al) 7 (O, N) 10 : Li + single crystal particles.
- this sample is a Ba 1 Si 7 N 10- based crystal containing Li and Eu.
- Ba 1 Si 7 N 10 crystals can replace part or all of Ba with Sr while maintaining the crystal structure. That is, the crystal of A 1 Si 7 N 10 (A is one or two or a mixture selected from Ba and Sr) has the same crystal structure as the Ba 1 Si 7 N 10 crystal. Furthermore, a part of Si can be replaced with Al and a part of N can be replaced with oxygen, and it is confirmed that this crystal is one composition of a crystal group having the same crystal structure as Ba 1 Si 7 N 10 It was done.
- Example 2 to Example 14 and Comparative Example According to the design composition shown in Table 2 and Table 3, the raw materials were weighed so as to have the mixed composition (molar ratio) shown in Table 4. Depending on the type of raw material used, the composition may differ between the design composition in Tables 2 and 3 and the mixed composition in Table 4. In this case, the mixed composition was determined so that the amount of metal ions matched. These raw material powders were weighed in a glove box with a nitrogen atmosphere of oxygen and moisture of 1 ppm or less so as to have the above mixed composition, and mixed for 5 minutes using a pestle and mortar made of a silicon nitride sintered body. Next, the obtained mixed powder was put into a crucible made of a boron nitride sintered body. The bulk density of the mixed powder (powder) was about 33%.
- the crucible containing the mixed powder was set in a graphite resistance heating type electric furnace.
- Table 5 shows the firing conditions.
- the firing operation is as follows. First, the firing atmosphere is set to a vacuum of 1 ⁇ 10 ⁇ 1 Pa or less with a diffusion pump, heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity is 99.999 vol% at 800 ° C. Nitrogen was introduced to set the pressure in the furnace to 1 MPa, the temperature was raised to a predetermined temperature at 500 ° C. per hour, and the temperature was maintained for a predetermined time.
- the synthesized compound was pulverized using an agate mortar, and powder X-ray diffraction measurement was performed using Cu K ⁇ rays.
- the main product phase is shown in Table 6.
- the phase having the same crystal structure as that of the Ba 1 Si 7 N 10 crystal was the main product phase.
- the composite contains rare earth elements, alkaline earth metals, Si, and N, and optionally contains Al and O.
- the presence of Li was confirmed by laser ablation ICP mass spectrum measurement.
- the synthesized product was a phosphor containing an inorganic compound in which a light emitting ion M such as Eu or a solid solution was dissolved in a crystal having the same crystal structure as that of the Ba 1 Si 7 N 10 crystal.
- the fired body thus obtained was coarsely pulverized and then pulverized by hand with a silicon nitride sintered crucible and mortar, and passed through a 30 ⁇ m sieve.
- the average particle size was 3 to 8 ⁇ m.
- the part in which the mixed raw material composition differs from the chemical composition of the composite is mixed in a small amount in the composite as the impurity second phase.
- FIG. 4 is a graph showing the result of powder X-ray diffraction of the phosphor synthesized in Example 14.
- FIG. 5 is a diagram showing an excitation spectrum and an emission spectrum of the phosphor powder synthesized in Example 14.
- the powder X-ray diffraction result (FIG. 4) of the synthesized phosphor shows a good agreement with the structure analysis result (FIG. 2).
- the X-ray diffraction pattern is the same as that of the Ba 1 Si 7 N 10 crystal, It was confirmed that a crystal having the same crystal structure as the Ba 1 Si 7 N 10 crystal was the main component. Furthermore, in Example 14, from the laser ablation ICP mass spectrum measurement and the EDS measurement, it was confirmed that the composite contained Li, Eu, Ba, Si, Al, and N. Moreover, it was confirmed that the ratio of (Ba + Eu) :( Si + Al) was 1: 7.
- the synthesized product was a phosphor mainly composed of an inorganic compound in which Li and Eu were dissolved in a Ba 1 Si 7 N 10- based crystal.
- Example 14 it was found that excitation was most efficient at 298 nm, and the emission spectrum when excited at 298 nm showed emission having a peak at 472 nm.
- the emission color of the phosphor of Example 14 was within the ranges of 0.25 ⁇ x ⁇ 0.45 and 0.25 ⁇ y ⁇ 0.45 in the CIE1931 chromaticity coordinates.
- the phosphor of Comparative Example 1 emits blue light
- the phosphors of Examples 1 to 14 emit white light from white with blue to white with red. You can see that This shows that when the Ba 1 Si 7 N 10- based crystal contains Li, the emission color has changed dramatically from blue light emission to white light emission.
- FIG. 6 is a diagram showing the object color of the phosphor synthesized in Example 14. Here, it is shown in black and white due to restrictions on application documents, but the original is in color, and a color diagram can be submitted upon request.
- Example 14 had a white object color and was excellent in color development. Although not shown, the composites of other examples also showed similar object colors. It has been found that the composite of the present invention can be used as a pigment or a fluorescent pigment.
- FIG. 7 is a schematic view showing a lighting fixture (bullet type LED lighting fixture) according to the present invention.
- a so-called bullet-type white light-emitting diode lamp (1) shown in FIG. 7 was produced.
- the lower electrode of the ultraviolet light emitting diode element (4) and the bottom surface of the recess are electrically connected by a conductive paste, and the upper electrode and the other lead wire (3) are electrically connected by a gold wire (5). It is connected to the.
- the phosphor (7) is dispersed in the resin and mounted in the vicinity of the light emitting diode element (4).
- the first resin (6) in which the phosphor is dispersed is transparent and covers the entire ultraviolet light emitting diode element (4).
- the tip of the lead wire including the recess, the blue light emitting diode element, and the first resin in which the phosphor is dispersed are sealed with a transparent second resin (8).
- the transparent second resin (8) has a substantially cylindrical shape as a whole, and has a lens-shaped curved surface at the tip, which is commonly called a shell type.
- FIG. 8 is a schematic view showing a lighting fixture (substrate mounted LED lighting fixture) according to the present invention.
- a chip-type white light emitting diode lamp (11) for board mounting shown in FIG. 8 was produced.
- Two lead wires (12, 13) are fixed to a white alumina ceramic substrate (19) having a high visible light reflectivity, and one end of each of these wires is located at a substantially central portion of the substrate, and the other end is external. It is an electrode that is soldered when mounted on an electric board.
- One of the lead wires (12) has a blue light emitting diode element (14) having an emission peak wavelength of 450 nm placed and fixed at one end of the lead wire so as to be at the center of the substrate.
- the lower electrode of the blue light emitting diode element (14) and the lower lead wire are electrically connected by a conductive paste, and the upper electrode and the other lead wire (13) are electrically connected by a gold thin wire (15). Connected.
- the first resin (16) and the white phosphor (17) produced in Example 14 are mounted in the vicinity of the light emitting diode element.
- the first resin in which the phosphor is dispersed is transparent and covers the entire blue light emitting diode element (14).
- a wall surface member (20) having a shape with a hole in the center is fixed on the ceramic substrate.
- the wall member (20) has a central portion serving as a hole for holding the resin (16) in which the blue light emitting diode element (14) and the phosphor (17) are dispersed, and the portion facing the center is a slope. It has become. This slope is a reflection surface for extracting light forward, and the curved surface shape of the slope is determined in consideration of the light reflection direction.
- the surface constituting the reflecting surface is a surface having a high visible light reflectance having white or metallic luster.
- the wall member (20) is made of a white silicone resin.
- the hole at the center of the wall member forms a recess as the final shape of the chip-type light-emitting diode lamp.
- the first resin in which the blue light-emitting diode element (14) and the phosphor (17) are dispersed A transparent second resin (18) is filled so as to seal all of 16).
- the same epoxy resin was used for the first resin (16) and the second resin (18).
- the addition ratio of the phosphor, the achieved chromaticity, etc. are substantially the same as in Example 15.
- FIG. 9 is a schematic view showing an image display device (plasma display panel) according to the present invention.
- the electrodes (39, 40, 41, 42) are energized, vacuum ultraviolet rays are generated by Xe discharge in the cell, which excites all phosphors and emits red, green, blue, and white visible light. Light is observed from the outside through the protective layer (46), the dielectric layer (45), and the glass substrate (48), and functions as an image display device.
- FIG. 10 is a schematic view showing an image display device (field emission display panel) according to the present invention.
- the white phosphor (56) of Example 14 of the present invention is applied to the inner surface of the anode (53).
- a voltage between the cathode (52) and the gate (54) electrons (57) are emitted from the emitter (55).
- the electrons are accelerated by the voltage of the anode (53) and the cathode, collide with the white phosphor (56), and white fluorescence is emitted from the white phosphor (56).
- the whole is protected by glass (51).
- the figure shows one light-emitting cell consisting of one emitter and one white phosphor, but in fact, a display that produces a variety of colors by arranging many blue, red, and green cells in addition to white. Is configured.
- the phosphor used for the green or red cell is not particularly specified, but a phosphor that emits high luminance with a low-speed electron beam may be used.
- the phosphor of the present invention has emission characteristics (emission color, excitation characteristics, emission spectrum) that are different from those of conventional phosphors, and has high emission intensity even when combined with an LED of 470 nm or less. It is suitable for VFD, FED, PDP, CRT, white LED and the like because it is stable and has little decrease in phosphor brightness when exposed to an excitation source. In the future, it can be expected to contribute greatly to the development of the industry in material design for various display devices.
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Abstract
Description
前記Li元素と前記M元素とは、前記無機結晶に固溶していてもよい。
前記Li元素は、前記無機結晶に侵入型固溶していてもよい。
前記無機結晶が、(1)A1(D,E)7X10で示される結晶、(2)Sr1Si7N10結晶またはSr1Si7N10と同一の結晶構造を有する結晶、(3)Ba1Si7N10結晶またはBa1Si7N10と同一の結晶構造を有する結晶のいずれかであってもよい。
前記A元素がSrとBaから選ばれる1種または2種の混合であり、前記D元素がSiであり、前記E元素がAlであり、前記X元素がNまたはNとOの混合であり、前記M元素がEuであってもよい。
前記無機結晶が、単斜晶系の結晶であり、空間群Pcの対称性を持ち、
格子定数a、b、cおよび角度α、β、γが、
a = 0.68875±0.05 nm
b = 0.67102±0.05 nm
c = 0.96756±0.05 nm
α = 90±1.5度
β = 106.17±1.5度
γ = 90±1.5度
の範囲の値であってもよい。
前記無機化合物は、組成式LcMdAeDfEgXh(ただし、式中c+d+e+f+g+h=1であり、LはLi元素、Mは、Mn、Ce、Pr、Nd、Sm、Eu、Tb、Dy、Ybから選ばれる1種または2種以上の元素、Aは、Mg、Ca、Sr、Baから選ばれる1種または2種以上の元素、Dは、Si、Ge、Sn、Ti、Zr、Hfから選ばれる1種または2種以上の元素、Eは、B、Al、Ga、In、Sc、Y、Laから選ばれる1種または2種以上の元素、Xは、O、N、Fから選ばれる1種または2種以上の元素)で示され、パラメータc、d、e、f、g、hが、
0.001≦ c ≦0.7
0.00001≦ d ≦0.05
0.01≦ e ≦0.1
0.1≦ f ≦ 0.4
0 ≦ g ≦ 0.1
0.15 ≦ h ≦ 0.65
の条件を全て満たす範囲の組成で表されてもよい。
前記パラメータd、e、f、g、hが、
(d+e)/(d+e+f+g)=1/8±0.014
の条件を全て満たす範囲の値であってもよい。
前記パラメータf、gが、
0.8 ≦ f/(f+g)≦ 1.0
の条件を満たしてもよい。
前記無機化合物中に含まれるNの原子数であるh1とOの原子数であるh2(但し、h1+h2=h)の比が、
0/10 ≦ h2/(h2+h1)≦ 2/10
の条件を満たしてもよい。
前記無機化合物中に含まれるNの原子数であるh1とOの原子数であるh2(但し、h1+h2=h)の比が、
0/10 ≦ h2/(h2+h1)≦ 1/10
の条件を満たしてもよい。
前記E元素として少なくともホウ素を含み、前記パラメータgにおけるホウ素の値は、
0.00001 ≦ g ≦ 0.01
の条件を満たしてもよい。
前記無機化合物の組成式がパラメータw、p、q、z、s、tを用いて
Liw(Sr,Ba,Eu)pSiqAlzNsOt
ただし、
q+z=7
s+t=10
w+2p+4q+3z=3s+2t
で示されてもよい。
前記無機化合物が、平均粒径0.1μm以上100μm以下の単結晶粒子あるいは前記単結晶粒子の集合体であってもよい。
前記無機化合物に含まれる、Fe、Co、Ni不純物元素の合計が500ppm以下であってもよい。
前記蛍光体は、前記無機化合物に加えて他の結晶相あるいはアモルファス相をさらに含み、前記無機化合物の含有量が20質量%以上であってもよい。
前記他の結晶相あるいはアモルファス相が導電性を持つ無機物質であってもよい。
前記導電性を持つ無機物質がZn、Al、Ga、In、Snから選ばれる1種または2種以上の元素を含む酸化物、酸窒化物、または窒化物、あるいはこれらの混合物であってもよい。
前記他の結晶相あるいはアモルファス相が前記無機化合物とは異なる種類の無機化合物からなる無機蛍光体であってもよい。
励起源を照射することにより470nmから620nmの範囲の波長にピークを持つ蛍光を発光してもよい。
前記励起源が100nm以上410nm以下の波長を持つ真空紫外線、紫外線または可視光、電子線またはX線であってもよい。
励起源が照射されたときに発光する色がCIE1931色度座標上の(x,y)の値で、
0.25 ≦ x ≦ 0.45
0.25 ≦ y ≦ 0.45
の条件を満たしてもよい。
Ba1Si7N10結晶にLiとAlとEuが固溶してなり、280nmから410nmの光を照射すると、CIE1931色度座標上の(x,y)の値で、
0.25 ≦ x ≦ 0.45
0.25 ≦ y ≦ 0.45
の範囲の色度を持つ光を発してもよい。
本発明の製造方法は、金属化合物の混合物であって焼成することにより、上述の蛍光体を構成しうる原料混合物を、窒素を含有する不活性雰囲気中において1200℃以上2200℃以下の温度範囲で焼成し、これにより上記課題を解決する。
前記金属化合物の混合物が、Liを含有する化合物と、Mを含有する化合物と、Aを含有する化合物と、Dを含有する化合物と、必要に応じてEを含有する化合物と、Xを含有する化合物(ただし、Mは、Mn、Ce、Pr、Nd、Sm、Eu、Tb、Dy、Ybから選ばれる1種または2種以上の元素、Aは、Mg、Ca、Sr、Baから選ばれる1種または2種以上の元素、Dは、Si、Ge、Sn、Ti、Zr、Hfから選ばれる1種または2種以上の元素、Eは、B、Al、Ga、In、Sc、Y、Laから選ばれる1種または2種以上の元素、Xは、O、N、Fから選ばれる1種または2種以上の元素)とからなってもよい。
前記Mを含有する化合物が、Mを含有する金属、ケイ化物、酸化物、炭酸塩、窒化物、酸窒化物、塩化物、フッ化物、または酸フッ化物から選ばれる単体または2種以上の混合物であり、前記Aを含有する化合物が、Aを含有する金属、ケイ化物、酸化物、炭酸塩、窒化物、酸窒化物、塩化物、フッ化物、または酸フッ化物から選ばれる単体または2種以上の混合物であり、前記Dを含有する化合物が、Dを含有する金属、ケイ化物、酸化物、炭酸塩、窒化物、酸窒化物、塩化物、フッ化物、または酸フッ化物から選ばれる単体または2種以上の混合物であってもよい。
前記Liを含有する化合物が、Liを含有する金属、Liの窒化物、Liの酸化物、Liの塩化物、Liのフッ化物から選ばれてもよい。
前記金属化合物の混合物が、少なくとも、ユーロピウムの窒化物または酸化物と、ストロンチウムの窒化物または酸化物または炭酸塩と、酸化ケイ素または窒化ケイ素と、Liの窒化物とを含有してもよい。
前記窒素を含有する不活性雰囲気が0.1MPa以上100MPa以下の圧力範囲の窒素ガス雰囲気であってもよい。
焼成炉の発熱体、断熱体、に黒鉛を、試料容器に黒鉛または窒化ホウ素を使用してもよい。
粉体または凝集体形状の金属化合物を、嵩密度40%以下の充填率に保持した状態で容器に充填した後に焼成してもよい。
金属化合物の粉体粒子または凝集体の平均粒径が500μm以下であってもよい。
スプレイドライヤ、ふるい分け、または風力分級により、金属化合物の凝集体の平均粒径を500μm以下に制御してもよい。
粉砕、分級、酸処理から選ばれる1種ないし複数の手法により、焼成により合成した蛍光体粉末の平均粒径を50nm以上20μm以下に粒度調整してもよい。
焼成後の蛍光体粉末、あるいは粉砕処理後の蛍光体粉末、もしくは粒度調整後の蛍光体粉末を、1000℃以上で焼成温度以下の温度で熱処理してもよい。
前記金属化合物の混合物に、焼成温度以下の温度で液相を生成する無機化合物を添加して焼成し、必要に応じて焼成後に溶剤で洗浄することにより焼成温度以下の温度で液相を生成する無機化合物の含有量を低減させてもよい。
前記焼成温度以下の温度で液相を生成する無機化合物が、Li、Na、K、Mg、Ca、Sr、Baから選ばれる1種または2種以上の元素のフッ化物、塩化物、ヨウ化物、臭化物、あるいはリン酸塩の1種または2種以上の混合物であってもよい。
本発明の発光装置は、少なくとも励起発光体と蛍光体とから構成され、少なくとも上述の蛍光体を用いることを特徴とし、これにより上記課題を解決する。
前記励起発光体が330~410nmの波長の光を発する発光ダイオード(LED)、レーザダイオード(LD)、半導体レーザ、または有機EL発光体(OLED)であってもよい。
前記発光装置が、白色発光ダイオード、または白色発光ダイオードを複数含む照明器具、あるいは液晶パネル用バックライトであってもよい。
前記励起発光体がピーク波長300~410nmの紫外または可視光を発し、上述の蛍光体が、CIE1931色度座標上の(x,y)の値で、
0.25 ≦ x ≦ 0.45
0.25 ≦ y ≦ 0.45
の範囲の色度である光を発してもよい。
前記発光装置は、前記励起発光体によりピーク波長450nm~500nm以下の光を発する青色蛍光体をさらに含んでもよい。
前記青色蛍光体が、AlN:(Eu,Si)、BaMgAl10O17:Eu、SrSi9Al19ON31:Eu、LaSi9Al19N32:Eu、α-サイアロン:Ce、JEM:Ceから選ばれてもよい。
前記発光装置は、前記励起発光体によりピーク波長500nm以上550nm以下の光を発する緑色蛍光体をさらに含んでもよい。
前記緑色蛍光体が、β-サイアロン:Eu、(Ba,Sr,Ca,Mg)2SiO4:Eu、(Ca,Sr,Ba)Si2O2N2:Eu、La3Si6N11:Ceから選ばれてもよい。
前記発光装置は、前記励起発光体によりピーク波長550nm以上600nm以下の光を発する黄色蛍光体をさらに含んでもよい。
前記黄色蛍光体が、YAG:Ce、α-sialon:Eu、CaAlSiN3:Ce、La3Si6N11:Ceから選ばれてもよい。
前記発光装置は、前記発光体によりピーク波長600nm以上700nm以下の光を発する赤色蛍光体をさらに含んでもよい。
前記赤色蛍光体が、CaAlSiN3:Eu、(Ca,Sr)AlSiN3:Eu、Ca2Si5N8:Eu、Sr2Si5N8:Euから選ばれてもよい。
前記発光装置において、前記励起発光体が300~410nmの波長の光を発するLEDであってもよい。
前記発光装置において、さらに、410nm以下の光を吸収し420nm以上の光を透過する短波長光吸収部材を有してもよい。
本発明の画像表示装置は、励起源と蛍光体から構成され、少なくとも上述の蛍光体を用いることを特徴とし、これにより上記課題を解決する。
前記画像表示装置が、蛍光表示管(VFD)、フィールドエミッションディスプレイ(FED)、プラズマディスプレイパネル(PDP)、陰極線管(CRT)、液晶ディスプレイ(LCD)のいずれかであってもよい。
本発明の顔料または紫外線吸収剤は、上述の無機化合物を含む。
本発明の蛍光体は、少なくともA元素とD元素とX元素(ただし、Aは、Mg、Ca、Sr、Baから選ばれる1種または2種以上の元素、Dは、Si、Ge、Sn、Ti、Zr、Hfから選ばれる1種または2種以上の元素、Xは、O、N、Fから選ばれる1種または2種以上の元素)を含み、必要に応じてE元素(ただし、Eは、B、Al、Ga、In、Sc、Y、Laから選ばれる1種または2種以上の元素)を含む無機結晶が、さらに、Li元素とM元素(ただしMは、Mn、Ce、Pr、Nd、Sm、Eu、Tb、Dy、Ybから選ばれる1種または2種以上の元素)とを含む無機化合物を主成分とする。
a = 0.68875±0.05 nm
b = 0.67102±0.05 nm
c = 0.96756±0.05 nm
α = 90±1.5度
β = 106.17±1.5度
γ = 90±1.5度
の範囲のものは結晶が特に安定であり、これらをホスト結晶とする蛍光体は発光強度が高い。この範囲を外れると結晶が不安定となり発光強度が低下することがある。
0.001≦ c ≦0.7
0.00001≦ d ≦0.05
0.01≦ e ≦0.1
0.1≦ f ≦ 0.4
0 ≦ g ≦ 0.1
0.15 ≦ h ≦ 0.65
の条件を全て満たす蛍光体は特に発光強度が高い。
(d+e)/(d+e+f+g)=1/8±0.014
の条件を全て満たす範囲の値の結晶は結晶構造が安定であり特に発光強度が高い。なかでも、
(d+e)/(d+e+f+g)=1/8
の条件を全て満たす値の結晶、すなわち、(M,A)1(D,E)7X10の組成を持つ結晶は、結晶構造が特に安定であり特に発光強度が高い。
0.8 ≦ f/(f+g)≦ 1.0
の条件を満たす組成は、結晶構造が安定であり発光強度が高い。
0/10 ≦ h2/(h2+h1)≦ 2/10
の条件を満たす組成は、結晶構造が安定であり発光強度が高い。なかでも、
無機化合物中に含まれるNとOの原子数であるh1とh2(但し、h1+h2=h)の比が、
0/10 ≦ h2/(h2+h1)≦ 1/10
の条件を満たす組成は、結晶構造が特に安定であり特に発光強度が高い。
0.00001 ≦ g ≦ 0.01
の条件を満たす組成は、結晶構造が安定であり、発光強度が高い。
Liw(Sr,Ba,Eu)pSiqAlzNsOt
ただし、
q+z=7
s+t=10
w+2p+4q+3z=3s+2t
で示される蛍光体は、安定な結晶構造を保ったままwとpとqとzとsとtのパラメータを変えることによる組成範囲でLi/(Sr+Ba+Eu)比、Si/Al比、N/O比を変化させることができる。これにより、励起波長や発光波長を連続的に変化させることができるため、材料設計がやりやすい蛍光体である。
0.25 ≦ x ≦ 0.45
0.25 ≦ y ≦ 0.45
範囲の蛍光体がある。例えば、
Liw(Sr,Ba,Eu)pSiqAlzNsOt
ただし、
q+z=7
s+t=10
w+2p+4q+3z=3s+2t
で示される組成に調整することにより、この範囲の色度座標の色を発色する蛍光体が得られる。白色LED等の白色発光の用途に用いると良い。
0.25 ≦ x ≦ 0.45
0.25 ≦ y ≦ 0.45
の範囲の色度を持つ光を発する蛍光体がある。白色LED等の白色発光の用途に用いると良い。
0.25 ≦ x ≦ 0.45
0.25 ≦ y ≦ 0.45
の範囲の色度である光を発する発光装置がある。
合成に使用した原料粉末は、比表面積11.2m2/gの粒度の、酸素含有量1.29重量%、α型含有量95%の窒化ケイ素粉末(宇部興産(株)製のSN-E10グレード)と、比表面積3.3m2/gの粒度の、酸素含有量0.82重量%の窒化アルミニウム粉末((株)トクヤマ製のEグレード)と、窒化リチウム((株)高純度化学製)と、純度99.5%の窒化ストロンチウム(Sr3N2;Materion Advanced Chemicals社製)と、純度99.5%の窒化バリウム(Ba3N2;Materion Advanced Chemicals社製)と、窒化セリウム(CeN;金属セリウムを窒素気流中で600℃で加熱して窒化したもの)と、窒化ユーロピウム(EuN;金属Euを窒素気流中で800℃に加熱することにより合成したもの)であった。
[単結晶の合成と構造解析]
窒化ケイ素(Si3N4)、窒化アルミニウム(AlN)、窒化リチウム(Li3N)、窒化ストロンチウム(Sr3N2)、窒化バリウム(Ba3N2)、および、窒化ユーロピウム(EuN)をモル比で2.33:1:0.667:0.5:0.133:0.1の割合で混合組成を設計した。これらの原料粉末を、酸素および水分が1ppm以下の窒素雰囲気のグローブボックス中で、上記混合組成となるように秤量し、窒化ケイ素焼結体製乳棒と乳鉢を用いて5分間混合を行なった。次いで、得られた混合粉末を、窒化ホウ素焼結体製のるつぼに投入した。混合粉末(粉体)の嵩密度は約33%であった。
a = 0.68875nm、b = 0.67102nm、c = 0.96756nmであり、角度α、β、γが、α=90°、β=109.166°、γ=90°であった。また原子位置は表1に示す通りであった。また、一般的にサイアロン系の結晶においてXが入る席には酸素と窒素が入ることができるが、Baは+2価、Srは+2価、Siは+4価、Alは+3価、Euは+2価であるので、原子位置とBaとSrとSiとAlとEuの比がわかれば、(O,N)位置を占めるOとNの比は結晶の電気的中性の条件から求められる。
Liw(Sr,Ba,Eu)pSiqAlzNsOt
ただし、
q+z=7
s+t=10
w+2p+4q+3z=3s+2tで示される組成としても記述できる。
表2および表3に示す設計組成に従って、原料を表4の混合組成(モル比)となるように秤量した。使用する原料の種類によっては表2および表3の設計組成と表4の混合組成で組成が異なる場合が生じるが、この場合は金属イオンの量が合致するように混合組成を決定した。これらの原料粉末を、酸素および水分が1ppm以下の窒素雰囲気のグローブボックス中で、上記混合組成となるように秤量し、窒化ケイ素焼結体製乳棒と乳鉢を用いて5分間混合を行なった。次いで、得られた混合粉末を、窒化ホウ素焼結体製のるつぼに投入した。混合粉末(粉体)の嵩密度は約33%であった。
図5は、実施例14で合成した蛍光体粉末の励起スペクトルおよび発光スペクトルを示す図である。
次ぎに、本発明の蛍光体を用いた発光装置について説明する。
図7は、本発明による照明器具(砲弾型LED照明器具)を示す概略図である。
図8は、本発明による照明器具(基板実装型LED照明器具)を示す概略図である。
図9は、本発明による画像表示装置(プラズマディスプレイパネル)を示す概略図である。
図10は、本発明による画像表示装置(フィールドエミッションディスプレイパネル)を示す概略図である。
2、3.リードワイヤ。
4.発光ダイオード素子。
5.ボンディングワイヤ。
6、8.樹脂。
7.蛍光体。
11.基板実装用チップ型白色発光ダイオードランプ。
12、13.リードワイヤ。
14.発光ダイオード素子。
15.ボンディングワイヤ。
16、18.樹脂。
17.蛍光体。
19.アルミナセラミックス基板。
20.側面部材。
31.赤色蛍光体。
32.緑色蛍光体。
33.青色蛍光体。
34.白色蛍光体。
35、36、37、38.紫外線発光セル。
39、40、41、42.電極。
43、44.誘電体層。
46.保護層。
47、48.ガラス基板。
51.ガラス。
52.陰極。
53.陽極。
54.ゲート。
55.エミッタ。
56.蛍光体。
57.電子。
Claims (54)
- 少なくともA元素とD元素とX元素(ただし、Aは、Mg、Ca、Sr、Baから選ばれる1種または2種以上の元素、Dは、Si、Ge、Sn、Ti、Zr、Hfから選ばれる1種または2種以上の元素、Xは、O、N、Fから選ばれる1種または2種以上の元素)を含み、必要に応じてE元素(ただし、Eは、B、Al、Ga、In、Sc、Y、Laから選ばれる1種または2種以上の元素)を含む無機結晶が、Li元素とM元素(ただしMは、Mn、Ce、Pr、Nd、Sm、Eu、Tb、Dy、Ybから選ばれる1種または2種以上の元素)とを含む無機化合物を含む蛍光体。
- 前記Li元素と前記M元素とは、前記無機結晶に固溶している、請求項1に記載の蛍光体。
- 前記Li元素は、前記無機結晶に侵入型固溶している、請求項2に記載の蛍光体。
- 前記無機結晶が、(1)A1(D,E)7X10で示される結晶、(2)Sr1Si7N10結晶またはSr1Si7N10と同一の結晶構造を有する結晶、(3)Ba1Si7N10結晶またはBa1Si7N10と同一の結晶構造を有する結晶のいずれかである、請求項1に記載の蛍光体。
- 前記A元素がSrとBaから選ばれる1種または2種の混合であり、
前記D元素がSiであり、
前記E元素がAlであり、
前記X元素がNまたはNとOの混合であり、
前記M元素がEuである、請求項1に記載の蛍光体。 - 前記無機結晶が、単斜晶系の結晶であり、空間群Pcの対称性を持ち、
格子定数a、b、cおよび角度α、β、γが、
a = 0.68875±0.05 nm
b = 0.67102±0.05 nm
c = 0.96756±0.05 nm
α = 90±1.5度
β = 106.17±1.5度
γ = 90±1.5度
の範囲の値である、請求項1に記載の蛍光体。 - 前記無機化合物は、組成式LcMdAeDfEgXh(ただし、式中c+d+e+f+g+h=1であり、LはLi元素、Mは、Mn、Ce、Pr、Nd、Sm、Eu、Tb、Dy、Ybから選ばれる1種または2種以上の元素、Aは、Mg、Ca、Sr、Baから選ばれる1種または2種以上の元素、Dは、Si、Ge、Sn、Ti、Zr、Hfから選ばれる1種または2種以上の元素、Eは、B、Al、Ga、In、Sc、Y、Laから選ばれる1種または2種以上の元素、Xは、O、N、Fから選ばれる1種または2種以上の元素)で示され、パラメータc、d、e、f、g、hが、
0.001≦ c ≦0.7
0.00001≦ d ≦0.05
0.01≦ e ≦0.1
0.1≦ f ≦ 0.4
0 ≦ g ≦ 0.1
0.15 ≦ h ≦ 0.65
の条件を全て満たす範囲の組成で表される、請求項1に記載の蛍光体。 - 前記パラメータd、e、f、g、hが、
(d+e)/(d+e+f+g)=1/8±0.014
の条件を全て満たす範囲の値である、請求項7に記載の蛍光体。 - 前記パラメータf、gが、
0.8 ≦ f/(f+g)≦ 1.0
の条件を満たす、請求項7に記載の蛍光体。 - 前記無機化合物中に含まれるNの原子数であるh1とOの原子数であるh2(但し、h1+h2=h)の比が、
0/10 ≦ h2/(h2+h1)≦ 2/10
の条件を満たす、請求項7に記載の蛍光体。 - 前記無機化合物中に含まれるNの原子数であるh1とOの原子数であるh2(但し、h1+h2=h)の比が、
0/10 ≦ h2/(h2+h1)≦ 1/10
の条件を満たす、請求項7に記載の蛍光体。 - 前記E元素として少なくともホウ素を含み、前記パラメータgにおけるホウ素の値は、
0.00001 ≦ g ≦ 0.01
の条件を満たす、請求項7に記載の蛍光体。 - 前記無機化合物の組成式がパラメータw、p、q、z、s、tを用いて
Liw(Sr,Ba,Eu)pSiqAlzNsOt
ただし、
q+z=7
s+t=10
w+2p+4q+3z=3s+2t
で示される、請求項1に記載の蛍光体。 - 前記無機化合物が、平均粒径0.1μm以上100μm以下の単結晶粒子あるいは前記単結晶粒子の集合体である、請求項1に記載の蛍光体。
- 前記無機化合物に含まれる、Fe、Co、Ni不純物元素の合計が500ppm以下である、請求項1に記載の蛍光体。
- 前記蛍光体は、前記無機化合物に加えて他の結晶相あるいはアモルファス相をさらに含み、前記無機化合物の含有量が20質量%以上である、請求項1に記載の蛍光体。
- 前記他の結晶相あるいはアモルファス相が導電性を持つ無機物質である、請求項16に記載の蛍光体。
- 前記導電性を持つ無機物質がZn、Al、Ga、In、Snから選ばれる1種または2種以上の元素を含む酸化物、酸窒化物、または窒化物、あるいはこれらの混合物である、請求項16に記載の蛍光体。
- 前記他の結晶相あるいはアモルファス相が前記無機化合物とは異なる種類の無機化合物からなる無機蛍光体である、請求項16に記載の蛍光体。
- 励起源を照射することにより470nmから620nmの範囲の波長にピークを持つ蛍光を発光する、請求項1に記載の蛍光体。
- 前記励起源が100nm以上410nm以下の波長を持つ真空紫外線、紫外線または可視光、電子線またはX線である、請求項20に記載の蛍光体。
- 励起源が照射されたときに発光する色がCIE1931色度座標上の(x,y)の値で、
0.25 ≦ x ≦ 0.45
0.25 ≦ y ≦ 0.45
の条件を満たす、請求項1に記載の蛍光体。 - Ba1Si7N10結晶にLiとAlとEuが固溶してなり、280nmから410nmの光を照射すると、CIE1931色度座標上の(x,y)の値で、
0.25 ≦ x ≦ 0.45
0.25 ≦ y ≦ 0.45
の範囲の色度を持つ光を発する、請求項1に記載の蛍光体。 - 金属化合物の混合物であって焼成することにより、請求項1に記載の蛍光体を構成しうる原料混合物を、窒素を含有する不活性雰囲気中において1200℃以上2200℃以下の温度範囲で焼成する、請求項1に記載の蛍光体の製造方法。
- 前記金属化合物の混合物が、Liを含有する化合物と、Mを含有する化合物と、Aを含有する化合物と、Dを含有する化合物と、必要に応じてEを含有する化合物と、Xを含有する化合物(ただし、Mは、Mn、Ce、Pr、Nd、Sm、Eu、Tb、Dy、Ybから選ばれる1種または2種以上の元素、Aは、Mg、Ca、Sr、Baから選ばれる1種または2種以上の元素、Dは、Si、Ge、Sn、Ti、Zr、Hfから選ばれる1種または2種以上の元素、Eは、B、Al、Ga、In、Sc、Y、Laから選ばれる1種または2種以上の元素、Xは、O、N、Fから選ばれる1種または2種以上の元素)とからなる、請求項24に記載の蛍光体の製造方法。
- 前記Mを含有する化合物が、Mを含有する金属、ケイ化物、酸化物、炭酸塩、窒化物、酸窒化物、塩化物、フッ化物、または酸フッ化物から選ばれる単体または2種以上の混合物であり、
前記Aを含有する化合物が、Aを含有する金属、ケイ化物、酸化物、炭酸塩、窒化物、酸窒化物、塩化物、フッ化物、または酸フッ化物から選ばれる単体または2種以上の混合物であり、
前記Dを含有する化合物が、Dを含有する金属、ケイ化物、酸化物、炭酸塩、窒化物、酸窒化物、塩化物、フッ化物、または酸フッ化物から選ばれる単体または2種以上の混合物である、請求項25に記載の蛍光体の製造方法。 - 前記Liを含有する化合物が、Liを含有する金属、Liの窒化物、Liの酸化物、Liの塩化物、Liのフッ化物から選ばれる、請求項24に記載の蛍光体の製造方法。
- 前記金属化合物の混合物が、少なくとも、ユーロピウムの窒化物または酸化物と、ストロンチウムの窒化物または酸化物または炭酸塩と、酸化ケイ素または窒化ケイ素と、Liの窒化物とを含有する、請求項24に記載の蛍光体の製造方法。
- 前記窒素を含有する不活性雰囲気が0.1MPa以上100MPa以下の圧力範囲の窒素ガス雰囲気である、請求項24に記載の蛍光体の製造方法。
- 焼成炉の発熱体、断熱体、に黒鉛を、試料容器に黒鉛または窒化ホウ素を使用する、請求項24に記載の蛍光体の製造方法。
- 粉体または凝集体形状の金属化合物を、嵩密度40%以下の充填率に保持した状態で容器に充填した後に焼成する、請求項24に記載の蛍光体の製造方法。
- 金属化合物の粉体粒子または凝集体の平均粒径が500μm以下である、請求項24に記載の蛍光体の製造方法。
- スプレイドライヤ、ふるい分け、または風力分級により、金属化合物の凝集体の平均粒径を500μm以下に制御する、請求項24に記載の蛍光体の製造方法。
- 粉砕、分級、酸処理から選ばれる1種ないし複数の手法により、焼成により合成した蛍光体粉末の平均粒径を50nm以上20μm以下に粒度調整する、請求項24に記載の蛍光体の製造方法。
- 焼成後の蛍光体粉末、あるいは粉砕処理後の蛍光体粉末、もしくは粒度調整後の蛍光体粉末を、1000℃以上で焼成温度以下の温度で熱処理する、請求項24に記載の蛍光体の製造方法。
- 前記金属化合物の混合物に、焼成温度以下の温度で液相を生成する無機化合物を添加して焼成し、必要に応じて焼成後に溶剤で洗浄することにより焼成温度以下の温度で液相を生成する無機化合物の含有量を低減させる、請求項24に記載の蛍光体の製造方法。
- 前記焼成温度以下の温度で液相を生成する無機化合物が、Li、Na、K、Mg、Ca、Sr、Baから選ばれる1種または2種以上の元素のフッ化物、塩化物、ヨウ化物、臭化物、あるいはリン酸塩の1種または2種以上の混合物である、請求項36に記載の蛍光体の製造方法。
- 少なくとも励起発光体と蛍光体とから構成される発光装置において、少なくとも請求項1に記載の蛍光体を用いることを特徴とする発光装置。
- 前記励起発光体が330~410nmの波長の光を発する発光ダイオード(LED)、レーザダイオード(LD)、半導体レーザ、または有機EL発光体(OLED)である、請求項38に記載の発光装置。
- 前記発光装置が、白色発光ダイオード、または白色発光ダイオードを複数含む照明器具、あるいは液晶パネル用バックライトである、請求項38に記載の発光装置。
- 前記励起発光体がピーク波長300~410nmの紫外または可視光を発し、請求項1に記載の蛍光体が、CIE1931色度座標上の(x,y)の値で、
0.25 ≦ x ≦ 0.45
0.25 ≦ y ≦ 0.45
の範囲の色度である光を発する、請求項38に記載の発光装置。 - 前記励起発光体によりピーク波長450nm~500nm以下の光を発する青色蛍光体をさらに含む、請求項38に記載の発光装置。
- 前記青色蛍光体が、AlN:(Eu,Si)、BaMgAl10O17:Eu、SrSi9Al19ON31:Eu、LaSi9Al19N32:Eu、α-サイアロン:Ce、JEM:Ceから選ばれる、請求項42に記載の発光装置。
- 前記励起発光体によりピーク波長500nm以上550nm以下の光を発する緑色蛍光体をさらに含む、請求項38に記載の発光装置。
- 前記緑色蛍光体が、β-サイアロン:Eu、(Ba,Sr,Ca,Mg)2SiO4:Eu、(Ca,Sr,Ba)Si2O2N2:Eu、La3Si6N11:Ceから選ばれる、請求項44に記載の発光装置。
- 前記励起発光体によりピーク波長550nm以上600nm以下の光を発する黄色蛍光体をさらに含む、請求項38に記載の発光装置。
- 前記黄色蛍光体が、YAG:Ce、α-sialon:Eu、CaAlSiN3:Ce、La3Si6N11:Ceから選ばれる、請求項46に記載の発光装置。
- 前記発光装置は、前記発光体によりピーク波長600nm以上700nm以下の光を発する赤色蛍光体をさらに含む、請求項38に記載の発光装置。
- 前記赤色蛍光体が、CaAlSiN3:Eu、(Ca,Sr)AlSiN3:Eu、Ca2Si5N8:Eu、Sr2Si5N8:Euから選ばれる、請求項48に記載の発光装置。
- 前記励起発光体が300~410nmの波長の光を発するLEDである、請求項38に記載の発光装置。
- さらに、410nm以下の光を吸収し420nm以上の光を透過する短波長光吸収部材を有する、請求項38に記載の発光装置。
- 励起源と蛍光体から構成される画像表示装置において、少なくとも請求項1に記載の蛍光体を用いることを特徴とする画像表示装置。
- 前記画像表示装置が、蛍光表示管(VFD)、フィールドエミッションディスプレイ(FED)、プラズマディスプレイパネル(PDP)、陰極線管(CRT)、液晶ディスプレイ(LCD)のいずれかである、請求項52に記載の画像表示装置。
- 請求項1に記載の無機化合物を含む顔料または紫外線吸収剤。
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JP6040500B2 (ja) | 2016-12-07 |
US20160060518A1 (en) | 2016-03-03 |
EP2990457A1 (en) | 2016-03-02 |
US9617471B2 (en) | 2017-04-11 |
JPWO2014175385A1 (ja) | 2017-02-23 |
EP2990457B1 (en) | 2018-12-05 |
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