WO2009096082A1 - Matière luminescente - Google Patents

Matière luminescente Download PDF

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Publication number
WO2009096082A1
WO2009096082A1 PCT/JP2008/071177 JP2008071177W WO2009096082A1 WO 2009096082 A1 WO2009096082 A1 WO 2009096082A1 JP 2008071177 W JP2008071177 W JP 2008071177W WO 2009096082 A1 WO2009096082 A1 WO 2009096082A1
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luminescent material
light
emission
luminescent
wavelength
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Ryosuke Hiramatsu
Naotoshi Matsuda
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Toshiba Corp
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Toshiba Corp
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    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • H10H20/8512—Wavelength conversion materials
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77342—Silicates
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    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
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    • H10W72/07252—Connecting or disconnecting of bump connectors characterised by changes in properties of the bump connectors during connecting changes in structures or sizes
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    • H10W72/00—Interconnections or connectors in packages
    • H10W72/20—Bump connectors, e.g. solder bumps or copper pillars; Dummy bumps; Thermal bumps
    • H10W72/221—Structures or relative sizes
    • H10W72/227—Multiple bumps having different sizes
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    • H10W72/00—Interconnections or connectors in packages
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    • H10W72/874—On different surfaces
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    • H10W72/00—Interconnections or connectors in packages
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    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
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    • H10W72/00—Interconnections or connectors in packages
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    • H10W72/941—Dispositions of bond pads
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    • H10W72/00—Interconnections or connectors in packages
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    • H10W72/941—Dispositions of bond pads
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    • H—ELECTRICITY
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    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
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    • H10W90/00—Package configurations
    • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
    • H10W90/721—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bump connectors
    • H10W90/722—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bump connectors between stacked chips
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    • H10W90/731—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors
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    • H10W90/756—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bond wires between a chip and a stacked lead frame, conducting package substrate or heat sink

Definitions

  • This invention relates to a luminescent material and also to a light-emitting device.
  • a light-emitting diode is generally constituted by a combination of an LED chip acting as an exciting light source with a luminescent material, and emits various luminescent colors, depending on this combination.
  • a white LED device which emits white light
  • an LED chip which emits a light in the ultraviolet or near- ultraviolet region
  • a mixture of luminescent materials may be composed of a blue luminescent material, a green or yellow luminescent material and a red luminescent material. It is required for the luminescent material to be used in a white LED device to be not only capable of effectively absorbing the light ranging from near- ultraviolet region to blue region, i.e. a wavelength of 360 to 500 nm, which corresponds to the emission wavelength of an LED chip acting as an exciting light source, but also capable of efficiently emitting visible light.
  • a BaMgAl ⁇ )0l7 : Eu luminescent material is proposed in JP-A 2007-39517 (KOKAI) as a blue luminescent material to be employed in a white LED device.
  • KOKAI KOKAI
  • this blue luminescent material is accompanied with a problem that when it is employed in combination with an LED chip which emits a light in the near-ultraviolet region having a wavelength ranging from 380 to 410 nm, the emission intensity greatly changes depending on the peak wavelength of an exciting light source to be employed. For this reason, it is required to adjust the quantity of the blue luminescent material being used in conformity with the variability of the emission wavelength of the LED chip to be used.
  • Li2(SrQ.88' Can.i, Eun.02)Si ⁇ 4 luminescent material As a europium- activated lithium alkaline earth metal silicate luminescent material.
  • a lithium calcium silicate luminescent material comprises a tetragonal crystal phase containing Li, Ca, Si and O; and an activator containing Eu.
  • a lithium calcium silicate luminescent material comprises a crystal phase containing Li, Ca, Si and O; and an activator containing Eu, the luminescent material exhibiting a peak wavelength of emission spectrum falling within a wavelength region of 470 to 490 nm when excited by light having an emission peak falling within a wavelength region of 360 to 460 nm.
  • a light-emitting device comprises a light- emitting element emitting light having a main emission peak in a wavelength ranging from 360 to 460 nm; and a luminescent layer comprising a luminescent material and designed to be irradiated with the light, at least a portion of the luminescent material being a first luminescent material formed of the aforementioned luminescent material.
  • FIG. 1 is a graph showing an emission spectrum of the conventional luminescent material and an emission spectrum of the luminescent material according to one embodiment ;
  • FIG. 2 shows an emission spectrum of the luminescent material according to another embodiment
  • FIG. 3 shows an emission spectrum of the luminescent material according to a further embodiment
  • FIG. 4 shows an emission spectrum of the luminescent material according to a further embodiment
  • FIG. 5 shows an excitation spectrum of the luminescent material according to a further embodiment
  • FIG. 6 shows an X-ray diffraction pattern of the luminescent material according to a further embodiment
  • FIG. 7 shows an X-ray diffraction pattern of the luminescent material according to the prior art
  • FIG. 8 shows a microphotograph obtained from the excitation of the luminescent material by a light having a wavelength of 365 nm according to a further embodiment ;
  • FIG. 9 is a cross-sectional view illustrating a light-emitting device according to one embodiment
  • FIG. 10 is a cross-sectional view illustrating a light-emitting device according to another embodiment
  • FIG. 11 is an enlarged cross-sectional view of a light-emitting element
  • FIG. 12 is a cross-sectional view illustrating a light-emitting device according to a further embodiment ;
  • FIG. 13 shows an emission spectrum of the white LED light-emitting device according to one embodiment
  • FIG. 14 shows an emission spectrum of the white LED light-emitting device according to another embodiment.
  • each of elements constituting the present invention may be modified in such a manner that a plurality of elements are integrated by the same single member to enable this single member to have the functions of the plurality of elements or, on the contrary, the functions of a single member are shared by a plurality of members.
  • lithium calcium silicate luminescent material which exhibits a peak wavelength of emission spectrum which falls within a wavelength region of 470 to 490 nm when excited by light having an emission peak falling within a wavelength region of 360 to 460 nm.
  • the term "lithium calcium silicate luminescent material” means a luminescent material having a crystal phase containing Li, Ca, Si and O. Since this luminescent material contains europiums as an activator and is formed of a tetragonal crystal phase, the luminescent material according to one embodiment emits light when excited by the light having a luminescence peak falling within a wavelength range of 360 to 460 nm.
  • This lithium calcium silicate can be represented generally by the following general formula (B) .
  • the ultraviolet-emitting LED emitting a light having a short wavelength of less than 360 nm is high in manufacturing cost and low in conversion efficiency of electricity to light. Moreover, since the resin in which the luminescent material is dispersed tends to be prominently degraded, the lower limit of the excitation wavelength is practically confined to 360 nm. On the other hand, if this LED is excited by a light having a wavelength of more than 460 nm, it is scarcely possible to obtain a target emission spectrum, so that the upper limit of the excitation wavelength is confined to 460 nm.
  • emission spectrum it is intended to mean herein a spectrum wherein a half band width of emission band to be measured at a wavelength region of a peak wavelength ranging from 470 to 490 nm is confined within 40 nm.
  • This emission spectrum can be determined by exciting a luminescent material by a light having an emission peak in a wavelength region of 360 to 460 nm to generate the emission of light, which is then measured by a spectrophotometer, thus determining the emission spectrum.
  • the exciting source it is possible to employ, for example, a near-ultraviolet region LED of 390 nm in wavelength or a blue region LED of 460 run in wavelength.
  • spectrophotometer it is possible to employ, for example, IMUC-7000 (trade name, Ohtsuka Electronics Co., Ltd.).
  • the lithium calcium silicate luminescent material according to one embodiment can be represented generally by the following general formula (A) .
  • the content of Eu (yl) is larger than 0.
  • the luminescent material is excited by a light having an emission peak falling within the range of 360-460 nm, it would be impossible to obtain an emission spectrum.
  • the content of Eu is excessively large, a concentration quenching phenomenon generates, thereby possibly weakening the emission intensity of the
  • Li a (Ca;L- x i_yi, M xl , Euy]Jb s ic o d luminescent material In order to avoid this problem, the upper limit in content of Eu (yl) should be regulated to 0.08. Further, the content yl should more preferably be confined to the range of 0. Ol ⁇ yl ⁇ O .06.
  • the luminescent material according to one embodiment exhibits an emission spectrum wherein the half band width thereof is confined within 40 nm and a peak wavelength falls within a wavelength region of 470 to 490 nm when excited by light having an emission peak falling within a wavelength region of 360 to 460 nm. Further, as a result of the measurement by powder X-ray diffractometry (XRD) , it was possible to confirm that the crystal structure of the luminescent material according this embodiment was of a tetragonal system. It was found out by the present inventors that this crystal structure was derived due to the content of each of the elements and that the color of emission to be derived therefrom was also closely related to this crystal structure.
  • XRD powder X-ray diffractometry
  • Sr which is an alkaline earth metal
  • the crystal structure is made hexagonal. Namely, it is assumed that when the crystal structure is made hexagonal in the europium-activated lithium alkaline earth metal silicate luminescent material, yellow emission is generated.
  • the europium-activated lithium alkaline earth metal silicate luminescent materials which have been known up to date are limited to those which emits only yellow.
  • the fact that the color of emission can be changed depending on the crystal structure thereof is not recognized up to date and is discovered for the first time by the present inventors. Namely, the present inventors have discovered the fact that as the ratio of Ca among the alkaline earth metal elements in the parent -composition is increased, the crystal structure thereof is turned hexagonal, enabling it to emit a blue light. More specifically, when the content of Ca (1-xl-yl) is increased to 0.59 or more in the aforementioned general formula (A) , it is possible to obtain blue emission.
  • part of the calcium site may be substituted by a bivalent cation (M) selected from barium, strontium and magnesium.
  • M bivalent cation
  • Ca and M (M is at least one selected from Ba, Sr and Mg) exist in a state of a complete solid solution.
  • Sr and Ca can be present as the same bivalent cation and the ionic radium thereof are relatively close to each other. Because of this, the influence thereof on the crystal structure is relatively small and hence can be preferably employed as a substituent element.
  • Eu to be employed as an activating element is larger in ionic radius than that of Ca.
  • Mg which is smaller in ionic radius than that of Ca, can be preferably employed in a case where the quantity of substitution is relatively small or where the concentration of the activating element is relatively high.
  • Sr or Mg is preferable for use as the M.
  • the content of M (xl) is too large, the crystal structure to be obtained can no longer be hexagonal. As a result, even if the luminescent material is excited with a light having an emission peak falling within the wavelength region of 360- 460 nm, it would be impossible to obtain blue emission.
  • the substituent element is Sr
  • the luminescent material to be obtained would become such that it emits yellow having a peak wavelength falling in the vicinity of 575 nm.
  • the content thereof (xl) should preferably be confined to 0.39 or less, more preferably 0.2 or less.
  • the ionic radius of Ba differs greatly from that of Ca, there is a limit in the quantity of Ba that can be incorporated in the Li2CaSiC>4 employed as a parent body.
  • the upper limit of the content (xl) should be set to 0.2. In the case of Ba, xl should more preferably be confined to 0.2 or less.
  • the content (xl) thereof should preferably be confined to 0.4 or less, more preferably 0.05 or less.
  • the lithium site may be substituted, in a small quantity, by at least one selected from sodium, potassium, rubidium and cesium.
  • the silicon site may be substituted by a small quantity of germanium.
  • the content of each of these elements in the luminescent material according to one embodiment can be analyzed, for example, by the following procedures.
  • a metal element such as Ca, M, Eu and Si
  • the luminescent material synthesized is subjected to alkali fusion.
  • the fused material thus obtained is then subjected to analysis by an ICP emission spectrochemical method which is an internal standard method and by IRIS Advantage (trade name, Thermo Fisher Scientific K. K.) or SPS1200AR (trade name, SII
  • the synthesized luminescent material is subjected to inert gas fusion.
  • the fused material is then analyzed by infrared absorption using, for example, TC-600 (trade name, LECO Co., Ltd.). In this manner, the composition of the luminescent material can be determined.
  • the luminescent material according to the embodiment described above can be combined with a light-emitting element having an emission peak falling within a wavelength region of 360-460 nm to obtain an LED light-emitting device representing one embodiment.
  • the LED light- emitting device Since a lithium calcium silicate luminescent material of a specific composition containing Eu as an activator is included in the emission layer, the LED light- emitting device according to this embodiment is enabled to enhance the emission efficiency and color rendering as compared with an LED light-emitting device using a conventional luminescent material.
  • the luminescent material according to one embodiment can be manufactured by employing the following method, for example.
  • the starting material it is possible to employ the oxide powder or carbonate powder of the constituent elements.
  • a starting material is weighed to obtain a predetermined quantity thereof to which a crystal growth-promoting agent is added and mixed together by, for example, a ball mill, etc.
  • the raw material for Eu it is possible to employ, for example, EU2O3, etc.
  • the raw material for Ca it is possible to employ, for example, CaCC>3, CaO, etc.
  • the raw material for Ba it is possible to employ, for example, BaCC>3, BaO, etc.
  • Sr it is possible to employ, for example, SrC ⁇ 3, SrO, etc.
  • Mg it is possible to employ, for example, MgCC>3,' MgO, etc.
  • the raw material for Si it is possible to employ, for example, SiC>2, etc.
  • Starting materials such as oxides are formulated in conformity with the composition ratio of the compound aimed at. These raw material powders can be mixed together by a dry mixing method wherein no solvent is employed. Alternatively, it is also possible to employ a wet mixing method wherein an organic solvent such as ethanol is employed.
  • the crystal growth-promoting agent it is possible to employ the chlorides, fluorides, bromides or iodides of alkaline metals. It is also possible to employ the chlorides, fluorides, bromides or iodides of alkaline earth metals and chlorides, fluorides, bromides or iodides of ammonium chloride. In order to prevent any increase in hygroscopic property of the luminescent material, the content of these crystal growth-promoting agents should preferably be confined to the range of 0.01 wt% to 0.3 wt% based on a total weight of these feedstock powders.
  • a mixed raw material obtained from the mixing of these feedstock powders is placed in a vessel such as a crucible and then subject to heat treatment to obtain a sintered product.
  • the heat treatment can be performed in air, N2/H2 or Ar/H2 atmosphere. By performing the heat treatment in any of these atmospheres, it is possible to prevent any increase in the hygroscopic property of the raw materials and to synthesize a matrix of a luminescent material, and, at the same time, it is possible to promote the reduction of europium in the oxides employed as feedstocks.
  • the conditions for the heat treatment are preferably 600- 1000°C in temperature and 2-48 hours in treatment time. When the treating temperature is too low or when the treating time is too short, it may become difficult to sufficiently achieve the reaction of raw material powders.
  • the treating temperature is too high or when the treating time is too long, the sublimation of feedstock powders or the product may occur.
  • the sintered product thus obtained may be subsequently pulverized to obtain the powder thereof, which is again placed in a vessel and subjected to secondary sintering in an N2/H2 or Ar/H2 atmosphere.
  • secondary sintering there is no particular regulation, so that the blocks of product of primary sintering may be pulverized in a mortar, etc., so as to increase the surface area thereof.
  • This luminescent material was formulated to contain Eu as an activator and hence confirmed as having a tetragonal crystal structure as measured by XRD. Therefore, this material was a luminescent material according to one embodiment.
  • the luminescent materials thus obtained were excited by a near-ultraviolet LED exhibiting a wavelength of 389 nm to measure the emission spectrum thereof.
  • the results are shown in FIG. 1.
  • FIG. 1 it was possible to derive from the Li2(CaQ.96, Euo.O4)SiC>4 luminescent material an emission spectrum originating from Eu ⁇ + and exhibiting a peak wavelength of 480 nm and a half band width of 30 nm.
  • a yellow emission having a peak wavelength of 575 nm and a half band width of 130 nm was obtained from the Li2(SrQ.96, Eug.04)Si ⁇ 4 luminescent material.
  • the ionic radius of the element to be substituted by- europium becomes larger in a situation where the crystal structure thereof is formed of the same parent crystal, the peak wavelength more likely shift toward the short wavelength side.
  • the reason for this may be attributed to the fact that the influence of atoms closely surrounding the substituted europium on the substituted europium becomes smaller in such a situation. Namely, the reason may be assumably attributed to the fact that since the influence of the crystal field becomes smaller, the energy partitioning of the 5d level of europium becomes smaller.
  • the ionic radius of strontium is larger than the ionic radius of calcium.
  • the Li2(Sr, Eu)SiC>4 luminescent material employing strontium exhibits a peak wavelength at a longer wavelength region than the Li2 (Ca, Eu)SiC>4 luminescent material where calcium is employed.
  • the reason for this may be attributed to a difference in peripheral environments of europium between the L ⁇ 2 (Ca, Eu) Si ⁇ 4 luminescent material and the Li2 (Sr, Eu)SiC>4 luminescent material.
  • the Li2 (Ca, Eu) SiC>4 luminescent material exhibits quite a different emission characteristic from that of the Li2 (Sr, Eu) Si ⁇ 4 luminescent material.
  • the europium-activated luminescent material having a composition of Li2CaSi ⁇ 4 as a parent body is formed of a tetragonal crystal structure and enabled to have a relatively large space around the europium as compared with a hexagonal crystal structure. Because of this, this europium-activated luminescent material generates a blue to green emission. As described above, the phenomenon that the emission color of an alkaline earth metal silicate luminescent material changes depending on the crystal structure thereof was first discovered by the present inventors.
  • an Li2(CaQ.99, Eun.oi)Si ⁇ 4 luminescent material and an Li2 (Cag .9i2f SrQ.048' E u 0.04)Si ⁇ 4 luminescent material were manufactured respectively according to the aforementioned method.
  • the luminescent materials thus obtained were excited by a near-ultraviolet LED exhibiting a peak wavelength of 391 nm and the emission spectrums thus obtained were measured. The results are shown in FIGS. 2 and 3, respectively. As shown in FIG.
  • the wavelength of the exciting light employed was varied to 380, 400, 420 and 440 nm.
  • the emission spectrums obtained through the employment of these exciting lights are shown in FIG. 4. It will be recognized that in any case where any one of these wavelengths was employed for the excitation, it was possible to confirm blue emission from the Li2(Cag.96, EUQ .04)SiC>4 luminescent material. Further, as the exciting light was made longer in wavelength, the intensity of emission was lowered. However, as far as the exciting wavelength region of 380 to 440 nm is concerned, it was only possible to confirm the lowering in intensity of emission to about 25%.
  • the variation in intensity of emission was confined within 40% as the luminescent material was excited by a light having an emission peak falling within the range of 360 to 460 ran.
  • This variation is very small as compared with the conventional blue luminescent material such as a BaMgAlioOl7 : Eu luminescent material.
  • the variation in intensity of emission increases up to 75% even if the exciting wavelength is confined to a narrow range of 370 to 420 nm.
  • this BaMgAl ⁇ nO17 : Eu luminescent material is employed in combination with an LED chip which emits light of the near-ultraviolet region having a wavelength ranging from 380 to 410 nm, the emission intensity of the luminescent material greatly varies depending on the peak wavelength of the exciting light source. Moreover, due to the variability of emission wavelength of the LED chip to be used, it may be sometimes required to adjust the quantity of the blue luminescent material to be used.
  • the variation in intensity of emission that may be caused depending on the exciting wavelength is relatively small as described above. Because of this, the quantity of the blue luminescent material is not required to be adjusted even if the emission wavelength of the LED chip to be used is varied, thus making this luminescent material very easy in handling.
  • the luminescent material having a composition represented by the aforementioned general formula (A) was measured with respect to the excitation spectrum thereof. As a result, it was possible to confirm the existence of an excitation band in the vicinity of 470 nm and in the peripheral region of the emission peak wavelength.
  • the excitation spectrum can be obtained by measuring a luminescent material powder by diffusion scattering using, for example, a fluorospectrophotometer F-3000 (trade name, Hitachi Ltd. ) .
  • FIG. 5 shows an excitation spectrum which was obtained through the observation of the emission of 480 nm of the Li2(Can.96, Euo.O4)SiC>4 luminescent material. It will be recognized from FIG. 5 that the Li2(Cag.96, EuQ.04)Si ⁇ 4 luminescent material was capable of being excited at the wavelength range of
  • the diffraction patterns obtained were compared with JCPDS (Joint Committee on Powder Diffraction Standards) cards, thereby performing the identification of the crystal phase.
  • JCPDS Joint Committee on Powder Diffraction Standards
  • a sample of the synthesized luminescent material is measured with respect to the diffraction pattern by, for example, M18XHF 22 -SRA (trade name, Mac/Science Company Co., Ltd. (Blueker AXS K.K.)) and then, the resultant diffraction pattern is compared with that of the JCPDS card.
  • FIGS. 6 and 7 show the resultant X-ray diffraction patterns, respectively.
  • the diffraction pattern obtained was found to be approximately identical with the diffraction pattern of tetragonal system Li2CaSi ⁇ 4 phase shown in the JCPDS card #27-290. It will be recognized from this result that in the case of the Li a ⁇ (Ca ⁇ -xi-yi, M x ⁇ ,
  • the diffraction patterns obtained from the Li2(SrQ.96, EUQ.04) ⁇ 104 luminescent material was found to be approximately identical with the diffraction pattern of hexagonal system Li2SrSi ⁇ 4 phase shown in the JCPDS card #55-217.
  • the diffraction pattern of the luminescent material having a composition represented by the aforementioned general formula (A) has a peak which is identical with the peak of the tetragonal Li2CaSi ⁇ 4 phase in the XRD measurement as described above, it can be said that the tetragonal Li2CaSiC>4 phase has been generated therein.
  • the luminescent material thus synthesized has a structure wherein an activating element Eu as well as an additive element such as M, etc. is incorporated therein as a substituent element, the diffraction peak to be obtained from the XRD measurement will be affected by the change of lattice constant that may be caused due to ionic radius of the substituting elements. For this reason, the diffraction pattern to be obtained may not be accurately identical to the diffraction pattern of Li2CaSi ⁇ 4 phase described in the JCPDS card #27-290. However, even if the 2 ⁇ thereof is shifted in peak by several degrees, the diffraction pattern thus obtained can be regarded as being identical to the diffraction pattern of Li2CaSiC>4 phase.
  • a similar peak shift may generate in the substitution of a monovalent cation element for the lithium site or in the substitution of a tetravalent cation element for the silicon site.
  • observation by a fluorescence microscope was performed on the Li2(CaQ.96' Eu().04)Si ⁇ 4 luminescent material. This microscopic observation was performed in such a manner that a synthesized sample of luminescent material was excited by irradiating it with an exciting light having a wavelength of 365 nm to generate the emission from the luminescent material, which emission was observed by ECLIPSE80i (trade name, Nikon Corporation) for example.
  • the synthesized Li2(CaQ.96, EuQ.04)Si ⁇ 4 luminescent material was formed of particles having a particle diameter ranging from around 5 to 30 ⁇ m and uniformly emitting blue light due to the irradiation thereof with an exciting light having a wavelength of 365-435 nm.
  • FIG. 8 shows the results of the microscopic observation of the Li2(CaQ.96' Euo.O4) s i°4 luminescent material as it was irradiated with an exciting light having a wavelength of 365 nm.
  • the luminescent material according to this embodiment can be manufactured, basically, by a process wherein various raw materials powder are mixed together and then subjected to sintering as described above.
  • the luminescent material thus sintered should preferably be subjected to any appropriate post- treatment, such as washing with pure water, on the occasion of applying the luminescent material to an emission device, etc.
  • the quenching of the Li a ⁇ (Ca ⁇ _ x ⁇ _y ⁇ , M x ⁇ , EUyX)J 3 ISi 0 XO 1 Ji luminescent material can be scarcely recognized, indicating that this luminescent material is quite stable. Namely, since the luminescent material according to this embodiment is stable in an air atmosphere as well as in an aqueous solution, the degree of freedom with regard to the post-treatment to be performed on a sample after the sintering thereof is very high.
  • a surface-covering material may be coated on the surface of luminescent particles manufactured.
  • the surface-covering material to be employed herein may be formed of at least one selected from the group consisting of silicone resin, epoxy resin, fluororesin, tetraethoxy silane (TEOS) , silica, zinc silicate, aluminum silicate, calcium polyphosphate, silicone oil and silicone grease.
  • Zinc silicate and aluminum silicate may be represented, for example, by ZnO-cSi ⁇ 2 (l ⁇ c ⁇ 4) and Al2 ⁇ 3 -dSi ⁇ 2 (l ⁇ d ⁇ lO), respectively.
  • the surface of the luminescent particles need not be completely covered with the surface-covering material, so that part of the surface of the luminescent particles may be exposed.
  • This surface-covering material can be applied to the surface of the luminescent particles by a fluid dispersion containing the surface-covering material or by use of a solution of the surface-covering material. Specifically, the luminescent particles are immersed in the fluid dispersion or the solution for a predetermined period of time and then dried by heating, etc., thus depositing the surface-covering material on the surface of luminescent particles.
  • the quantity of the surface- covering material should preferably be confined to about 0.1-5% by volume based on the luminescent particles .
  • the luminescent material according to this embodiment is classified depending on the coating method to be applied to an emission device. For example, for an ordinary white LED where an exciting light of 360-460 nm in wavelength is employed, the luminescent material is employed after the luminescent material has been classified into 5 to 50 ⁇ m or so. If the particle diameter of luminescent material is too small, such as 1 ⁇ m or less, the ratio of the non- emission surface layer may be undesirably increased, thus deteriorating the intensity of emission.
  • the luminescent materials according to this embodiment should preferably be employed after the classification thereof within the range of 5 to 50 ⁇ m or so.
  • the luminescent material according to this embodiment is a bluish luminescent material. Therefore, it is possible to obtain a white light- emitting device as this luminescent material is employed in combination with a yellow luminescent material. A white light-emitting device can be obtained even when this bluish luminescent material is employed in combination with a greenish luminescent material and a reddish luminescent material, or even when this bluish luminescent material is employed in combination with a yellowish luminescent material and a reddish luminescent material.
  • the luminescent material according to this embodiment can be employed in combination with a greenish luminescent material and a reddish luminescent material, thereby making it possible to provide a white light-emitting device.
  • the greenish luminescent material or the yellowish luminescent material can be defined as being a luminescent material having a major emission peak in a wavelength region ranging from 510 to 580 nm.
  • silicate luminescent materials such as (Sr, Ca, Ba)2Si ⁇ 4:Eu, Ca3(Sc, Mg) 2S13O12 :Ce, CaSc2 ⁇ 4:Ce, etc.; aluminate luminescent materials such as (Y, Gd) 3 (Al, Ga) 5012 1 Ce, BaMgAl ⁇ o ⁇ l7 : Eu, Mn, etc.; sulfide luminescent materials such as (Ca, Sr, Ba)Ga2S4:Eu, etc.; alkaline earth oxynitride luminescent materials such as (Ca, Sr, Ba) Si2 ⁇ 2N2 : Eu, etc.; and rare earth silicate nitride luminescent materials such as (Y, La, G
  • the term "major emission peak” it is intended to mean a wavelength at which the peak intensity of the emission spectrum as reported so far in the prior documents or patent publications becomes the largest.
  • the fluctuation of emission peak of around 10 nm due to the addition of a small amount of an element or due to slight changes in composition on the occasion of manufacturing the luminescent material may be regarded as being the major emission peak that has been reported so far.
  • the red luminescent material can be defined as being a luminescent material having a major emission peak in a wavelength region ranging from orange to red and having a wavelength of 580 to 680 nm.
  • red luminescent material it is possible to employ, for example, silicate luminescent materials such as (Sr, Ca, Ba)2SiC>4:Eu, etc.; tungstate luminescent materials such as Li(Eu, Sm)W2 ⁇ g, etc.; oxyfluoride luminescent materials such as 3.5MgO- 0.5MgF2 • Ge ⁇ 2 :Mn ⁇ + , etc.; oxide luminescent materials such as YV ⁇ 4:Eu, etc.; oxysulfide luminescent materials such as (La, Gd, Y)2 ⁇ 2S:Eu, etc.; sulfide luminescent materials such as (Ca, Sr, Ba) S: Eu, etc.; and nitride luminescent materials such as (Sr, Ba, Ca) 2Si5Ng:Eu, (Sr, Ca) AlSiN3 : Eu, etc.
  • silicate luminescent materials such as (Sr, Ca, Ba)2SiC>
  • the emission device shown in FIG. 9 is constituted by a resin stem 200.
  • This resin stem 200 comprises two leads 201 and 202 constituting a lead frame and a resin portion 203 which is formed integral with the lead frame.
  • This resin portion 203 is provided with a recess 205 having an upper opening which is wider than the bottom thereof.
  • This recess is provided, on the sidewall thereof, with a reflective surface 204.
  • a light-emitting chip 206 is mounted on a central portion of the approximately circular bottom of the recess 205 by an Ag paste, etc. As the light-emitting chip 206, it is possible to employ those which are capable of emitting an ultraviolet ray or light of the visible region.
  • the electrodes (not shown) of the light-emitting chip 206 are connected, through bonding wires 207 and 208 made of Au and the like, with the lead 201 and the lead 202, respectively.
  • the arrangement of these leads 201 and 202 can be optionally modified.
  • a luminescent layer 209 is disposed in the recess 205 of the resin portion 203.
  • This luminescent layer 209 can be formed by dispersing the luminescent material 210 of this embodiment in a resin layer 211 made of, for example, silicone resin at a ratio ranging from 5 to 50 wt%.
  • the luminescent material can be adhered by various kinds of binders, such as an organic material, a resin for example, or an inorganic material, such as glass.
  • the binder formed of an organic material it is suitable to use a transparent resin which is highly light-proof, such as epoxy resin, acrylic resin other than the aforementioned silicone resin.
  • the binder formed of an inorganic material it is suitable to use a low-melting glass wherein alkaline earth borate, etc. is employed; an ultra-fine powder of silica or alumina, etc. for enabling the luminescent material of a relatively large grain size to be adhered; or an alkaline earth phosphate that can be obtained by sedimentation.
  • These binders may be employed singly or in combination of two of more kinds.
  • the luminescent material to be employed in the luminescent layer may be applied with surface-coating as required.
  • This surface-coating is effective in preventing the luminescent material from being deteriorated by external factors such as heat, moisture and ultraviolet rays. Further, this surface-coating is also effective in adjusting the dispersibility of the luminescent material, thus facilitating the design of the luminescent layer.
  • the light-emitting chip 206 it is also possible to employ a flip-chip structure wherein an n- type electrode and a p-type electrode are both disposed on the same surface thereof. In this case, it is possible to overcome the problems accompanied with wiring, such as the cut-off or peeling of wire and the absorption of light by the wire, thereby making it possible to obtain a semiconductor light-emitting device which is excellent in reliability and in luminance. Further, an n-type substrate may be employed for forming the light-emitting chip 206, thus fabricating the following structure.
  • an n-type electrode is formed on the underside of the n-type substrate and a p-type electrode is formed on the top surface of the semiconductor layer on the substrate with either the n- type electrode or the p-type electrode being mounted on the lead.
  • the n-type electrode or the p- type electrode may be connected with the other lead by wire.
  • the size of the light-emitting chip 206 as well as the size and configuration of the recess 205 may be optionally modified.
  • the emission device shown in FIG. 10 comprises a resin stem 100, a semiconductor light-emitting element 106F mounted on the resin stem 100, and a sealing body 111 covering the semiconductor light-emitting element 106F.
  • the resin stem 100 comprises two leads 101 and 102 constituting a lead frame and a resin portion 103 which is formed integral with the lead frame. These leads 101 and 102 are disposed in such a manner that one end of each of these leads faces close to the other. The other end of each of these leads is extended in a direction opposite to the other and protruded out of the resin portion 103.
  • the resin portion 103 is provided with an opening 105, on the bottom of which a protective Zener diode 106E is mounted by an adhesive 107.
  • a protective Zener diode 106E is mounted on this protective Zener diode 106E. Namely, a diode 106E is mounted on the lead 101.
  • a wire 109 is connected at one end thereof with the diode 106E and at the other end with the lead 102.
  • the semiconductor light-emitting element 106F is surrounded by the inner walls of the resin portion 103.
  • the inner walls are inclined in the light-extracting direction, thereby enabling them to act as a reflective surface 104 for reflecting light.
  • the sealing body 111 filled in the opening 105 contains a luminescent material 110.
  • the semiconductor light-emitting element 106F is laminated on the protective Zener diode 106E.
  • As the luminescent material 110 a luminescent material according to this embodiment can be employed.
  • the protective Zener diode 106E is formed of a planar structure wherein a p-type region 152 is formed on the surface of an n-type silicon substrate 150.
  • a p-side electrode 154 is formed in a p-type region 152 and an n-side electrode 156 is formed on the underside of the substrate 150.
  • an n-side electrode 158 is formed also on the top surface of the Zener diode 106E.
  • These two n-side electrodes 156 and 158 are connected with each other through a wiring layer 160 which is provided on the sidewall of the Zener diode 106E.
  • a high reflection film 162 is formed on the top surface of the Zener diode 106E on which the p-side electrode 154 and the n-side electrode 158 are provided.
  • This high reflection film 162 is a film which exhibits a high reflectance to the light to be emitted from the light-emitting element 106F.
  • a buffer layer 122, an n-type contact layer 123, an n-type clad layer 132, an active layer 124, a p-type clad layer 125 and a p-type contact layer 126 are successively laminated on a translucent substrate 138. Further, an n-side electrode 127 is deposited on the n- type contact layer 123, and a p-side electrode 128 is deposited on the p-type contact layer 126. The light emitted from the active layer 124 is taken up through the translucent substrate 138.
  • the light-emitting element 106F constructed in this manner is flip-chip-mounted via a bump on the diode 106E.
  • the p-side electrode 128 of the light-emitting element 106F is electrically connected through a bump 142 with the n-side electrode 158 of the diode 106E.
  • the n-side electrode 127 of the light-emitting element 106F is electrically connected through a bump 144 with the p-side electrode 154 of the diode 106E.
  • One end of a wire 109 is bonded to the p-side electrode 154 of the diode 106E and the other end of the wire 109 is connected with the lead 102.
  • a semiconductor light-emitting element 51 is mounted, through a mounting material 52, on a lead 50' and covered with a pre-dipping material 54.
  • a lead 50 is connected with the semiconductor light-emitting element 51 and the resultant composite body is sealed with a casting material 55.
  • the luminescent material according to this embodiment is contained in the pre-dipping material 54.
  • a light-emitting device for example a white LED, employs a blue luminescent material exhibiting a narrow-band emission spectrum. Because of this, the light-emitting device according to this embodiment is most suited for use not only as an ordinary illumination substituting for a fluorescent lamp, but also as a luminescence device where a filter such as a color filter is used in combination with a light source, for example, as a light source for the backlight of a liquid crystal device.
  • the white LED according to this embodiment since it can be combined with a light exhibiting a spectrum of a narrow half-band width, it is possible to efficiently utilize a specific wavelength when employed in combination with a filter.
  • rare earth silicate nitride luminescent materials such as (Y, La, Gd, Lu) 2Si3 ⁇ 3N 4 :Tb,Ce, (La, Y, Gd, Lu) 3Si8C>4Ni ⁇ : Tb, Ce, etc. are employed as a green luminescent material, and oxyfluoride luminescent materials such as 3.5MgO- 0.5MgF2 -GeC ⁇ : Mn 4+ , etc.
  • the light-emitting device according to this embodiment is most suited for use as a backlight of a liquid crystal device.
  • Example 1 A Li2(Can.96, Euo.04) sio 4 luminescent material was prepared.
  • the raw material powder 14.8g of Li2CC>3 powder, 19.2g of CaCC>3 powder, 12. Iq of Si ⁇ 2 powder, and 1.4g of EU2O3 powder were prepared.
  • 0.3g of NH4CI was employed as a crystal growth promoting agent and these starting materials were uniformly mixed in a ball mill.
  • the mixed raw material thus obtained was placed in a sintering vessel and sintered under the following sintering conditions. First of all, in a reducing atmosphere of N2/H2, the mixed raw material was sintered at a temperature ranging from 700 to 1000°C for 3-24 hours to obtain a primary sintered product.
  • This primary sintered product was pulverized and then placed again in a crucible, which was then placed in a furnace. The interior of the crucible was purged with nitrogen in vacuum. Furthermore, the resultant product was again sintered for 2-24 hours in a reducing atmosphere of N2/H2 containing hydrogen at a concentration of 5%-less than 99% and at a temperature ranging from 700 to 1000°C to obtain a secondary- sintered product.
  • This secondary sintered product was pulverized in water, sieved and dehydrated by suction filtration.
  • the resultant powder was dried at a temperature of 100°C in a drying oven and then sieved to obtain a luminescent material of this example.
  • the luminescent material of Example 1 thus obtained was subjected to quantitative analysis by an ICP emission spectrometric method, the luminescent material of this example was confirmed as having a composition corresponding approximately to the raw materials charged.
  • each of constituent elements was varied as shown in the following Table 1, thus manufacturing the luminescent materials of Examples 2-9 and Comparative Example 1.
  • a BaMgAIi Q Ol7 Eu luminescent material which was available in the market was employed as Comparative Example 2.
  • the luminescent material of Comparative Example 1 contained no Ca and was constituted by only Sr. Table 1 shows the peak wavelength of each of the luminescent materials as they were excited at a wavelength of 390 nm, the crystal structures thereof, the peak intensity as they were excited at a wavelength of 380 nm, and changes of peak intensity as they were excited at a wavelength of 420 nm.
  • the crystal structure thereof was hexagonal and found to exhibit yellow emission having a peak wavelength of 575nm and a half-band width of 130 nm upon excitation with a light of 400 nm in wavelength.
  • the luminescent material of Comparative Example 2 i.e. the BaMgAlI Q C 1 I7 : Eu luminescent material
  • blue emission having a peak wavelength of 450 nm and a half-band width of 55 nm upon excitation with a light of 400 nm in wavelength.
  • the exciting wavelength was fluctuated from 380 to 420 nm
  • the ratio of intensity of peak wavelength was lowered by as large as 75%, thus indicating a strong dependency of emission intensity on the exciting wavelength.
  • this luminescent material is accompanied with the drawback that, on the occasion of designing it to obtain white light, the quantity of the luminescent material to be incorporated is required to be greatly changed depending on the variability of the exciting light source, etc.
  • a (Y, Gd) 3 (Al, Ga)5 ⁇ i2 :Ce luminescent material which was a yellow luminescent material and available in the market, was used in combination with a blue LED chip to manufacture a white LED device.
  • This white LED device was employed as Comparative Example 3. More specifically, as shown in FIG. 10, this LED chip was mounted via a bump on a diode, thus creating a light- emitting device having a so-called flip-chip structure.
  • the content of the luminescent materials of the white LED device of Comparative Example 3 was adjusted so as to regulate the color temperature thereof to 4000K.
  • Example 13 As is apparent from the comparison between Example 13 and Comparative Example 3, the white LED device of Example 13 was more excellent in average color rendering index Ra as compared with that of Comparative Example 3.
  • the luminescent material of Example 3 a synthesized green luminescent material constituted by a (Y, La, Gd, Lu) 2Si3 ⁇ 3N4 :Tb, Ce luminescent material and a red luminescent material available in the market and constituted by a (La, Gd, Y)2 ⁇ 2S:Eu luminescent material were mixed together to obtain a mixture of luminescent materials. This mixture was then dispersed in silicone resin to prepare a resinous mixture. The resinous mixture thus obtained was used in combination with a near-ultraviolet LED of 391 nm in peak wavelength to manufacture a white LED light-emitting device. More specifically, a light-emitting device of a surface-mounting structure as shown in FIG.
  • Example 11 was manufactured, which was identified as Example 14.
  • the content of the luminescent materials of the white LED device of Example 14 was adjusted so as to regulate the color temperature thereof to 4000K.
  • the emission spectrum obtained as the color temperature thereof was adjusted to 4000K is shown in FIG. 14.
  • a blue luminescent material which emits light when excited by a light having an emission peak falling within the range of 360 nm to 460 nm and to provide a light-emitting device employing such a luminescent material.

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne une matière luminescente de silicate de lithium et de calcium, qui comprend une phase cristalline quadratique contenant Li, Ca, Si et O et un activateur contenant Eu. La matière luminescente présente une longueur d'onde de pic du spectre d'émission tombant à l'intérieur d'une région de longueurs d'onde de 470 à 490 nm lorsqu'elle est excitée par de la lumière ayant un pic d'émission tombant à l'intérieur d'une région de longueurs d'onde de 360 à 460 nm.
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