JP4168776B2 - Light emitting device and lighting device using the same - Google Patents

Light emitting device and lighting device using the same Download PDF

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JP4168776B2
JP4168776B2 JP2003036722A JP2003036722A JP4168776B2 JP 4168776 B2 JP4168776 B2 JP 4168776B2 JP 2003036722 A JP2003036722 A JP 2003036722A JP 2003036722 A JP2003036722 A JP 2003036722A JP 4168776 B2 JP4168776 B2 JP 4168776B2
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light
emitting device
phosphor
light emitting
device according
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JP2003306675A (en
JP2003306675A5 (en
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直人 木島
孝俊 瀬戸
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三菱化学株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805Shape
    • H01L2224/4809Loop shape
    • H01L2224/48091Arched
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481Disposition
    • H01L2224/48151Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181Encapsulation

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a light-emitting device, and more specifically, a first light emitter that emits light from ultraviolet light to visible light region by a power source, and absorbs light in the visible light region from the ultraviolet light to generate long-wavelength visible light. Wavelength conversion material having a phosphor in which the base compound that emits contains a luminescent center ionWhenThe present invention relates to a light-emitting device that can generate high-intensity light emission with good color rendering regardless of the use environment by combining with the second light-emitting body.
[0002]
[Prior art]
In order to generate white and other various colors uniformly and with good color rendering by mixing blue, red, and green, a light emitting device in which the light emission color of an LED or LD is converted with a phosphor has been proposed. For example, in Japanese Patent Publication No. 49-1221, a laser beam that emits a radiation beam having a wavelength of 300 to 530 nm is used as a phosphor (Y3-xyCexGdyMFive- zGazO12(Y represents Y, Lu, or La, M represents Al, Al—In, or Al—Sc)), and this is emitted to form a display. Further, in recent years, a white light emitting device configured by combining a gallium nitride (GaN) LED or LD with high luminous efficiency, which has been attracting attention as a blue light emitting semiconductor light emitting element, and a phosphor as a wavelength conversion material. However, it has been proposed as a light-emitting source for an image display device and a lighting device, taking advantage of the feature of low power consumption and long life. Actually, Japanese Patent Application Laid-Open No. 10-242513 discloses a light emitting device using this nitride semiconductor LED or LD chip and using yttrium, aluminum, garnet as a phosphor. .
[0003]
However, so far, a known light emission in which an yttrium-aluminum-garnet phosphor as disclosed in Japanese Patent Laid-Open No. 10-242513 is combined as a second light emitter with respect to a first light emitter such as an LED. The apparatus cannot be said to have sufficient light emission intensity, and further improvements have been demanded as light sources such as displays, backlight light sources, and traffic lights.
[0004]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described prior art to develop a light emitting device with extremely high light emission intensity. Accordingly, the present invention is a double light emitter type that is easy to manufacture and has extremely high light emission intensity. An object is to provide a light emitting device.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the inventor of the present invention has a first light emitter that emits light of 350 to 415 nm and a second light that generates visible light by irradiation of light from the first light emitter. When using a phosphor containing a crystal phase having the following specific chemical composition as the second phosphor, the phosphor is irradiated with light in the vicinity of 350-415 nm, The inventors have found that the object can be achieved as a result of causing visible light emission with high intensity, and have reached the present invention. That is, the present invention relates to a light emitting device having a first light emitter that generates light of 350 to 415 nm and a second light emitter that generates visible light by irradiation of light from the first light emitter. The gist of the light emitting device is characterized in that the second light emitter contains a phosphor having a crystal phase having a chemical composition represented by the general formula [1].
[0006]
[Chemical 2]
M1 aEubM2 cMThree dOe・ ・ ・ ・ ・ ・ [1]
(However, M1Represents a metal element containing a total of 90 mol% or more of at least one element selected from the group consisting of Ba, Sr, and Ca;2Represents a metal element containing at least 90 mol% in total of at least one element selected from the group consisting of Mg and Zn,ThreeRepresents a metal element containing 90 mol% or more in total of at least one element selected from the group consisting of Si and Ge, a is a number satisfying 2.5 ≦ a ≦ 3.3, and b is 0.0001 ≦ b ≦ 1.0, c is 0.9 ≦ c ≦ 1.1, d is 1.8 ≦ d ≦ 2.2, e is 7.2 ≦ e ≦ 8 Is a number satisfying .8. )
BaThreeMgSi2O8, SrThreeMgSi2O8The crystal phases themselves are known, and Ba and Sr of these are Eu.2+It is also known that other divalent metal elements can be substituted. The present invention is based on Ba3-xEUXMgSi2O8And Sr3-XEUXMgSi2O8When the phosphor having a crystal phase having the chemical composition of the general formula [1] including the chemical composition of the above is irradiated with 350 to 415 nm light from the first light emitter, it is more remarkable than the other phosphors. It is based on the fact that it generates high intensity light. The phosphor is a general blue light emitting BaMgAl.TenO17: Eu or yellow light emitting YThreeAlFiveO12: Light with an intensity much higher than Ce was generated.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a light-emitting device in which a first light-emitting body that emits light of 350 to 415 nm and a second light-emitting body that is a phosphor are combined, and the second light-emitting body is represented by the following general formula [1]. It contains a phosphor having a crystal phase having a chemical composition.
[0008]
[Chemical 3]
M1 aEubM2 cMThree dOe・ ・ ・ ・ ・ ・ [1]
Where M1Represents a metal element containing at least 90 mol% or more, preferably 95 mol% or more in total of at least one element selected from the group consisting of Ba, Sr and Ca. Above all, M1It is preferable that all the elements corresponding to are at least one selected from the group consisting of Ba, Sr and Ca. As a result, a larger emission intensity can be obtained. M1As for it, it is preferable to contain Ba and / or Sr, and it is especially preferable to contain Ba. When Ba is contained, the molar ratio of Ba to Sr is preferably 0.05 or more from the viewpoint of easy adjustment of emission wavelength, emission intensity, and the like. In this case, the amount of Sr may be 0 (in this case, the molar ratio is infinite), but preferably also contains Sr, and the molar ratio is usually 100 or less.
[0009]
In the general formula [1], M2Represents a metal element containing at least 90 mol% or more, preferably 95 mol% or more in total of at least one element selected from the group consisting of Mg and Zn. Above all, M2It is preferable that all the elements corresponding to are at least one selected from the group consisting of Mg and Zn. As a result, a larger emission intensity can be obtained. M2It is particularly preferable to contain Mg.
[0010]
In the general formula [1], MThreeRepresents a metal element containing at least 90 mol% or more, preferably 95 mol% or more in total of at least one element selected from the group consisting of Si and Ge. Above all, MThreeIt is preferable that all the elements corresponding to are at least one selected from the group consisting of Si and Ge. As a result, a larger emission intensity can be obtained. MThreeIt is particularly preferable to contain Si.
[0011]
M1, M2, MThreeA metal element other than the above can be contained in the crystal with the upper limit of 10 mol%, preferably 5 mol% as the upper limit, more preferably 3 mol% as the upper limit. In this case, there is no particular limitation on the metal element, but it is preferable that the same valence as that of Ba, Mg, and Si, that is, a bivalent, divalent, and tetravalent metal element is contained in order because the crystal structure is easily retained. . Divalent and tetravalent metallic elements and Eu as the emission center2+A small amount of a metal element such as monovalent, trivalent, pentavalent, or hexavalent may be introduced in the meaning of assisting crystallization of the composite oxide by diffusion in the solid during firing. For example, BaThreeMgSi2O8: Ba in Eu phosphor2+Or Mg2+A part of equimolar Li+And Ga2+Thus, the replacement can be performed while maintaining the charge compensation effect.
[0012]
In the general formula [1], a, b, c, d, and e are M in order.1Molar ratio of metal elements corresponding to the above, the molar ratio of europium atoms, M2Molar ratio of metal elements corresponding toThreeRepresents the molar ratio of the metal element corresponding to the above and the molar ratio of the oxygen atom. The values of a + b, c, d, and e are generally 3, 1, 2, and 8 in order, but even if some cation deficiency or some oxygen deficiency occurs, the fluorescence performance is not greatly affected. For reasons, it has a tolerance that encompasses the above values.
[0013]
a is a number satisfying 2.5 ≦ a ≦ 3.3, preferably 2.7 or more, more preferably 2.8 or more, further preferably 2.9 or more, and preferably 3 .2 or less, more preferably 3.1 or less. b is a number satisfying 0.0001 ≦ b ≦ 1.0, preferably 0.001 or more, more preferably 0.003 or more, and preferably 0.5 or less, more preferably 0. .3 or less, more preferably 0.15 or less, and particularly preferably 0.1 or less. When the content of the luminescent center ion is less than the above range, the luminescence intensity tends to decrease. On the other hand, when the content exceeds the above range, the luminescence intensity also tends to decrease due to a phenomenon called concentration quenching. Moreover, it is preferable that 2.7 ≦ a + b ≦ 3.3 is satisfied in that a crystal phase with few crystal defects is obtained and emission intensity is increased. c is a number satisfying 0.9 ≦ c ≦ 1.1, preferably 0.93 or more, more preferably 0.95 or more, and preferably 1.07 or less, more preferably 1 .05 or less. d is a number satisfying 1.8 ≦ d ≦ 2.2, preferably 1.85 or more, more preferably 1.9 or more, preferably 2.15 or less, more preferably 2 .1 or less. e is a number satisfying 7.2 ≦ e ≦ 8.8, preferably 7.4 or more, more preferably 7.6 or more, most preferably 7.8 or more, and preferably 8 .6 or less, more preferably 8.4 or less, and most preferably 8.2 or less.
[0014]
The typical crystal structure of the phosphor used in the present invention is Ba.ThreeMgSi2O8Structure, SrThreeMgSi2O8Structure or CaThreeMgSi2O8It is a structure. CaThreeMgSi2O8The structure is usually called merwinite structure. BaThreeMgSi2O8Structure and SrThreeMgSi2O8Strictly speaking, the structure is not a merwinite structure, but a similar structure. BaThreeMgSi2O8Structure and SrThreeMgSi2O8The structure is orthorhombic, and their lattice constants are usually a = 5.5Å, b = 9.8Å, c = 7.6 及 び, and a = 5.4Å, b = 9.6Å, c = 7.2, respectively. It is about cocoon. CaThreeMgSi2O8The structure is monoclinic, space group P21 / a, and the lattice constants are usually about a = 13.254Å, b = 5.293Å, and c = 9.328Å. 1, 2 and 3, respectively, BaThreeMgSi2O8, SrThreeMgSi2O8, And CaThreeMgSi2O8X-ray diffraction pattern is shown (from powder X-ray diffraction database). In these crystal structures, Ba, Sr, Ca, and other divalent metals have a wide composition range in which they are in solid solution with each other, and thus are considered to be close in structure. The crystal phase of the phosphor used in the present invention is usually Ba.ThreeMgSi2O8Structure, SrThreeMgSi2O8Structure or CaThreeMgSi2O8Eu as an activator for structural materials2+Corresponds to the replacement.
[0015]
The phosphor used in the present invention is excited by light of 350 to 415 nm from the first light emitter, and generates visible light. The phosphor generates visible light having a very strong emission intensity by excitation of light of 350 to 415 nm.
The phosphor used in the present invention is an M represented by the general formula [1].1Source, M2 Source, MThreeAfter pulverizing the source compound and the element compound (Eu) source compound of the luminescent center ion using a dry pulverizer such as a hammer mill, roll mill, ball mill, jet mill, etc., ribbon blender, V-type blender, Henschel mixer, etc. Mix by a mixer, or mix and then pulverize using a dry pulverizer, or add these compounds to a medium such as water, and use a wet pulverizer such as a medium agitating pulverizer. The slurry prepared by pulverizing and mixing, or by pulverizing these compounds with a dry pulverizer and adding to a medium such as water and mixing, was prepared by a wet method of drying by spray drying or the like. The pulverized mixture can be produced by heat treatment and baking.
[0016]
Among these pulverization and mixing methods, in particular, in the element source compound of the luminescent center ion, it is preferable to use a liquid medium because it is necessary to uniformly mix and disperse a small amount of the compound over the whole. The latter wet method is preferable from the viewpoint of obtaining uniform mixing in the element source compound as a whole, and the heat treatment method is usually 800 to 1600 ° C. in a heat-resistant container such as an alumina or quartz crucible or tray. The heating is preferably performed at a temperature of 1000 to 1400 ° C. for 10 minutes to 24 hours in a single or mixed atmosphere of a gas such as air, oxygen, carbon monoxide, carbon dioxide, nitrogen, hydrogen, and argon. In addition, after heat processing, washing | cleaning, drying, a classification process, etc. are made | formed as needed.
[0017]
As the heating atmosphere, an atmosphere necessary for obtaining an ion state (valence) in which the element of the emission center ion contributes to light emission is selected. In the case of divalent Eu or the like in the present invention, a neutral or reducing atmosphere such as carbon monoxide, nitrogen, hydrogen, and argon is preferable, but it can be selected even under an oxidizing atmosphere such as air and oxygen. . Where M1Source, M2Source and MThreeAs the source compound and the element source compound of the luminescent center ion, M1, M2And MThreeAnd oxides, hydroxides, carbonates, nitrates, sulfates, oxalates, carboxylates, halides, etc. of the elements of the luminescent center ion. And non-generation of NOx, SOx, etc. during firing is selected.
[0018]
Metal element M1With respect to Ba, Sr, and Ca, which are preferable with respect to M, their M1Specific examples of source compounds include BaO and Ba (OH) as Ba source compounds.2・ 8H2O, BaCOThree, Ba (NOThree)2, BaSOFour, Ba (OCO)2・ 2H2O, Ba (OCOCHThree)2, BaCl2As Sr source compounds, SrO, Sr (OH)2・ 8H2O, SrCOThree, Sr (NOThree)2, SrSOFour, Sr (OCO)2・ H2O, Sr (OCOCHThree)2・ 0.5H2O, SrCl2In addition, as Ca source compounds, CaO, Ca (OH)2, CaCOThree, Ca (NOThree)2・ 4H2O, CaSOFour・ 2H2O, Ca (OCO)2・ H2O, Ca (OCOCHThree)2・ H2O, CaCl2Etc., respectively.
[0019]
Metal element M2With respect to the Mg and Zn, which are preferable to the above, their M2Specific examples of source compounds include MgO and Mg (OH) as Mg source compounds.2, MgCOThree, Mg (OH)2・ 3MgCOThree・ 3H2O, Mg (NOThree)2・ 6H2O, MgSOFour, Mg (OCO)2・ 2H2O, Mg (OCOCHThree)2・ 4H2O, MgCl2In addition, Zn source compounds include ZnO and Zn (OH)2ZnCOThree, Zn (NOThree)2Zn (OCO)2, Zn (OCOCHThree)2ZnCl2Etc., respectively.
[0020]
Metal element MThreeFor the Si and Ge that are preferred for theThreeAs a specific example of the source compound, the Si source compound is SiO.2, HFourSiOFour, Si (OCOCHThree)FourAs a Ge source compound, GeO2, Ge (OH)Four, Ge (OCOCHThree)Four, GeClFourEtc., respectively.
Further, with respect to Eu, which is preferable as the element of the luminescent center ion, if the element source compound is specifically illustrated, Eu2OThree, Eu2(SOFour)Three, Eu2(OCO)6, EuCl2, EuClThreeEtc.
[0021]
In the present invention, the first light emitter that irradiates the phosphor with light generates light having a wavelength of 350 to 415 nm. Preferably, a light emitter that generates light having a peak wavelength in the wavelength range of 350 to 415 nm is used. Specific examples of the first light emitter include a light emitting diode (LED) or a laser diode (LD). In particular, a laser diode is preferable in that power consumption can be suppressed. Further, a GaN-based LED or LD using a GaN-based compound semiconductor is preferable. This is because GaN-based LEDs and LDs have significantly higher light emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and are extremely bright with very low power when combined with the phosphor. This is because light emission can be obtained. For example, for a current load of 20 mA, the GaN system usually has a light emission intensity 100 times or more that of the SiC system. In GaN LED and LD, AlXGaYN light emitting layer, GaN light emitting layer, or InXGaYThose having an N light emitting layer are preferred. Among GaN-based LEDs, InXGaYThose having an N light emitting layer are particularly preferred because the light emission intensity is very strong.XGaYA multi-quantum well structure of an N layer and a GaN layer is particularly preferable because the emission intensity is very strong. In the above, the value of X + Y is usually in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics. GaN-based LEDs have these light-emitting layers, p-layers, n-layers, electrodes, and substrates as basic components, and the light-emitting layers are made of n-type and p-type Al.XGaYN layer, GaN layer, or InXGaYThose having a heterostructure sandwiched between N layers and the like have high luminous efficiency, and those having a heterostructure having a quantum well structure further have high luminous efficiency, and are more preferable.
[0022]
In the present invention, it is particularly preferable to use a surface-emitting type illuminant, particularly a surface-emitting GaN-based laser diode, as the first illuminant because the luminous efficiency of the entire light-emitting device is increased. A surface-emitting type illuminant is an illuminant that emits strong light in the surface direction of a film. In a surface-emitting GaN-based laser diode, the crystal growth of a light-emitting layer or the like is controlled, and a reflective layer or the like is successfully performed. By devising, the light emission in the surface direction can be made stronger than the edge direction of the light emitting layer. When the surface emitting type is used, the light emission cross-sectional area per unit light emission amount can be increased compared to the type that emits light from the edge of the light emitting layer. As a result, the phosphor of the second light emitter is irradiated with the light. Since the irradiation area can be made very large with the same amount of light and the irradiation efficiency can be improved, stronger light emission can be obtained from the phosphor that is the second light emitter.
[0023]
When a surface-emitting type is used as the first light emitter, the second light emitter is preferably a film. As a result, the cross-sectional area of the light from the surface-emitting type light emitter is sufficiently large. Therefore, when the second light emitter is formed into a film in the direction of the cross section, the irradiation cross-section area of the phosphor from the first light emitter is irradiated. Becomes larger per unit amount of phosphor, so that the intensity of light emitted from the phosphor can be further increased.
[0024]
Further, when a surface-emitting type is used as the first light emitter and a film-like one is used as the second light emitter, the second light emitter directly in the form of a film on the light-emitting surface of the first light emitter. It is preferable that the shape is made to contact. Contact here means to create a state in which the first light emitter and the second light emitter are in perfect contact with each other without air or gas. As a result, it is possible to avoid a light amount loss in which light from the first light emitter is reflected by the film surface of the second light emitter and oozes out, so that the light emission efficiency of the entire apparatus can be improved.
[0025]
FIG. 4 is a schematic perspective view showing the positional relationship between the first light emitter and the second light emitter in an example of the light emitting device of the present invention. In FIG. 4, reference numeral 1 denotes a film-like second light emitter having the phosphor, 2 denotes a surface-emitting GaN-based LD as the first light emitter, and 3 denotes a substrate. In order to create a state in which they are in contact with each other, the LD 2 and the second light emitter 1 may be formed separately and the surfaces may be brought into contact with each other by an adhesive or other means. A second light-emitting body may be formed (molded) on the top. As a result, the LD 2 and the second light emitter 1 can be brought into contact with each other.
[0026]
The light from the first illuminant and the light from the second illuminant are usually directed in all directions. However, when the phosphor powder of the second illuminant is dispersed in the resin, the light is out of the resin. A part of the light is reflected when exiting, so the direction of the light can be adjusted to some extent. Accordingly, since light can be guided to a certain degree in an efficient direction, it is preferable to use a phosphor in which the phosphor powder is dispersed in a resin as the second luminous body. Further, when the phosphor is dispersed in the resin, the total irradiation area of the light from the first light emitter to the second light emitter is increased, so that the light emission intensity from the second light emitter can be increased. It also has the advantage of being able to. Examples of resins that can be used in this case include epoxy resins, polyvinyl resins, polyethylene resins, polypropylene resins, polyester resins, and the like. From the viewpoint of good dispersibility of the phosphor powder, epoxy resins are preferable. It is. When the powder of the second luminous body is dispersed in the resin, the weight ratio of the powder of the second luminous body to the whole resin is usually 10 to 95%, preferably 20 to 90%, more preferably Is 30-80%. If the phosphor is too much, the luminous efficiency may be reduced due to aggregation of the powder, and if it is too little, the luminous efficiency may be lowered due to light absorption or scattering by the resin.
[0027]
  The light-emitting device of the present invention comprises the phosphor as a wavelength conversion material and a light-emitting element that generates light of 350 to 415 nm.RecordA phosphor is a light-emitting device that absorbs 350-415 nm light emitted from a light-emitting element, has good color rendering regardless of the use environment, and can generate high-intensity visible light. And a light source such as an image display device such as a color liquid crystal display or a lighting device such as a surface light emission.
[0028]
The light emitting device of the present invention will be described with reference to the drawings. FIG. 5 is a schematic cross-sectional view showing an embodiment of a light emitting device having a first light emitter (350-415 nm light emitter) and a second light emitter. 4 is a light emitting device, 5 is a mount lead, 6 is an inner lead, 7 is a first light emitter (350-415 nm light emitter), 8 is a phosphor-containing resin portion as a second light emitter, 9 Is a conductive wire, and 10 is a mold member.
[0029]
As shown in FIG. 5, the light emitting device as an example of the present invention has a general bullet shape, and a first light emitter made of a GaN-based light emitting diode or the like is disposed in the upper cup of the mount lead 5. (350-415 nm phosphor) 7 is a phosphor-containing resin formed as a second phosphor by mixing and dispersing a phosphor in a binder such as an epoxy resin or an acrylic resin and pouring the mixture into a cup. It is fixed by being covered with the part 8. On the other hand, the first light emitter 7 and the mount lead 5, and the first light emitter 7 and the inner lead 6 are each electrically connected by a conductive wire 9, and these are entirely covered with a mold member 10 made of epoxy resin or the like, Protected.
[0030]
In addition, as shown in FIG. 9, the surface emitting illumination device 98 incorporating the light emitting element 1 has a large number of light emission on the bottom surface of a rectangular holding case 910 whose inner surface is light-opaque such as a white smooth surface. The device 91 is arranged with a power supply and a circuit (not shown) for driving the light emitting element 91 provided outside thereof, and a milky white acrylic plate or the like is provided at a position corresponding to the lid portion of the holding case 910. The diffusion plate 99 is fixed for uniform light emission.
[0031]
Then, the surface emitting illumination device 98 is driven to apply light to the first light emitter of the light emitting element 91 to emit light of 350 to 415 nm, and a part of the light emission is used as the second light emitter. The phosphor in the phosphor-containing resin part absorbs and emits visible light, while light emission with high color rendering properties is obtained by mixing with blue light or the like that is not absorbed by the phosphor. 99 is emitted upward in the drawing, and illumination light with uniform brightness is obtained within the surface of the diffusion plate 99 of the holding case 910.
[0032]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In addition, relative intensity shows the magnitude | size of emitted light intensity when the emitted light intensity of the fluorescent substance of the comparative example 1 is set to 100.
Example 1
M1BaCO as source compoundThree0.0553 mol, M2Basic magnesium carbonate (Mole number of 0.0186 mol) as source compound, and MThreeSiO as source compound20.0372 mol, and Eu as the element source compound of the luminescent center ion2OThree; 0.00018 mol together with pure water was pulverized and mixed in an alumina container and bead wet ball mill, dried, passed through a nylon mesh, and the resulting pulverized mixture was 4% in an alumina crucible. The phosphor was produced by heating at 1200 ° C. for 2 hours under a nitrogen gas stream containing hydrogen, followed by washing with water, drying, and classification.
[0033]
FIG. 6 shows the obtained phosphor Ba.2.98Eu0.02MgSi2O8The X-ray diffraction pattern of is shown. The peak pattern in FIG. 6 is represented by Ba in FIG.ThreeMgSi2O8It can be seen that the crystal structure is consistent with that of. FIG. 7 shows an emission spectrum when this phosphor is excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode. Table 1 shows the wavelength and relative intensity of the emission peak.
[0034]
Example 2
M1SrCO as source compoundThreeA phosphor was produced in the same manner as in Example 1 except that 0.0553 mol was used. FIG. 8 shows the phosphor Sr.2.98Eu0.02MgSi2O8The X-ray diffraction pattern of is shown. The peak pattern of FIG. 8 is the Sr of FIG.ThreeMgSi2O8It can be seen that the crystal structure is consistent with that of. Table 1 shows the wavelength and relative intensity of the emission peak when the phosphor is excited at 400 nm, which is the dominant wavelength in the ultraviolet region of the GaN-based light emitting diode.
[0035]
Example 3
M1BaCO as source compoundThree0.0442 mol, CaCOThree0.0084 mol, and MnCOThreeA phosphor was produced in the same manner as in Example 1 except that 0.0028 mol was used. Table 1 shows the wavelength and relative intensity of the emission peak when the phosphor is excited at 400 nm, which is the dominant wavelength in the ultraviolet region of the GaN-based light emitting diode.
[0036]
Example 4
M2A phosphor was produced in the same manner as in Example 1 except that basic zinc carbonate (0.0186 mol of Zn) was used as the source compound. Table 1 shows the wavelength and relative intensity of the emission peak when the phosphor is excited at 400 nm, which is the dominant wavelength in the ultraviolet region of the GaN-based light emitting diode.
[0037]
Example 5
Eu, an element source compound of luminescent center ions2OThreeThe number of moles is changed to 0.000074 moles, and M1BaCO as source compoundThreeA phosphor was produced in the same manner as in Example 1 except that the number of moles of was changed to 0.0556 mole. Table 1 shows the wavelength and relative intensity of the emission peak when the phosphor is excited at 400 nm, which is the dominant wavelength in the ultraviolet region of the GaN-based light emitting diode.
[0038]
Example 6
A phosphor was manufactured in the same manner as in Example 1 except that the firing temperature was changed to 1300 ° C. Table 1 shows the wavelength and relative intensity of the emission peak when the phosphor is excited at 400 nm, which is the dominant wavelength in the ultraviolet region of the GaN-based light emitting diode.
[0039]
Example 7
BaCO3The blending amount of 0.0549 mol, Eu2O3The phosphor Ba was the same as in Example 1 except that the compounding amount of was changed to 0.00047 mol.2.95Eu0.05MgSi2O8Manufactured.
When this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of the GaN-based light emitting diode, the wavelength of the emission peak was 438 nm and the relative intensity was 299.
[0040]
Example 8
BaCO3The compounding amount of2O3Except that the blending amount of was changed to 0.00093 mol, the phosphor Ba was the same as in Example 1.2.9Eu0.1MgSi2O8Manufactured.
When this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, the wavelength of the emission peak was 440 nm and the relative intensity was 320.
[0041]
Example 9
BaCO3The blending amount of Eu to 0.0530 mol, Eu2O3The phosphor Ba was the same as in Example 1 except that the blending amount of was changed to 0.00140 mol.2.85Eu0.15MgSi2O8Manufactured.
When this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, the wavelength of the emission peak was 440 and the relative intensity was 261.
[0042]
Example 10
BaCO3The compounding amount of2O3Except for changing the compounding amount of the phosphor to 0.00186 mol, the phosphor Ba is the same as in Example 1.2.8Eu0.2MgSi2O8Manufactured.
When this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, the wavelength of the emission peak was 440 and the relative intensity was 199.
[0043]
Example 11
BaCO3The blending amount is 0.0502 mol, Eu2O3The phosphor Ba was the same as in Example 1 except that the blending amount of was changed to 0.00279 mol.2.7Eu0.3MgSi2O8Manufactured.
When this phosphor was excited at 400 nm, which is the dominant wavelength in the ultraviolet region of a GaN-based light emitting diode, the wavelength of the emission peak was 441 and the relative intensity was 113.
[0044]
Comparative Example 1
BaCOThree0.0103 mol, basic magnesium carbonate (0.0103 mol of Mg), and γ-Al2OThree0.0570 mol, and Eu as the element source compound of the luminescent center ion2OThree; 0.00057 mol was mixed with pure water in an alumina container and a wet ball mill of beads, dried, allowed to pass through a nylon mesh, and the resulting pulverized mixture was 4% in an alumina crucible. The phosphor is baked by heating at 1500 ° C. for 2 hours under a nitrogen gas stream containing hydrogen, followed by washing with water, drying, and classification to obtain a blue-emitting phosphor (Ba0. 9Eu0.1MgAlTenO17) Was manufactured. FIG. 7 shows an emission spectrum when the phosphor is excited at 400 nm, which is the dominant wavelength in the ultraviolet region of the GaN-based light emitting diode, and the performances of the blue light-emitting phosphors of Example 1 and Comparative Example 1 are compared. Table 1 shows the wavelength and relative intensity of the emission peak. It can be seen that the emission intensity of the phosphor of Example 1 excited by 400 nm is 2.8 times that of the phosphor of Comparative Example 1.
[0045]
Comparative Example 2
Y2OThree0.0238 mol, γ-Al2OThree0.0400 mol, and CeO as the element source compound of the luminescent center ion2; 0.00048 mol together with pure water was pulverized and mixed in an alumina container and bead wet ball mill, dried, passed through a nylon mesh, and the resulting pulverized mixture was 4% in an alumina crucible. The phosphor was baked by heating at 1500 ° C. for 2 hours under a nitrogen gas stream containing hydrogen, followed by washing with water, drying, and classification treatment to produce a yellow-emitting phosphor (Y2.98Ce0.03AlFiveO12) Was manufactured. Table 1 shows the wavelength and relative intensity of the emission peak. It can be seen that the emission intensity of the phosphor of Example 1 excited by 400 nm is 250 times that of the phosphor of Comparative Example 2.
[0046]
[Table 1]
[0047]
【The invention's effect】
According to the present invention, a light emitting device having high emission intensity can be provided.
[Brief description of the drawings]
[Figure 1] BaThreeMgSi2O8X-ray diffraction pattern (converted to X-ray source Cu Kα)
[Figure 2] SrThreeMgSi2O8X-ray diffraction pattern (converted to X-ray source Cu Kα)
[Fig. 3] CaThreeMgSi2O8X-ray diffraction pattern (converted to X-ray source Cu Kα)
4 is a schematic perspective view showing a positional relationship between a first light emitter and a second light emitter in an example of the light emitting device of the present invention. FIG.
FIG. 5 is a schematic cross-sectional view showing an embodiment of a light emitting device having a first light emitter (350-415 nm light emitter) and a second light emitter.
6 is an X-ray diffraction pattern (X-ray source: Cu Kα) of the phosphor of Example 1. FIG.
FIG. 7 shows an emission spectrum when the phosphors of Example 1 and Comparative Example 1 of the present invention are combined with a GaN-based light emitting diode having an emission wavelength of 400 nm.
8 is an X-ray diffraction pattern (X-ray source: Cu Kα) of the phosphor of Example 2. FIG.
FIG. 9 is a schematic cross-sectional view showing an example of a surface-emitting illumination device of the present invention.
[Explanation of symbols]
1: Second light emitter
2: Surface-emitting GaN LED
3; Substrate
4: Light emitting device
5: Mount lead
6; Inner lead
7; 1st light-emitting body (350-415 nm light-emitting body)
8: Resin part containing the phosphor of the present invention
9; Conductive wire
10: Mold member

Claims (13)

  1. In the light emitting device having a first light emitter that generates light of 350 to 415 nm and a second light emitter that generates visible light by irradiation of light from the first light emitter, the second light emitter Comprising a phosphor having a crystal phase having a chemical composition represented by the general formula [1].
    (However, M 1 represents a metal element containing 90 mol% or more in total of at least one element selected from the group consisting of Ba and Sr, M 2 represents a metal element containing 90 mol% or more of Mg , and M 3 represents Represents a metal element containing 90 mol% or more of Si , a is a number satisfying 2.5 ≦ a ≦ 3.3, b is a number satisfying 0.02 ≦ b <0.15 , and c is 0.9 ≦ (a number that satisfies c ≦ 1.1, d is a number that satisfies 1.8 ≦ d ≦ 2.2, and e is a number that satisfies 7.2 ≦ e ≦ 8.8.)
  2. The ratio of the total of Ba and Sr in M 1 , the ratio of Mg in M 2 , and the ratio of Si in M 3 are 95 mol% or more, respectively. Light emitting device.
  3. b is the light-emitting device according to claim 1 or 2, characterized in that it is 0.05 ≦ b ≦ 0.1.
  4. The light emitting device according to any one of claims 1 to 3 , wherein a molar ratio of Ba to Sr in M 1 is 0.05 or more.
  5. The light-emitting device according to claim 1, wherein the phosphor has a crystal structure similar to merwinite.
  6. The phosphor exhibits an emission spectrum having an emission peak wavelength of 438 to 440 nm when the phosphor is excited at 400 nm, which is a main wavelength in an ultraviolet region of a GaN-based light emitting diode. The light emitting device according to any one of 1 to 5.
  7.   The light emitting device according to claim 1, wherein the first light emitter is a laser diode or a light emitting diode.
  8.   The light emitting device according to claim 7, wherein the first light emitter is a laser diode or a light emitting diode using a GaN-based compound semiconductor.
  9.   9. The light emitting device according to claim 8, wherein the first light emitter is a surface emitting GaN-based laser diode.
  10.   The light emitting device according to claim 9, wherein the second light emitter is in the form of a film.
  11.   The high-efficiency light-emitting device according to claim 1, wherein the light-emitting surface of the first light-emitting body is in direct contact with the film surface of the second light-emitting body.
  12.   The light emitting device according to any one of claims 1 to 11, wherein the second light emitter is obtained by dispersing phosphor powder in a resin.
  13.   An illumination device comprising the light-emitting device according to claim 1.
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JP4617889B2 (en) * 2004-01-16 2011-01-26 三菱化学株式会社 Phosphor, and light emitting device, lighting device, and image display device using the same
US7608200B2 (en) 2004-01-16 2009-10-27 Mitsubishi Chemical Corporation Phosphor and including the same, light emitting apparatus, illuminating apparatus and image display
JP4617890B2 (en) * 2004-01-16 2011-01-26 三菱化学株式会社 Phosphor, and light emitting device, lighting device, and image display device using the same
CN101010413B (en) * 2004-09-07 2010-08-25 住友化学株式会社 Phosphor, phosphor paste and light-emitting device
KR20060034055A (en) * 2004-10-18 2006-04-21 엘지이노텍 주식회사 Phosphor and led using the same
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JP2006137851A (en) * 2004-11-12 2006-06-01 Sumitomo Chemical Co Ltd Silicate fluorescent substance powder and method for producing the same
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JP5770192B2 (en) * 2010-09-07 2015-08-26 宇部マテリアルズ株式会社 Blue light emitting phosphor and light emitting device using the blue light emitting phosphor
JP5736272B2 (en) * 2011-08-09 2015-06-17 宇部マテリアルズ株式会社 Blue light emitting phosphor and light emitting device using the blue light emitting phosphor
JP6187342B2 (en) * 2014-03-20 2017-08-30 宇部興産株式会社 Oxynitride phosphor powder and method for producing the same
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