WO2013180216A1 - 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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Definitions
- At least an A element, a D element, and an X element (where A is one or more elements selected from Li, Mg, Ca, Sr, and Ba, and D is Si, Ge, Sn, Ti) , Zr, or Hf, one or more elements selected from X, X is one or more elements selected from O, N, and F), and if necessary, E element (where E is , B, Al, Ga, In, Sc, Y, La), a crystal represented by A 3 (D, E) 8 X 14 , Sr 3 Si 8 O 4 crystal represented by N 10, inorganic crystals having the same crystal structure as the crystal represented by Sr 3 Si 8 O 4 N 10 , or the solid solution crystals of these crystals, M elements (where M is, Mn, Ce, One selected from Pr, Nd, Sm, Eu, Tb, Dy, Yb
- the present invention relates to a phosphor containing an inorganic compound in which two or more elements) are solid-dissolved, a method for
- 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 having an inorganic crystal containing nitrogen in the crystal structure as a base crystal such as an oxynitride phosphor and a nitride phosphor.
- 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.
- the phosphor has a light emission color determined by a combination of the host crystal and a metal ion (activated 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.
- phosphors it is possible to replace the type of constituent elements while maintaining the crystal structure of the host crystal, thereby changing the emission color.
- a phosphor obtained by adding Ce to YAG emits green light
- a phosphor obtained by substituting a part of Y in the YAG crystal with Gd and a part of Al with Ga exhibits yellow light emission.
- Eu Eu
- CaAlSiN 3 the composition changes while maintaining a crystal structure by substituting part of Ca with Sr, and the emission wavelength is shortened. In this way, the phosphors that have undergone element substitution while maintaining the crystal structure are regarded as the same group of materials.
- 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
- the present invention is intended to meet such a demand, and one of the objects is an LED having emission characteristics (emission color, excitation characteristics, emission spectrum) different from those of conventional phosphors and having a wavelength of 470 nm or less. It is an object to provide an inorganic phosphor having high emission intensity even when combined with the above and chemically and thermally stable. 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.
- the inventors conducted detailed research on a new crystal containing nitrogen, and a phosphor having a crystal obtained by replacing a metal element or N in the crystal structure with another element as a base crystal, crystal represented by Sr 3 Si 8 O 4 N 10 , inorganic crystals having the same crystal structure as Sr 3 Si 8 O 4 N 10 , or, inorganic phosphor that these solid solution crystal as a host crystal, high intensity We found that it emits fluorescence. It was also found that a specific composition shows yellow to red light emission.
- this phosphor it is possible to obtain a white light emitting diode (light emitting device) having high luminous efficiency and small temperature fluctuation, a lighting fixture using the same, and a vividly 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 according to 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 Li, Mg, Ca, Sr, and Ba, and D is Si, Ge, One or more elements selected from Sn, Ti, Zr, and Hf, and X is one or more elements selected from O, N, and F), and an E element as required , E is a crystal represented by Sr 3 Si 8 O 4 N 10 containing one or more elements selected from B, Al, Ga, In, Sc, Y, and La, or Sr 3 Si
- An inorganic crystal having the same crystal structure as that represented by 8 O 4 N 10 is added to M element (where M is Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb or Phosphors containing inorganic compounds in which two or more elements are dissolved It may be a "phosphor (1)" hereinafter). This solves the above problem.
- the inorganic crystal having the same crystal structure as the crystal represented by Sr 3 Si 8 O 4 N 10 is a crystal whose composition is represented by A 3 (D, E) 8 X 14. Yes, The crystal represented by A 3 (D, E) 8 X 14 contains at least Sr or Ca in the A element, Si in the D element, Al in the E element as necessary, and N in the X element.
- a phosphor (referred to as “phosphor (2)”) containing O in the X element as necessary may be used.
- the Sr 3 Si 8 O 4 inorganic crystal having the same crystal structure and crystal represented by N 10 is, Sr 3 Si 8 O 4 N 10, Ca 3 Si 8 O It may be a phosphor (referred to as “phosphor (3)”) that is 4 N 10 or (Sr, Li) 3 Si 8 O 4 N 10 .
- an inorganic crystal having the same crystal structure as the crystal represented by the Sr 3 Si 8 O 4 N 10 is Sr 3 Si 8 -x Al x N 10-.
- a phosphor (referred to as “phosphor (4)”) represented by the formula may be used.
- any of these phosphors (1) to (4) may be a phosphor (referred to as “phosphor (5)”) in which the M element is Eu.
- phosphor (7) A phosphor having a value in the range (referred to as “phosphor (7)”) may be used.
- “ ⁇ 0.05” indicates an allowable range. For a, for example, it can mean a range of 0.48170 ⁇ 0.05 ⁇ a ⁇ 0.48170 + 0.05 (the same applies hereinafter). .
- ⁇ 0.05 indicates an allowable range.
- d + e for example, it may mean a range of (3/25) ⁇ 0.05 ⁇ d + e ⁇ (3/25) +0.05. Yes (the same applies below).
- the parameters f and g are 3/8 ⁇ f / (f + g) ⁇ 8/8 A phosphor (referred to as “phosphor (10)”) that satisfies the above condition may be used.
- a phosphor (referred to as “phosphor (11)”) that satisfies the above condition may be used.
- any of these phosphors (1) to (11) may be a phosphor (referred to as “phosphor (12)”) containing at least Eu as the M element.
- the A element contains at least Sr or Ca
- the D element contains at least Si
- the E element contains at least Al
- the X It may be a phosphor (referred to as “phosphor (13)”) containing at least O and N as elements.
- the composition formula of the inorganic compound is Eu y Sr 3-y Si 8-x Al x N 10-x O 4 + x , Eu y using parameters x and y.
- the phosphor (referred to as “phosphor (14)”) indicated by
- the inorganic compound is a single crystal particle or an aggregate of single crystals having an average particle size of 0.1 ⁇ m or more and 20 ⁇ m or less (“phosphor (15 ) ”).
- a phosphor in which the total of Fe, Co, and Ni impurity elements contained in the inorganic compound is 500 ppm or less. There may be.
- any one of these phosphors (1) to (16) in addition to the inorganic compound, another crystalline phase or an amorphous phase (collectively referred to as “second phase”) different from the inorganic compound is further added. And a phosphor (referred to as “phosphor (17)”) in which the content of the inorganic compound is 20% by mass or more.
- the other crystal phase or amorphous phase (second phase) may be a phosphor (referred to as “phosphor (18)”), which is a conductive inorganic substance. .
- the conductive inorganic substance is an oxide, oxynitride, or nitride containing one or more elements selected from Zn, Al, Ga, In, and Sn.
- a phosphor referred to as “phosphor (19)” which is a mixture of these may be used.
- the other crystal phase or amorphous phase is an inorganic substance made of a compound (referred to as “second compound”) different from the inorganic compound. It may be a phosphor (referred to as “phosphor (20)”) which is a phosphor.
- any one of these phosphors (1) to (20) emits fluorescence having a peak in a wavelength range of 560 nm to 650 nm by irradiating an excitation source (referred to as “phosphor (21)”). ).
- This phosphor (21) is a phosphor (referred to as “phosphor (22)”) in which the excitation source is vacuum ultraviolet rays, ultraviolet rays or visible light, electron beams or X-rays having a wavelength of 100 nm to 450 nm. May be.
- phosphor (23) a phosphor in which Eu is dissolved in the crystal and emits yellow to red fluorescence of 560 nm to 650 nm when irradiated with light of 360 nm to 450 nm.
- the color emitted when the excitation source is irradiated is a value of (x0, y0) on the CIE1931 chromaticity coordinates, 0.1 ⁇ x0 ⁇ 0.7 0.2 ⁇ y0 ⁇ 0.9
- a phosphor (referred to as “phosphor (24)”) that satisfies the above condition may be used.
- the value on the CIE1931 chromaticity coordinate is represented by (x, y), but in order to avoid confusion with x and y used in the composition formula, x is x0 and y is y0 (hereinafter referred to as “x0”). The same).
- the production method of any one of the phosphors (1) to (24) according to the present invention is a mixture of metal compounds and is fired to constitute each inorganic compound of the phosphors (1) to (24).
- the manufacturing method (it is called “manufacturing method (25)") which bakes the raw material mixture which can be performed in the temperature range of 1200 to 2200 degreeC in the inert atmosphere containing nitrogen. This solves the above problem.
- the mixture of the said metal compound contains the compound containing M, the compound containing A, the compound containing D, the compound containing X, and E as needed (Wherein M is one or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb, and A is Li, Mg, Ca, Sr, Ba) One or more elements selected, D is one or more elements selected from Si, Ge, Sn, Ti, Zr, and Hf, E is B, Al, Ga, In, Sc, One or two or more elements selected from Y and La, and X is one or two or more elements selected from O, N, and F) (referred to as “manufacturing method (26)”) ).
- the compound containing M is a metal, silicide, oxide, carbonate, nitride, oxynitride, chloride, fluoride, or acid containing M.
- a simple substance or a mixture of two or more selected from oxyfluorides wherein the compound containing D is a metal, silicide, oxide, carbonate, nitride, oxynitride, chloride containing D , Fluoride, or oxyfluoride, or a production method (referred to as “production method (27)”) that is a mixture of two or more.
- the mixture of the metal compounds contains at least europium nitride or oxide, strontium nitride or oxide or carbonate, silicon oxide or silicon nitride.
- production method (28) a production method (referred to as “production method (28)”).
- the inert atmosphere containing nitrogen is a nitrogen gas atmosphere in a pressure range of 0.1 MPa or more and 100 MPa or less (“production method (29) ").
- Any one of these production methods (25) to (29) may be a production method (referred to as “production method (30)”) in which graphite is used for the heating element, heat insulator, or sample container of the firing furnace. .
- production method (32) in which the container used for firing is made of boron nitride may be used.
- production method (33) even if the average particle diameter of the metal compound powder particles or aggregates is 500 ⁇ m or less (referred to as “production method (33)”) Good.
- the average particle size of the aggregate of the metal compound is controlled to 500 ⁇ m or less by spray dryer, sieving, or air classification (“production method (34) ").
- the sintering means is a means by a normal pressure sintering method or a gas pressure sintering method exclusively without using a hot press (“production method (35 ) ”).
- the average particle size of the phosphor powder synthesized by firing is set to 50 nm or more and 20 ⁇ m or less by one or more methods selected from pulverization, classification, and acid treatment.
- the manufacturing method (referred to as “manufacturing method (36)”) to be adjusted may be used.
- the phosphor powder after firing, the phosphor powder after pulverization treatment, or the phosphor powder after particle size adjustment is at a temperature of 1000 ° C. or more and the firing temperature or less. It may be a manufacturing method (referred to as “manufacturing method (37)”) in which heat treatment is performed.
- an inorganic compound that generates a liquid phase at a temperature equal to or lower than the firing temperature is added to the mixture of the metal compounds and fired (“production method (38 ) ”).
- the inorganic compound that generates a liquid phase at a temperature equal to or lower than the firing temperature is one or more selected from Li, Na, K, Mg, Ca, Sr, and Ba. It may be a manufacturing method (referred to as “manufacturing method (39)”) that is a fluoride, chloride, iodide, bromide, or a mixture of two or more of two or more elements. .
- production method (40) the content of the inorganic compound that forms a liquid phase at a temperature lower than the firing temperature is reduced by washing with a solvent after firing (“production method (40) ").
- the light emitting device includes at least a light emitter and a phosphor (referred to as a “first phosphor”), and at least one of the phosphors (1) to (24) is the phosphor (first phosphor). It may be a light emitting device (referred to as “light emitting device (41)”) used as a phosphor.
- the light emitting device is a light emitting diode (LED), a laser diode (LD), a semiconductor laser, or an organic EL light emitting device (OLED) that emits light having a wavelength of 330 to 500 nm. (Referred to as “light emitting device (42)”).
- LED light emitting diode
- LD laser diode
- OLED organic EL light emitting device
- the light emitting device is a white light emitting diode, a lighting fixture including a plurality of white light emitting diodes, or a backlight for a liquid crystal panel (“light emitting device (43)”). May be used).
- the light emitter emits ultraviolet or visible light having a peak wavelength of 300 to 450 nm, and the blue (red) light emitted from the phosphor (first phosphor)
- a light emitting device that emits white light or light other than white light by mixing with light having a wavelength of 450 nm or more emitted from another phosphor (“light emitting device (44)”) May be used).
- the light emitting device further includes a blue phosphor (referred to as “third phosphor”) that emits light having a peak wavelength of 420 nm to 500 nm or less by the light emitter.
- third phosphor blue phosphor
- Light emitting device (45) This may mean, for example, that the second phosphor includes the third phosphor.
- the blue phosphor includes 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, a light emitting device (referred to as “light emitting device (46)”) may be used.
- the light emitting device further includes a green phosphor that emits light having a peak wavelength of 500 nm or more and 550 nm or less by the light emitter (referred to as “light emitting device (47)”). There may be.
- the green phosphor is ⁇ -sialon: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4 : Eu, (Ca, Sr, Ba) Si 2 O 2 N 2 : Eu.
- a light emitting device referred to as “light emitting device (48)” selected from
- the light emitting device further includes a yellow phosphor (referred to as “fourth phosphor”) that emits light having a peak wavelength of 550 nm to 600 nm inclusive by the light emitter.
- fourth phosphor yellow phosphor
- Light-emitting device (49) This may mean, for example, that the second phosphor includes the fourth phosphor.
- the yellow phosphor (fourth phosphor) is selected from YAG: Ce, ⁇ -sialon: Eu, CaAlSiN 3 : Ce, La 3 Si 6 N 11 : Ce (Referred to as “light emitting device (50)”).
- the light-emitting device further includes a red phosphor (referred to as “fifth phosphor”) that emits light having a peak wavelength of 600 nm to 700 nm inclusive by the light emitter.
- “Light emitting device (51)” This may mean, for example, that the second phosphor includes the fifth phosphor.
- the red phosphor (fifth phosphor) is CaAlSiN 3 : Eu, (Ca, Sr) AlSiN 3 : Eu, Ca 2 Si 5 N 8 : Eu, Sr 2 Si 5 N 8 : Light emitting device selected from Eu (referred to as “light emitting device (52)”).
- the light emitting device may be a light emitting device (referred to as “light emitting device (53)”), which is an LED that emits light having a wavelength of 320 to 450 nm. .
- An image display device includes an excitation source and a phosphor (referred to as “first phosphor”), and at least one of the phosphors (1) to (24) is used as the phosphor (first phosphor). It may be an image display device used as a phosphor.
- the image display device is 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). It may be an image display device.
- VFD fluorescent display tube
- FED field emission display
- PDP plasma display panel
- CRT cathode ray tube
- LCD liquid crystal display
- the pigment according to the present invention may be composed of the inorganic compound described in any one of the phosphors (1) to (24).
- the ultraviolet absorbent according to the present invention may be composed of the inorganic compound described in any one of the phosphors (1) to (24).
- a crystal represented by Sr 3 Si 8 O 4 N 10 another inorganic crystal having the same crystal structure as this, or a solid solution crystal thereof (hereinafter collectively referred to as Sr 3 Si 8 O 4 N 10- based crystal) is used as a base crystal, and element M functions as a phosphor when it is dissolved in the solid crystal.
- the phosphor of the present invention contains such an inorganic compound as a main component, thereby exhibiting high-luminance emission, and is excellent as a yellow to red phosphor in a specific composition.
- this phosphor does not decrease in luminance, so it is suitably used for light emitting devices such as white light emitting diodes, lighting fixtures, backlight sources for liquid crystals, VFD, FED, PDP, CRT, etc.
- the present invention provides a useful phosphor.
- this fluorescent substance absorbs an ultraviolet-ray, it is suitable for a pigment and a ultraviolet absorber.
- Sr 3 Si 8 O 4 N 10 shows a powder X-ray diffraction using the calculated CuK ⁇ ray from the crystal structure of the crystal.
- FIG. FIG. 16 shows an excitation spectrum and an emission spectrum of a synthesized product synthesized in Example 17.
- FIG. The figure which shows a mode that the object color (yellow or orange) of the compound synthesize
- 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 Li, Mg, Ca, Sr, and Ba, and D is Si, Ge, One or more elements selected from Sn, Ti, Zr, and Hf, and X is one or more elements selected from O, N, and F), and an E element as required , E is, B, Al, Ga, in , Sc, Y, comprise one or more elements) selected from La, represented by Sr 3 Si 8 O 4 N 10 crystal, Sr 3 Si 8 O 4 Inorganic crystals having the same crystal structure as those represented by N 10 , or solid solution crystals of these crystals, M element (where M is Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, 1 or 2 or more elements selected from Yb)
- the compound contains as a main component. Thereby, a phosphor that emits blue to red light can be provided.
- the crystal represented by Sr 3 Si 8 O 4 N 10 is a crystal that has not been reported before the present invention, which was newly synthesized by the present inventor and confirmed to be a new crystal by crystal structure analysis.
- FIG. 1 is a view showing a crystal structure of a Sr 3 Si 8 O 4 N 10 crystal.
- the Sr 3 Si 8 O 4 N 10 crystal belongs to the monoclinic system, and the P2 1 / n space group ( It belongs to the International Tables for Crystallography No. 14 space group) and occupies the crystal parameters and atomic coordinate positions shown in Table 1.
- the 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.
- Sr Sr
- Si Si
- O N
- O and N obtained the analysis result which exists in 14 types of the same seats (O, N (1) to O, N (14)).
- the structure of the Sr 3 Si 8 O 4 N 10 crystal is the structure shown in FIG. 1, and a tetrahedron composed of a combination of Si and O or N is connected. It was found that the skeleton had a structure containing Sr element. In this crystal, the M element that becomes an activating ion such as Eu is incorporated into the crystal in a form that replaces a part of the Sr element.
- inorganic crystals having the same crystal structure as the synthesized and structurally analyzed Sr 3 Si 8 O 4 N 10 crystal, A 3 (D, E) 8 X 14 crystal, A 3 Si 8 O 4 N 10 crystal and A 3 ( Si, Al) 8 (O, N) 14 crystals.
- a typical A element is Sr, Ca, or a mixture of Sr and Li.
- the Sr 3 Si 8 O 4 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 Sr 3 Si 8 O 4 N 10 crystal shown in the present invention there is a crystal represented by A 3 (D, E) 8 X 14 .
- a crystal in which the lattice constant or the atomic position is changed by replacing a constituent element with another element in the Sr 3 Si 8 O 4 N 10 crystal.
- the constituent element is replaced with another element, for example, a part or all of Sr in the Sr 3 Si 8 O 4 N 10 crystal is an A element other than Sr (where A is Li, Mg, , Ca, Sr, Ba or one or more elements selected from M) (where M is one selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb or There are those substituted with two or more elements.
- part or all of Si in the crystal is replaced with D element other than Si (where D is one or more elements selected from Si, Ge, Sn, Ti, Zr, and Hf). There is something.
- O or N in the crystal is substituted with N and / or fluorine, respectively, or O and / or fluorine. These substitutions are made so that the overall charge in the crystal is neutral. Those whose crystal structure does not change as a result of these element substitutions are Sr 3 Si 8 O 4 N 10 series 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 lattice constant of the Sr 3 Si 8 O 4 N 10- based crystal is changed by replacing its constituent components with other elements or by activating elements such as Eu being dissolved, but the crystal structure and atoms occupy it.
- the atomic position given by the site and its coordinates does not change so much that the chemical bond between the skeletal atoms is broken.
- the length of chemical bonds of Al—N and Si—N calculated from lattice constants and atomic coordinates obtained by Rietveld analysis of the results of X-ray diffraction and neutron diffraction in the P2 1 / n space group.
- FIG. 2 is a diagram showing powder X-ray diffraction using CuK ⁇ rays calculated from the crystal structure of Sr 3 Si 8 O 4 N 10 crystal.
- FIG. 2 By comparing FIG. 2 with a substance to be compared, it is possible to easily determine whether or not it is a Sr 3 Si 8 O 4 N 10- based crystal.
- the main peak of the Sr 3 Si 8 O 4 N 10- based crystal may be determined by about 10 having strong diffraction intensity.
- Table 1 is important in that sense and serves as a reference in specifying Sr 3 Si 8 O 4 N 10- based crystals.
- the approximate structure of the crystal structure of the Sr 3 Si 8 O 4 N 10 system crystal can be defined by using another crystal system of a monoclinic crystal. In that case, different space groups, lattice constants, and planes can be defined. Although it is expressed using an index, the X-ray diffraction result (for example, FIG.
- 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 Sr 3 Si 8 O 4 N 10- based crystal and the type and amount of the activation element, it may be selected according to the application.
- a phosphor having a particularly high luminance is a phosphor having a host crystal of Sr 3 Si 8 (O, N) 14 crystal in which A is Sr, D is Si, and X is a combination of N and O.
- An inorganic crystal having the same crystal structure as that shown by Sr 3 Si 8 O 4 N 10 is Sr 3 Si 8 O 4 N 10 , Ca 3 Si 8 O 4 N 10 , or (Sr, Li) 3 Si
- the phosphor of 8 O 4 N 10 has a stable crystal and high emission intensity.
- Inorganic crystals having the same crystal structure as the crystal represented by Sr 3 Si 8 O 4 N 10 are Sr 3 Si 8-x Al x N 10-x O 4 + x , Ca 3 Si 8-x Al x N 10-x O 4 + x , (Sr, Li) 3 Si 8-x Al x N 10-x O 4 + x , 0 ⁇ x ⁇ 8), a phosphor having a host crystal as a host crystal is a phosphor that has high emission intensity and can control the change in color tone by changing the composition.
- the activator element Eu As the activator element Eu, a phosphor with particularly high emission intensity can be obtained.
- inorganic crystals having the same crystal structure as the crystal represented by Sr 3 Si 8 O 4 N 10 crystals in which the inorganic crystals are monoclinic are particularly stable, and phosphors using these as host crystals have emission intensity. Is expensive.
- the crystals are particularly stable, and the phosphors using these as host crystals have high emission intensity. Outside this range, the crystal becomes unstable and the light emission intensity may decrease.
- the parameter d is the addition amount of the activator element. If it is less than 0.00001, the amount of the activator ion (luminescent ion) 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 the activated ions.
- the parameter e is a parameter representing the composition of the A element such as Sr, and if it is less than 0.05 or higher than 0.3, the crystal structure becomes unstable and the emission intensity decreases.
- the parameter f is a parameter representing the composition of a D element such as Si, and if it is less than 0.15 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 the E element such as Al, and if it is higher than 0.15, the crystal structure becomes unstable and the emission intensity decreases.
- the parameter h is a parameter representing the composition of the X element such as O, N, F, etc. If it is less than 0.45 or higher than 0.65, the crystal structure becomes unstable and the light 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.
- parameters f and g are 3/8 ⁇ f / (f + g) ⁇ 8/8
- 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.
- the M element is Eu
- a composition satisfying the above condition can be a phosphor emitting yellow to red light.
- a phosphor containing at least Eu as an M element as an activator is a phosphor having a high emission intensity in the present invention, and a yellow to red phosphor can be obtained with a specific composition.
- a composition containing at least Sr or Ca as the A element, containing at least Si as the D element, optionally containing at least Al as the E element, and containing at least O and N as the X element has a stable crystal structure and emits light. High strength. Note that 0.001% by mass to 1% by mass of boron may be further included as the E element. This stabilizes the crystal structure and increases the emission intensity.
- the composition formula of the above-described inorganic compound is Eu y Sr 3-y Si 8-x Al x N 10-x O 4 + x , Eu y Ca 3-y Si 8-x Al x N 10-x O 4 + x or Eu y (Sr, Li) 3-y Si 8-x Al x N 10-x O 4 + x
- the phosphor represented by the following formula is Eu / Sr ratio, Eu / Ca ratio, Eu / (Sr + Li) ratio, Si / Al ratio, N
- the / O ratio can be changed. Thereby, since the excitation wavelength and the emission wavelength can be continuously changed, the phosphor is easy to design a material.
- a phosphor that is a single crystal particle or an aggregate of single crystals having an average particle diameter of 0.1 ⁇ m or more and 20 ⁇ m or less has high luminous efficiency and good operability when mounted on an LED. It is better to control.
- 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 present invention is composed of a mixture of a phosphor having a Sr 3 Si 8 O 4 N 10 series crystal as a base crystal and another crystal phase or an amorphous phase, and Sr 3 Si 8 O 4 N 10.
- a phosphor whose content of the phosphor of the system crystal is 20% by mass or more.
- This embodiment may be used when the desired characteristics cannot be obtained with a single Sr 3 Si 8 O 4 N 10 crystal phosphor or when functions such as conductivity are added.
- the content of the Sr 3 Si 8 O 4 N 10- based crystal phosphor may be adjusted according to the intended characteristics, but if it is less than 20% by mass, the emission intensity may be lowered.
- the phosphor of the present invention preferably contains 20% by mass or more as the main component of the above-mentioned inorganic compound.
- the phosphor When the phosphor is required to have conductivity such as for electron beam excitation, it is preferable to add an inorganic substance having conductivity as another crystal phase or amorphous phase.
- 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.
- a second other phosphor may be added.
- Other phosphors include BAM phosphor, ⁇ -sialon phosphor, ⁇ -sialon phosphor, (Sr, Ba) 2 Si 5 N 8 phosphor, CaAlSiN 3 phosphor, (Ca, Sr) AlSiN 3 phosphor Etc.
- a phosphor having a peak in a wavelength range of 560 nm to 650 nm by irradiating an excitation source there is a phosphor having a peak in a wavelength range of 560 nm to 650 nm by irradiating an excitation source.
- a phosphor of Sr 3 Si 8 O 4 N 10- based crystal activated with Eu has a light emission peak in this range by adjusting the composition.
- a phosphor that emits light with vacuum ultraviolet light, ultraviolet light, visible light, electron beam, or X-ray having an excitation source with a wavelength of 100 nm to 450 nm. By using these excitation sources, light can be emitted efficiently.
- Eu is dissolved in an inorganic crystal having the same crystal structure as the crystal represented by Sr 3 Si 8 O 4 N 10 and the crystal represented by Sr 3 Si 8 O 4 N 10 .
- the composition when the light of 360 nm to 450 nm is irradiated, the yellow to red fluorescence of 560 nm to 650 nm is emitted. Therefore, it is preferably used for yellow to red light emission such as a white LED.
- the color emitted when the excitation source is irradiated is a value of (x0, y0) on the CIE1931 chromaticity coordinates, 0.1 ⁇ x0 ⁇ 0.7 0.2 ⁇ y0 ⁇ 0.9
- phosphors for example, Eu y Sr 3-y Si 8-x Al x N 10-x O 4 + x
- a phosphor that develops a color having a chromaticity coordinate in this range can be obtained. It may be used for yellow to red light emission such as white LED.
- the phosphor of the present invention has a broad excitation range of electron beam, X-ray, and ultraviolet to visible light, and emits light from blue to red, compared with normal oxide phosphors and existing sialon phosphors.
- the specific composition is characterized in that it exhibits a yellow to red color of 560 nm to 650 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.
- the phosphor is a mixture of metal compounds, and is fired to convert the Sr 3 Si 8 O 4 N 10 series crystal into a base crystal.
- the main crystal of the present invention is monoclinic and belongs to the space group P2 1 / n, there may be a case where a crystal having a different crystal system or space group is mixed depending on the synthesis conditions such as the firing temperature. Even in this case, since the change in the light emission characteristics is slight, it can be used as a high-luminance phosphor.
- a mixture of metal compounds is a compound containing M, a compound containing A, a compound containing D, a compound containing X, and a compound containing E as necessary.
- M is one or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, and Yb
- A is selected from Li, Mg, Ca, Sr, and Ba.
- D is one or more elements selected from Si, Ge, Sn, Ti, Zr, and Hf
- E is B, Al, Ga, In, Sc, Y,
- X may be one or more elements selected from O, N, and 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 preferably a simple substance or a mixture of two or more selected from oxides, nitrides, oxynitrides, fluorides, and oxyfluorides, since the raw materials are easily available and excellent in stability.
- the compound containing E is a simple substance or a mixture of two or more selected from metals containing E, silicides, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, or oxyfluorides. Can be used.
- 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.
- 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. Unless otherwise specified, in the present invention, the relative bulk density is simply referred to as bulk density.
- 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 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 of the phosphor powder is preferably from 50 nm to 200 ⁇ m in terms of volume-based median diameter (d50) because the emission intensity is high.
- 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, which acts as a flux and promotes reaction and grain growth to obtain stable crystals. This 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 may be increased by washing with a solvent after firing to reduce 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 a light emitting body or a light emitting light source and the phosphor of the present invention.
- Examples of light emitters or light sources include LED light emitting devices, laser diode (LD) light emitting devices, organic EL (OLED) light emitting devices, fluorescent lamps, and semiconductor lasers.
- 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 the white light emitting diodes, and 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 light emitting body or light emitting light source emits ultraviolet or visible light having a peak wavelength of 300 to 450 nm
- the phosphor of the present invention emits blue to red light
- the other phosphor of the present invention includes
- a light-emitting device that emits white light or light other than white light by mixing light having a wavelength of 450 nm or more.
- a blue phosphor that emits light having a peak wavelength of 420 nm to 500 nm or less by a 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.
- 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 320 to 450 nm is used as a light emitter or a light-emitting light source, the light-emitting efficiency is high, so that a highly efficient light-emitting device can be configured.
- the image display device of the present invention is composed of at least an excitation source and the phosphor of the present invention, and is a fluorescent display tube (VFD), a field emission display (FED), a plasma display panel (PDP), a cathode ray tube (CRT), a liquid crystal.
- a display There is a display (LCD).
- 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 mainly composed of an inorganic compound crystal phase having a specific chemical composition can be used as a pigment or a fluorescent pigment because it has a yellow or orange object color. That is, when the phosphor of the present invention is irradiated with illumination such as sunlight or a fluorescent lamp, a yellow or orange object color is observed, but since the color development is good and it does not deteriorate for a long time, The phosphor is suitable for an inorganic pigment. 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 nitride 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.).
- 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% by volume at 800 ° C. Nitrogen was introduced to bring the pressure in the furnace to 1 MPa, and the temperature was raised to 1700 ° C. at 500 ° C. per hour and held at that temperature for 2 hours.
- the synthesized product was observed with an optical microscope, and crystal particles having a size of 9.8 ⁇ m ⁇ 34 ⁇ m ⁇ 2.8 ⁇ m were collected from the synthesized product.
- the particles were analyzed 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). Analysis was carried out. As a result, the presence of Sr, Si, O, and N elements was confirmed, and the ratio of the number of atoms contained in Sr and Si was measured to be 3: 8.
- 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).
- the obtained crystal structure data is shown in Table 1, and a diagram of the crystal structure is shown in FIG. Table 1 describes the crystal system, space group, lattice constant, atom type and atom position, and this data can be used to determine the shape and size of the unit cell and the arrangement of atoms in it. .
- Si and Al enter at the same atomic position, and oxygen and nitrogen enter at the same atomic position, and when they are averaged as a whole, the composition ratio of the crystal is obtained.
- the atomic positions are as shown in Table 1.
- O and N are present at a certain ratio determined by the composition at the same atomic position.
- oxygen and nitrogen can enter the seat where X enters.
- the Sr 3 Si 8 O 4 N 10 crystal can substitute a part or all of Sr with Li, Ca or Ba while maintaining the crystal structure. That is, the crystal of A 3 Si 8 O 4 N 10 (A is one or two or a mixture selected from Sr, Li, Ca, or Ba) has the same crystal structure as the Sr 3 Si 8 O 4 N 10 crystal. . Further, a part of Si can be replaced with Al, a part of Al can be replaced with Si, and a part of N can be replaced with oxygen. This crystal has the same crystal structure as Sr 3 Si 8 O 4 N 10 It was confirmed to be one composition of inorganic crystals.
- the raw materials were weighed so as to have the raw material mixture composition (mass ratio) shown in Table 4.
- the composition may differ between the design composition in Tables 2 and 3 and the mixed composition in Table 4.
- the mixed composition was determined so that the amount of metal ions matched.
- the weighed raw material powders were mixed for 5 minutes using a silicon nitride sintered pestle and mortar. Thereafter, the mixed powder was put into a crucible made of a boron nitride sintered body. The bulk density of the powder was about 20% to 30%.
- 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% by volume at 800 ° C. Nitrogen was introduced to bring the pressure in the furnace to 1 MPa, the temperature was raised to 500 ° C. per hour to the set temperature shown in Table 5, and the temperature was maintained for 2 hours.
- the synthesized compound was pulverized using an agate mortar, and powder X-ray diffraction measurement using Cu K ⁇ rays was performed.
- the results are shown in FIG. 3 and the main production phases are shown in Table 6. Furthermore, it was confirmed by EDS measurement that the composite contains a rare earth element, an alkaline earth metal, Si, Al, O, and N. ICP mass spectrometer measurement confirmed that the compound contained Li (Examples 15 and 16).
- FIG. 3 is a graph showing the result of powder X-ray diffraction of the synthesized product in Example 22.
- the XRD pattern in FIG. 3 is in good agreement with the X-ray diffraction pattern of the Sr 3 Si 8 O 4 N 10 crystal by the structural analysis shown in FIG. 2, and has the same crystal structure as the Sr 3 Si 8 O 4 N 10 crystal. It was confirmed that the crystal was the main component. Further, the composite of Example 22 contains Eu, Sr, Si, O, and N by EDS measurement, and the ratio of Eu: Sr: Si is 0.1: 2.9: 8. confirmed. From the above, it was confirmed that the composite of Example 22 was an inorganic compound in which Eu was dissolved in Sr 3 Si 8 O 4 N 10 crystals. Although not shown, similar results were obtained in other examples.
- the phase having the same crystal structure as that of the Sr 3 Si 8 O 4 N 10 crystal contains 20% by mass or more as a main product phase. confirmed.
- the difference between the mixed raw material composition and the chemical composition of the synthesized product suggests that a minute amount of the impurity second phase is mixed in the synthesized product.
- the main phase and subphase were quantitatively determined by Rietveld analysis.
- the composite of the example of the present invention was an inorganic compound in which an activating ion M such as Eu or Ce was dissolved in a Sr 3 Si 8 O 4 N 10- based crystal.
- the obtained fired body was coarsely pulverized, and then manually pulverized using a silicon nitride sintered crucible and a mortar, and passed through a 30 ⁇ m sieve. When the particle size distribution was measured, the average particle size was 3 to 8 ⁇ m.
- FIG. 4 is a diagram showing an excitation spectrum and an emission spectrum of the synthesized product synthesized in Example 17.
- FIG. 5 is a diagram showing an excitation spectrum and an emission spectrum of the synthesized product in Example 22.
- FIG. 4 shows that the synthesized product of Example 17 can be excited most efficiently at 439 nm, and the emission spectrum when excited at 439 nm has a peak at 618 nm and emits red light.
- FIG. 5 shows that the synthesized product of Example 22 can be excited most efficiently at 372 nm, and the emission spectrum when excited at 372 nm has a peak at 580 nm and emits yellow light.
- the composite of the present invention is a phosphor capable of being excited by ultraviolet rays of 300 nm to 380 nm, violet or blue light of 380 nm to 450 nm, and emitting blue to red light. .
- the composite of the example of the present invention is an inorganic compound in which an activating ion M such as Eu or Ce is dissolved in a Sr 3 Si 8 O 4 N 10- based crystal, and this inorganic compound is a phosphor.
- an activating ion M such as Eu or Ce
- this inorganic compound is a phosphor.
- Table 3 and Table 7 it can be seen that a phosphor emitting yellow to red light having a peak at a wavelength in the range of 560 nm to 650 nm can be obtained by controlling to a specific composition.
- FIG. 6 is a diagram showing the object color of the composite synthesized in Example 17.
- Example 17 When the composite of Example 17 was observed, an orange object color was observed. It was confirmed that other examples also showed yellow to orange object colors.
- the inorganic compound that is the composite of the present invention exhibits a yellow or orange object color when illuminated by sunlight or illumination such as a fluorescent lamp, and thus has been found to be applicable to pigments or fluorescent pigments.
- 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.
- the phosphor powder prepared by mixing the yellow phosphor prepared in Example 22 and the JEM: Ce blue phosphor at a mass ratio of 7: 3 was mixed with an epoxy resin at a concentration of 37% by weight, and this was added to a dispenser.
- the first resin (6) in which the appropriate amount (7) mixed with the phosphor was dispersed was formed by dropping an appropriate amount.
- 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 positioned 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.
- a mixture of the first resin (16), the phosphor prepared in Example 22 and the phosphor (17) in which the CaAlSiN 3 : Eu red phosphor is mixed at a mass ratio of 9: 1 is 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. Further, at least 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, and the like are substantially the same as in Example 23.
- FIG. 9 is a schematic view showing an image display device (plasma display panel) according to the present invention.
- the red phosphor (CaAlSiN 3 : Eu) (31), the green phosphor (32) and the blue phosphor (BAM: Eu 2+ ) (33) of Example 13 of the present invention were placed on the glass substrate (44) on the electrode ( 37, 38, 39) and the inner surface of each cell (34, 35, 36) disposed via the dielectric layer (41).
- the electrodes (37, 38, 39, 40) are energized, vacuum ultraviolet rays are generated by Xe discharge in the cell, which excites the phosphor and emits red, green, and blue visible light, which is the protective layer. (43), observed from the outside through the dielectric layer (42) and the glass substrate (45), 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 red phosphor (56) of Example 20 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 red phosphor (56), and the phosphor emits light.
- the whole is protected by glass (51).
- the figure shows one light-emitting cell consisting of one emitter and one phosphor.
- a display that can produce a variety of colors is constructed by arranging a number of green and blue cells in addition to red. The Although it does not specify in particular about the fluorescent substance used for a green or blue cell, what emits high brightness
- the nitride phosphor of the present invention has emission characteristics (emission color, excitation characteristics, emission spectrum) different from those of conventional phosphors, and has high emission intensity even when combined with an LED of 470 nm or less. It is a nitride phosphor that is suitably used for VFD, FED, PDP, CRT, white LED, etc. because it is thermally 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.
Abstract
Description
前記A3(D,E)8X14で示される結晶は、少なくともA元素にSrまたはCaを含み、D元素にSiを含み、必要に応じてE元素にAlを含み、X元素にNを含み、必要に応じてX元素にOを含む、蛍光体(「蛍光体(2)」という)でもよい。
格子定数a、b、cが、
a = 0.48170±0.05 nm
b = 2.42320±0.05 nm
c = 1.05600±0.05 nm
の範囲の値である、蛍光体(「蛍光体(7)」という)であってもよい。ここで、「±0.05」は、許容範囲を示し、aについていえば、例えば、 0.48170-0.05 ≦ a ≦ 0.48170+0.05という範囲を意味することができる(以下同様)。
0.00001 ≦ d ≦ 0.05
0.05 ≦ e ≦ 0.3
0.15 ≦ f ≦ 0.4
0 ≦ g ≦ 0.15
0.45 ≦ h ≦ 0.65
の条件を全て満たす範囲の組成で表される、蛍光体(「蛍光体(8)」という)であってもよい。
d+e = (3/25)±0.05
f+g = (8/25)±0.05
h = (14/25)±0.05
の条件を全て満たす範囲の値である、蛍光体(「蛍光体(9)」という)であってもよい。ここで、「±0.05」は、許容範囲を示し、d+eについていえば、例えば、(3/25)-0.05 ≦ d+e ≦ (3/25)+0.05という範囲を意味することができる(以下同様)。
3/8 ≦ f/(f+g) ≦ 8/8
の条件を満たす、蛍光体(「蛍光体(10)」という)であってもよい。
0/14 ≦ h1/(h1+h2) ≦ 8/14
の条件を満たす、蛍光体(「蛍光体(11)」という)であってもよい。
EuySr3-ySi8-xAlxN10-xO4+x、EuyCa3-ySi8-xAlxN10-xO4+x、または、Euy(Li,Sr)3-ySi8-xAlxN10-xO4+x
ただし、
0 ≦ x < 8
0.0001 ≦ y ≦ 2
で示される、蛍光体(「蛍光体(14)」という)であってもよい。
0.1 ≦ x0 ≦ 0.7
0.2 ≦ y0 ≦ 0.9
の条件を満たす、蛍光体(「蛍光体(24)」という)であってもよい。尚、通常、CIE1931色度座標上の値は、(x,y)で示されるが、組成式に用いるx及びyとの混同を避けるために、xをx0と、yをy0としている(以下、同様)。
Sr3Si8-xAlxN10-xO4+x、Ca3Si8-xAlxN10-xO4+x、(Sr,Li)3Si8-xAlxN10-xO4+x(ただし、0 ≦ x < 8)の組成式で示される結晶を母体結晶(ホスト)とする蛍光体は、発光強度が高く、組成を変えることにより色調の変化が制御できる蛍光体である。
a = 0.48170±0.05 nm
b = 2.42320±0.05 nm
c = 1.05600±0.05 nm
の範囲のものは結晶が特に安定であり、これらを母体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。
0.00001 ≦ d ≦ 0.05
0.05 ≦ e ≦ 0.3
0.15 ≦ f ≦ 0.4
0 ≦ g ≦ 0.15
0.45 ≦ 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 = (3/25)±0.05
f+g = (8/25)±0.05
h = (14/25)±0.05
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 = 3/25
f+g = 8/25
h = 14/25
の条件を全て満たす値の結晶、すなわち、(M,A)3(D,E)8X14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。
3/8 ≦ f/(f+g) ≦ 8/8
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。
0/14 ≦ h1/(h1+h2) ≦ 8/14
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。
0.00001 ≦ d ≦ 0.05
0.1 ≦ e ≦ 0.2
0.25 ≦ f ≦ 0.35
g = 0
0.5 ≦ h ≦ 0.6
の条件を満たす組成は、黄色から赤色発光する蛍光体となり得る。
EuySr3-ySi8-xAlxN10-xO4+x、EuyCa3-ySi8-xAlxN10-xO4+x、または、Euy(Sr,Li)3-ySi8-xAlxN10-xO4+x
ただし、
0 ≦ x < 8
0.0001 ≦ y ≦ 2
で示される蛍光体は、安定な結晶構造を保ったままxとyのパラメータを変えることによる組成範囲でEu/Sr比、Eu/Ca比、Eu/(Sr+Li)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。
0.1 ≦ x0 ≦ 0.7
0.2 ≦ y0 ≦ 0.9
範囲の蛍光体がある。例えば、
EuySr3-ySi8-xAlxN10-xO4+x
ただし、
0 ≦ x < 8
0.0001 ≦ y ≦ 2
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等の黄色から赤色発光の用途に用いると良い。
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、二酸化ケイ素粉末(SiO2;高純度化学研究所製)と、比表面積13.2m2/gの粒度の酸化アルミニウム粉末(大明化学工業製タイミクロン)と、炭酸リチウム(高純度化学製)と、窒化ホウ素(電気化学工業製)と、酸化カルシウム(高純度化学製)と、純度99.5%の窒化ストロンチウム(Sr3N2;セラック製)と、酸化ストロンチウム(高純度化学製)と、酸化セリウム(CeO2;純度99.9%、信越化学工業(株)製)と、酸化ユーロピウム(Eu2O3;純度99.9%信越化学工業(株)製)と、希土類酸化物(純度99.9%信越化学工業製)とであった。
窒化ケイ素(Si3N4)、二酸化ケイ素(SiO2)、および、酸化ストロンチウム(SrO)をモル比で2.33:1:3の割合で混合組成を設計した。これらの原料粉末を、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。
Sr3Si8-xAlxN10-xO4+x、Ca3Si8-xAlxN10-xO4+x、(Sr,Li)3Si8-xAlxN10-xO4+x、Ba3Si8-xAlxN10-xO4+x、(Sr,Ba)3Si8-xAlxN10-xO4+x(ただし、0 ≦ x < 8)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の原料混合組成(質量比)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。秤量した原料粉末を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。その後、混合粉末を窒化ホウ素焼結体製のるつぼに投入した。粉体の嵩密度は約20%から30%であった。
図5は、実施例22で合成した合成物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、35、36.紫外線発光セル。
37、38、39、40.電極。
41、42.誘電体層。
43.保護層。
44、45.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 (57)
- 少なくともA元素とD元素とX元素(ただし、Aは、Li、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、Sr3Si8O4N10で示される結晶、あるいは、Sr3Si8O4N10で示される結晶と同一の結晶構造を有する無機結晶に、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)が固溶した無機化合物を含む、蛍光体。
- 前記Sr3Si8O4N10で示される結晶と同一の結晶構造を有する無機結晶は、その組成がA3(D,E)8X14で示される結晶であり、
前記A3(D,E)8X14で示される結晶は、少なくともA元素にSrまたはCaを含み、D元素にSiを含み、必要に応じてE元素にAlを含み、X元素にNを含み、必要に応じてX元素にOを含む、請求項1に記載の蛍光体。 - 前記Sr3Si8O4N10で示される結晶と同一の結晶構造を有する無機結晶が、Sr3Si8O4N10、Ca3Si8O4N10、または、(Sr,Li)3Si8O4N10である、請求項1に記載の蛍光体。
- 前記Sr3Si8O4N10で示される結晶と同一の結晶構造を有する無機結晶が、
Sr3Si8-xAlxN10-xO4+x、Ca3Si8-xAlxN10-xO4+x、または、(Sr,Li)3Si8-xAlxN10-xO4+x(ただし、0 ≦ x < 8)の組成式で示される、請求項1に記載の蛍光体。 - 前記M元素がEuである、請求項1に記載の蛍光体。
- 前記Sr3Si8O4N10で示される結晶と同一の結晶構造を有する無機結晶が、単斜晶系の結晶である、請求項1に記載の蛍光体。
- 前記Sr3Si8O4N10で示される結晶と同一の結晶構造を有する無機結晶が、単斜晶系の結晶であり、空間群P21/nの対称性を持ち、
格子定数a、b、cが、
a = 0.48170±0.05 nm
b = 2.42320±0.05 nm
c = 1.05600±0.05 nm
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MdAeDfEgXh(ただし、式中d+e+f+g+h = 1であり、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、Li、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d、e、f、g、hが、
0.00001 ≦ d ≦ 0.05
0.05 ≦ e ≦ 0.3
0.15 ≦ f ≦ 0.4
0 ≦ g ≦ 0.15
0.45 ≦ 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 = (3/25)±0.05
f+g = (8/25)±0.05
h = (14/25)±0.05
の条件を全て満たす範囲の値である、請求項8に記載の蛍光体。 - 前記パラメータf、gが、
3/8 ≦ f/(f+g) ≦ 8/8
の条件を満たす、請求項8に記載の蛍光体。 - 前記X元素がNとOとを含み、組成式MdAeDfEgOh1Nh2(ただし、式中d+e+f+g+h1+h2 = 1、および、h1+h2 = hである)で示され、
0/14 ≦ h1/(h1+h2) ≦ 8/14
の条件を満たす、請求項8に記載の蛍光体。 - 前記M元素として少なくともEuを含む、請求項8に記載の蛍光体。
- 前記A元素として少なくともSrまたはCaを含み、前記D元素として少なくともSiを含み、必要に応じて前記E元素として少なくともAlを含み、前記X元素として少なくともOとNを含む、請求項8に記載の蛍光体。
- 前記無機化合物の組成式がパラメータxとyを用いて
EuySr3-ySi8-xAlxN10-xO4+x、EuyCa3-ySi8-xAlxN10-xO4+x、または、Euy(Li,Sr)3-ySi8-xAlxN10-xO4+x
ただし、
0 ≦ x < 8
0.0001 ≦ y ≦ 2
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20μm以下の単結晶粒子あるいは単結晶の集合体である、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。
- 前記無機化合物に加えて、前記無機化合物とは異なる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17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18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無機蛍光体である、請求項17に記載の蛍光体。
- 励起源を照射することにより560nm以上650nm以下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450nm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21に記載の蛍光体。
- 前記Sr3Si8O4N10で示される結晶および前記Sr3Si8O4N10で示される結晶と同一の結晶構造を有する無機結晶にEuが固溶してなり、360nmから450nmの光を照射すると560nm以上650nm以下の黄色から赤色の蛍光を発する、請求項1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(x0,y0)の値で、
0.1 ≦ x0 ≦ 0.7
0.2 ≦ y0 ≦ 0.9
の条件を満たす、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に記載の無機化合物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、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、Xを含有する化合物と、必要に応じてE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、Li、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25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26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を含有する、請求項25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25に記載の蛍光体の製造方法。
- 焼成炉の発熱体、断熱体、または試料容器に黒鉛を使用する、請求項25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25に記載の蛍光体の製造方法。
- 焼成に使う容器が窒化ホウ素製である、請求項25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25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25に記載の蛍光体の製造方法。
- 焼結手段がホットプレスによることなく、専ら常圧焼結法もしくはガス圧焼結法による手段である、請求項25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25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25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する、請求項25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38に記載の蛍光体の製造方法。
- 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38に記載の蛍光体の製造方法。
- 少なくとも発光体と蛍光体(第1の蛍光体)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に記載の蛍光体を前記蛍光体(第1の蛍光体)として用いる、発光装置。
- 前記発光体が、330~500nm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41に記載の発光装置。
- 前記発光装置が、白色発光ダイオード、白色発光ダイオードを複数含む照明器具、または、液晶パネル用バックライトである、請求項41に記載の発光装置。
- 前記発光体がピーク波長300~450nmの紫外または可視光を発し、
請求項1に記載の蛍光体が発する青色から赤色光と、他の蛍光体が発する450nm以上の波長の光とを混合することにより白色光または白色光以外の光を発する、請求項41に記載の発光装置。 - 前記発光体によりピーク波長420nm~500nm以下の光を発する青色蛍光体をさらに含む、請求項41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45に記載の発光装置。
- 前記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41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から選ばれる、請求項47に記載の発光装置。
- 前記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41に記載の発光装置。
- 前記黄色蛍光体が、YAG:Ce、α-サイアロン:Eu、CaAlSiN3:Ce、La3Si6N11:Ceから選ばれる、請求項49に記載の発光装置。
- 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41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51に記載の発光装置。
- 前記発光体が320~450nmの波長の光を発するLEDである、請求項41に記載の発光装置。
- 励起源と蛍光体(第1の蛍光体)と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に記載の蛍光体を前記蛍光体(第1の蛍光体)として用いる、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54に記載の画像表示装置。
- 請求項1に記載の無機化合物からなる顔料。
- 請求項1に記載の無機化合物からなる紫外線吸収剤。
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EP13797674.2A EP2801599B1 (en) | 2012-05-31 | 2013-05-30 | Phosphor, method for manufacturing same, light emitting device, and image display device |
JP2014518722A JP5713305B2 (ja) | 2012-05-31 | 2013-05-30 | 蛍光体、その製造方法、発光装置および画像表示装置 |
KR1020147032307A KR101662925B1 (ko) | 2012-05-31 | 2013-05-30 | 형광체, 그 제조 방법, 발광 장치 및 화상 표시 장치 |
US14/368,927 US9458379B2 (en) | 2012-05-31 | 2013-05-30 | Phosphor, method for manufacturing same, light emitting device, and image display device |
CN201380004652.6A CN104024375B (zh) | 2012-05-31 | 2013-05-30 | 荧光体及其制备方法、发光装置及图像显示装置 |
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JPWO2013180216A1 (ja) | 2016-01-21 |
JP5713305B2 (ja) | 2015-05-07 |
EP2801599B1 (en) | 2016-01-13 |
TWI476268B (zh) | 2015-03-11 |
US20150070875A1 (en) | 2015-03-12 |
EP2801599A1 (en) | 2014-11-12 |
EP2801599A4 (en) | 2015-03-18 |
CN104024375A (zh) | 2014-09-03 |
TW201402783A (zh) | 2014-01-16 |
KR20150005978A (ko) | 2015-01-15 |
US9458379B2 (en) | 2016-10-04 |
CN104024375B (zh) | 2017-05-24 |
KR101662925B1 (ko) | 2016-10-05 |
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