CN103443942A - Semiconductor light-emitting element and light-emitting device - Google Patents

Semiconductor light-emitting element and light-emitting device Download PDF

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Publication number
CN103443942A
CN103443942A CN2012800154210A CN201280015421A CN103443942A CN 103443942 A CN103443942 A CN 103443942A CN 2012800154210 A CN2012800154210 A CN 2012800154210A CN 201280015421 A CN201280015421 A CN 201280015421A CN 103443942 A CN103443942 A CN 103443942A
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light
oxygen
layer
quantum dot
dielectric film
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春日井秀纪
吉田真治
山中一彦
大崎裕人
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/44—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
    • H—ELECTRICITY
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    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
    • H—ELECTRICITY
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
    • H01L2224/491—Disposition
    • H01L2224/49105—Connecting at different heights
    • H01L2224/49107—Connecting at different heights on the semiconductor or solid-state body
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
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    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0095—Post-treatment of devices, e.g. annealing, recrystallisation or short-circuit elimination
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    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H01L33/504—Elements with two or more wavelength conversion materials
    • H—ELECTRICITY
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    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/505—Wavelength conversion elements characterised by the shape, e.g. plate or foil

Abstract

Disclosed is a semiconductor light-emitting element with which a decline in light emission efficiency due to oxidation of quantum dot phosphors can be suppressed. A semiconductor light-emitting element (1) according to the present invention comprises: a semiconductor layer containing an active layer (13); a first metal layer (16) formed on the semiconductor layer; a first insulating film (18) formed on the first metal layer (16) so as to cover the upper face and side face of the semiconductor layer; a second insulating film (20) containing fine semiconductor particles formed on the first insulating film (18); and a third insulating film (21) formed on the second insulating film (20). The second insulating film (20) is covered by the first insulating film (18) and the third insulating film (21).

Description

Semiconductor light-emitting elements and light-emitting device
Technical field
The present invention relates to, luminescent coating has been utilized to semiconductor light-emitting elements and the light-emitting device of quantum dot fluorescence body.
Background technology
White LED (Light Emitting Diode) for illumination light source, LCD backlight with light source etc., the semiconductor light-emitting elements of combination radiation blue light and the fluorophor that sends green, yellow, red etc. fluorescence are realized.The kind of fluorophor has, rare-earth phosphor, organic fluorescent or quantum dot fluorescence body of consisting of semiconductor etc.
At present, general White LED is utilized to rare-earth phosphor.Rare-earth phosphor is, added as the oxide of the rare earth ion of activator and nitride etc.After electronics in rare earth ion is energized, while transferring to ground state, send fluorescence.
On the other hand, for the quantum dot fluorescence body, owing to directly utilizing absorption edge, luminous, therefore can realize high-quantum efficiency.Particularly, the quantum dot fluorescence body is, the compound semiconductor crystallization become to the semiconductor microactuator particle of the particle of nano-scale, can utilize quantum limitation effect.What have is characterized as, and changes by the particle diameter that makes this semiconductor microactuator particle, thereby can adjust fluorescent peak wavelength etc.
For such combination fluorophor and the White LED of semiconductor light-emitting elements, at packaging body configuring semiconductor light-emitting component, fluorophor is comprised in the transparent material of resin etc., is configured to cover the semiconductor light-emitting elements in packaging body, usings as structure in the past.For example, patent documentation 1 illustrates, and has utilized the structure of the light-emitting device of rare-earth phosphor.
Figure 28 is the sectional view that the disclosed light-emitting device in the past of patent documentation 1 is shown.
As Figure 28 illustrates, the structure of light-emitting device in the past is, semiconductor light-emitting elements 1011 is configured in the terminal 1012 exposed in container 1018, and, the resin 1015 that comprises fluorophor 1016, be filled in container 1018 in the mode that covers semiconductor light-emitting elements 1011.
On the other hand, proposed following method, that is, on semiconductor light-emitting elements, directly configuration packet contains the luminescent coating of fluorophor, thereby forms more simply the semiconductor light-emitting elements that radiates the white light same with White LED.For example, patent documentation 2 illustrates, and has utilized the structure of the semiconductor light-emitting elements in the past of rare-earth phosphor.
Figure 29 is the sectional view that the disclosed semiconductor light-emitting elements in the past of patent documentation 2 is shown.
As Figure 29 illustrates, for semiconductor light-emitting elements in the past, at first, on sapphire substrate 1001, stack gradually Si Doped n-type GaN layer 1002, Si Doped n-type AlGaN layer 1003, non-Doped GaN active layer 1004, Mg doped p type AlGaN layer 1005, Mg doped p type GaN layer 1006 and form laminated section, excavate the part on surface of this laminated section until reach Si Doped n-type GaN layer 1002, form n lateral electrode 1009 on Si Doped n-type GaN layer 1002.And, form p-type electrode 1008 on Mg doped p type GaN layer 1006, form the GaN based semiconductor light-emitting device of output luminescence-utraviolet.
And then, on this GaN based semiconductor light-emitting device, be coated in resin the luminescent coating 1007 (resin that for example, has disperseed Y2O3:Eu3+) that has disperseed fluorophor.It is implemented to mask pattern, carry out ultraviolet exposure, only make to want remaining partly solidified as luminescent coating 1007, remove unwanted part.Accordingly, form the semiconductor light-emitting elements that only in p lateral electrode 1008 part in addition on Mg doped p type GaN layer 1006 top, has formed luminescent coating 1007.
(prior art document)
(patent documentation)
Patent documentation 1: the flat 11-500584 communique of Japanese Unexamined Patent Application Publication
Patent documentation 2: Japanese kokai publication hei 10-012916 communique
Brief summary of the invention
The problem that invention will solve
Yet, for the semiconductor light-emitting elements of Figure 29, in the situation that form the luminescent coating that has disperseed fluorophor on semiconductor light-emitting elements, obviously there are the following problems.At first, in the situation that utilize rare-earth phosphor to form luminescent coating, the rare-earth phosphor particle that need in very thin film, contain ormal weight on the GaN based semiconductor light-emitting device.In the case, the concentration of the rare-earth phosphor particle in luminescent coating becomes very high, by the density of the rare earth ion of each effective unit volume, uprises.Its result is, the reduction that produces the quantum efficiency of fluorophor because of concentration quenching.
On the other hand, can enumerate following method, that is, for fear of such concentration quenching, the unfavorable rare earth ion that is used as fluorophor, and utilize the quantum dot fluorescence body as fluorophor.Yet, in the situation that utilize the quantum dot phosphor to form luminescent coating on the GaN based semiconductor light-emitting device, following problem occurs.
For the quantum dot fluorescence body, this particle size is very little, and therefore, quantum efficiency depends on the surface characteristic of surface structure and surface crystallization etc. very much.Therefore, quantum efficiency, because the defect on the surface that is formed on the quantum dot fluorescence body sharply reduces.
Oxygen sees through the resin disperseed the quantum dot fluorescence body etc. and reaches the quantum dot fluorescence body, makes the surface oxidation of quantum dot fluorescence body, thereby produces this defect that is formed on surface.And then this oxidative phenomena, because the light sent from semiconductor light-emitting elements is accelerated.
Therefore, in the situation that by the quantum dot fluorescence body be configured in semiconductor light-emitting elements nearby, the optical density that shines the quantum dot fluorescence body becomes very strong, the fierce oxidation of quantum dot fluorescence body.
Summary of the invention
In order to solve described problem, the object of the present invention is to provide a kind of semiconductor light-emitting elements and light-emitting device, oxygen by suppressing one of reason as the oxidation of quantum dot fluorescence body (semiconductor microactuator particle) contacts with fluorophor particle, thereby can suppress the reduction of the quantum efficiency of quantum dot phosphor, can realize long-term reliability.
For the means of dealing with problems
In order to solve described problem, one of embodiment of the semiconductor light-emitting elements the present invention relates to, wherein, semiconductor layer, comprise active layer; The first metal layer, be formed on semiconductor layer; The first dielectric film, be formed on the first metal layer, and in the mode of the top and side that covers described semiconductor layer and be formed; The second dielectric film, be formed on the first dielectric film and comprise the semiconductor microactuator particle; And the 3rd dielectric film, being formed on the second dielectric film, the second dielectric film is covered by the first dielectric film and the 3rd dielectric film.
According to the present embodiment, the second dielectric film that comprises semiconductor microactuator particle (quantum dot fluorescence body) is covered by the 3rd dielectric film, therefore can suppress oxygen and see through to the second dielectric film.Accordingly, can suppress contacting of oxygen and semiconductor microactuator particle, the quantum efficiency that therefore can suppress semiconductor microactuator particle (quantum dot fluorescence body) reduces.
And preferably, in one of embodiment of the semiconductor light-emitting elements the present invention relates to, described the first dielectric film on described the first metal layer is formed with peristome.
And, preferably, in one of embodiment of the semiconductor light-emitting elements the present invention relates to, at peristome, being formed with the second metal level, this second metal level is connected with the first metal layer.
And preferably, in the embodiment of the semiconductor light-emitting elements the present invention relates to, the first metal layer is transparency electrode, the material of transparency electrode is, has been added some among the indium oxide of tin, the tin oxide that has been added antimony and zinc oxide.
And preferably, in one of embodiment of the semiconductor light-emitting elements the present invention relates to, the semiconductor microactuator particle is the quantum dot fluorescence body, the semiconductor microactuator particle is constituted as and absorbs luminous from active layer, and sends the luminous different light from active layer.
And, preferably, in one of embodiment of the semiconductor light-emitting elements the present invention relates to, the 3rd dielectric film is film and the high film of thermal conductivity that does not at least make oxygen see through, and the 3rd dielectric film is some among aluminium nitride, silicon nitride, silica nitrogen, Si oxide, zinc oxide, aluminum oxide and indium oxide.
And, preferably, in one of embodiment of the semiconductor light-emitting elements the present invention relates to, between the second dielectric film and the 3rd dielectric film, possessing the 4th dielectric film, the second dielectric film is covered by the 4th dielectric film, and the 4th dielectric film is covered by the 3rd dielectric film.
And one of embodiment of the light-emitting device the present invention relates to, be the light-emitting device that possesses described semiconductor light-emitting elements, possesses: packaging body consists of resin, and has recess; Lead frame, expose in the bottom surface of recess; Described semiconductor light-emitting elements, be arranged on the lead frame in recess; And resin portion, in recess, to cover the mode on described semiconductor light-emitting elements, being formed, resin portion comprises heat conduction particulate.
In order to solve described problem, one of embodiment of the first light-emitting device the present invention relates to wherein, possesses: packaging body consists of resin, and has recess; Lead frame, expose in the bottom surface of recess; Semiconductor light-emitting elements, be arranged on the lead frame in recess; And first resin portion, in recess, in the mode that covers semiconductor light-emitting elements, being formed, the first resin portion consists of the first absorbing particle of quantum dot fluorescence body and adsorb oxygen.
And then preferably, in one of embodiment of the first light-emitting device the present invention relates to, the particle diameter of the first absorbing particle is below 100nm.
And then, preferably, in one of embodiment of the first light-emitting device the present invention relates to, also possess the second resin portion, this second resin portion, be formed in the mode that covers the first resin portion of exposing in recess, the second resin portion, the second absorbing particle with adsorb oxygen.
And then preferably, in one of embodiment of the first light-emitting device the present invention relates to, the particle diameter of the first absorbing particle is below 100nm, the particle diameter of the second absorbing particle is below 100 μ m.
And then, preferably, in one of embodiment of the first light-emitting device the present invention relates to, on the surface of recess, the layer that is provided with adsorb oxygen or does not make oxygen see through.
And then preferably, in one of embodiment of the first light-emitting device the present invention relates to, the first absorbing particle and the second absorbing particle, do not absorb from the light wavelength of semiconductor light-emitting elements radiation and from the light wavelength of quantum dot fluorescence body radiation.
And then, preferably, in one of embodiment of the first light-emitting device the present invention relates to, on the top of the second resin portion, glass cover being arranged, glass cover and packaging body are bonding.
And, in one of other embodiments of the first light-emitting device the present invention relates to, wherein, the light-emitting device that possesses the wavelength converter section in the semiconductor light-emitting elements that is arranged on packaging body and packaging body, the wavelength converter section by resin and quantum dot fluorescence body and at least the absorbing particle of adsorb oxygen form.
According to described structure, evenly mixing quantum dot phosphor and at least absorbing particle of adsorb oxygen in resin, the oxygen that sees through resin is adsorbed by absorbing particle.Accordingly, can make the oxidation of quantum dot fluorescence body reduce.Its result is, can prevent that the luminous efficiency of the quantum dot fluorescence body that causes because of oxidation from reducing.
And then preferably, in one of other embodiments of the first light-emitting device the present invention relates to, the particle diameter of absorbing particle is below 100nm.
In the situation that the wavelength of visible region, the particle diameter of quantum dot fluorescence body is for roughly below 20nm.This is because under the absorbing particle diameter is several microns, tens micron-sized situations, the dispersion of quantum dot fluorescence body is inhomogeneous, and the even cause of irregular colour occurs.
And then, preferably, in one of other embodiments of the first light-emitting device the present invention relates to, the two-layer structure that the wavelength converter section is ground floor and the second layer, ground floor, hybrid resin and quantum dot fluorescence body and the absorbing particle of adsorb oxygen at least, and at least cover semiconductor light-emitting elements, the second layer, hybrid resin and the absorbing particle of adsorb oxygen at least, the second layer is formed on ground floor.
The layer that has disperseed absorbing particle is set in the second layer on ground floor, thereby the oxygen seen through to the second layer is adsorbed by absorbing particle.Therefore, can suppress significantly to see through to the oxygen of ground floor.
And then preferably, in one of other embodiments of the first light-emitting device the present invention relates to, the particle diameter of the absorbing particle of ground floor is below 100nm, the particle diameter of the absorbing particle of the second layer is below 100 μ m.
According to described structure, it is even that ground floor can suppress irregular colour.If 100 μ m are large for the size ratio of the absorbing particle of the second layer, the sedimentation caused according to the weight because of particle itself, dispersiveness degenerates, therefore, preferably below 100 μ m.
And, preferably, in one of other embodiments of the first light-emitting device the present invention relates to, between wavelength converter section and packaging body side, the layer that adsorb oxygen is set or does not make oxygen see through.Oxygen also sees through from the packaging body side, therefore can more suppress the oxidation of quantum dot phosphor.
And then preferably, in one of other embodiments of the first light-emitting device the present invention relates to, absorbing particle, do not absorb the wavelength of semiconductor light-emitting elements and the wavelength of quantum dot fluorescence body.
If absorbing particle absorbs the wavelength of semiconductor light-emitting elements and quantum dot fluorescence body, the luminous intensity of light-emitting device reduces.Therefore, preferably, utilize and do not absorb the absorbing particle from the wavelength of semiconductor light-emitting elements and quantum dot fluorescence body.
And then, preferably, in one of other embodiments of the first light-emitting device the present invention relates to, on the top of wavelength converter section, glass cover being arranged, glass cover and packaging body are bonding, thus sealing wavelength converter section.
Glass does not make oxygen see through, and therefore, the top of the oxygen absorbed layer arranged on the top of quantum dot fluorescence body layer is covered by glass, thereby can suppress significantly to see through to the oxygen of quantum dot phosphor layer.Its result is, can more prevent the reduction of the luminous efficiency of the quantum dot fluorescence body that causes because of oxidation, realizes long-term reliability.
In order to solve described problem, one of embodiment of the second light-emitting device the present invention relates to possesses: packaging body consists of resin, and has recess; Lead frame, expose in the bottom surface of described recess; The first oxygen absorbed layer, be formed in the mode that at least covers the lead frame exposed described bottom surface; Quantum dot fluorescence body layer, be formed on described the first oxygen absorbed layer; And the second oxygen absorbed layer, in the mode that covers described quantum dot fluorescence body layer, be formed.
So, the present embodiment, possess the layer (oxygen absorbed layer) of the absorbing particle that has disperseed the layer (quantum dot fluorescence body layer) of quantum dot fluorescence body and comprised at least adsorb oxygen of disperseing in resin in the semiconductor light-emitting elements that is installed on packaging body, resin, the top of quantum dot fluorescence body layer and bottom are covered by described oxygen absorbed layer.
According to described structure, be arranged on the absorbing particle adsorb oxygen of the oxygen absorbed layer of the top of quantum dot fluorescence body layer and bottom.Accordingly, can suppress to see through to the oxygen of quantum dot phosphor layer.Its result is, can suppress the reduction of the luminous efficiency of the quantum dot fluorescence body that causes because of oxidation.
And then, preferably, in one of embodiment of the second light-emitting device the present invention relates to, on the top of described the second oxygen absorbed layer, be provided with glass cover.That is to say, preferably, on the top of the oxygen absorbed layer on the top that is formed on quantum dot fluorescence body layer, glass cover is set.
Glass does not make oxygen see through, and therefore, the top of the oxygen absorbed layer arranged on the top of quantum dot fluorescence body layer is covered by glass, thereby can cover the face contacted with air layer by glass cover, accordingly, can suppress significantly to see through to the oxygen of quantum dot phosphor layer.Its result is, can more suppress the reduction of the luminous efficiency of the quantum dot fluorescence body that causes because of oxidation.
And then, preferably, in one of embodiment of the second light-emitting device the present invention relates to, at the inwall of described recess, the reflective metal layer that is provided with adsorb oxygen or does not make oxygen see through or the Porous particle layer of adsorb oxygen.That is to say, preferably, cover between the layer and packaging body side of the top of quantum dot phosphor layer or bottom the reflecting metallic film that is provided with adsorb oxygen and does not make oxygen see through or the Porous particle membrane of adsorb oxygen at quantum dot fluorescence body layer or by the oxygen absorbed layer.
According to this structure, can adsorb the oxygen seen through from the packaging body sidewall, therefore can more suppress the oxidation with the quantum dot fluorescence body of the quantum dot fluorescence body layer of packaging body sidewall contact.
And then, preferably, in one of embodiment of the second light-emitting device the present invention relates to, at the inwall of described recess, the reflective metal layer that is provided with adsorb oxygen or does not make oxygen see through or the Porous particle layer of adsorb oxygen.
And then, preferably, in one of embodiment of the second light-emitting device the present invention relates to, the absorbing particle comprised in described the first oxygen absorbed layer and the second oxygen absorbed layer comprises the some of titanium oxide, niobium oxide, hafnium oxide, indium oxide, tungsten oxide, tin-oxide, zinc oxide, Zirconium oxide, magnesium oxide, sb oxide, silicon dioxide, silica nitrogen.
And then preferably, in one of embodiment of the second light-emitting device the present invention relates to, described quantum dot fluorescence body layer comprises CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnZe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnZeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgSeTe, CdHgSTe, HgZnSS, HgZnSeTe, HgZnSTe, GaN, GaP, GaAs, GaSb, AlN, AlGaN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, InGaN, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb.
The invention effect
According to the present invention, can prevent the reduction of the luminous efficiency of the quantum dot fluorescence body that causes because of oxidation, therefore can realize having semiconductor light-emitting elements and the light-emitting device of long-term reliability.
The accompanying drawing explanation
Fig. 1 is the sectional view that the semiconductor light-emitting elements that embodiments of the invention 1 relate to is shown.
Fig. 2 is the amplification sectional view of the a-quadrant of the semiconductor light-emitting elements that relates to of embodiments of the invention 1.
Fig. 3 is the amplification sectional view in the B zone of the semiconductor light-emitting elements that relates to of embodiments of the invention 1.
Fig. 4 is the figure illustrated by the oxygen permeability of the dielectric film of resin material.
Fig. 5 is the figure illustrated for the oxygen permeability of the oxygen-proof membrane of embodiments of the invention 1.
Fig. 6 is the figure that the manufacture method of the semiconductor light-emitting elements that embodiments of the invention 1 relate to is shown.
Fig. 7 is the sectional view that the variation of the semiconductor light-emitting elements that embodiments of the invention 1 relate to is shown.
Fig. 8 is the sectional view that the semiconductor light-emitting elements that embodiments of the invention 2 relate to is shown.
Fig. 9 is the amplification sectional view in the C zone of the semiconductor light-emitting elements that relates to of embodiments of the invention 2.
Figure 10 is the amplification sectional view in the D zone of the semiconductor light-emitting elements that relates to of embodiments of the invention 2.
Figure 11 is the figure that the manufacture method of the semiconductor light-emitting elements that embodiments of the invention 2 relate to is shown.
Figure 12 is the sectional view that the variation of the semiconductor light-emitting elements that embodiments of the invention 2 relate to is shown.
Figure 13 is the sectional view that the light-emitting device that embodiments of the invention 3 relate to is shown.
Figure 14 is the sectional view that the semiconductor light-emitting elements that embodiments of the invention 4 relate to is shown.
Figure 15 is the figure that the manufacture method of the semiconductor light-emitting elements that embodiments of the invention 4 relate to is shown.
Figure 16 is the sectional view that the light-emitting device that embodiments of the invention 5 relate to is shown.
Figure 17 is the sectional view that the light-emitting device that embodiments of the invention 6 relate to is shown.
Figure 18 is the sectional view that the light-emitting device that embodiments of the invention 7 relate to is shown.
Figure 19 is the sectional view that the light-emitting device that embodiments of the invention 8 relate to is shown.
Figure 20 is the sectional view that the light-emitting device that embodiments of the invention 9 relate to is shown.
Figure 21 is the sectional view that the light-emitting device that embodiments of the invention 10 relate to is shown.
Figure 22 is the sectional view that the light-emitting device that embodiments of the invention 11 relate to is shown.
Figure 23 is the sectional view that the light-emitting device that embodiments of the invention 12 relate to is shown.
Figure 24 is the sectional view that the light-emitting device that embodiments of the invention 13 relate to is shown.
Figure 25 is the sectional view that the light-emitting device that embodiments of the invention 14 relate to is shown.
Figure 26 is the sectional view that the light-emitting device that embodiments of the invention 15 relate to is shown.
Figure 27 is the sectional view that the light-emitting device that embodiments of the invention 16 relate to is shown.
Figure 28 is the sectional view that light-emitting device in the past is shown.
Figure 29 is the sectional view that semiconductor light-emitting elements in the past is shown.
Embodiment
Below, for each embodiment of the present invention, with reference to accompanying drawing, describe, still, the present invention is according to the record of claims and definite.Therefore, in the inscape of following embodiment, inscape that there is no record in claim, in order to realize problem of the present invention, might not need, still, be illustrated as the key element that forms preferred form.And, in each figure, identical inscape is enclosed to identical symbol.And each figure is ideograph, might not be the figure tightly illustrated.
And preferably, the semiconductor light-emitting elements of each embodiment of the present invention is to have the semiconductor light-emitting elements that carrys out luminous active layer with the wavelength of 380nm to 480nm.And, for the semiconductor microactuator particle as the quantum dot fluorescence body, preferably, absorb the wavelength 380nm to 480nm of semiconductor light-emitting elements, luminous between 450nm to 700nm.
And, in the present embodiment, for example, among the scope of described wavelength, situation that luminous light wavelength is 450nm from the active layer of semiconductor light-emitting elements, describe.And, in the present embodiment, following situation is described,, the quantum dot fluorescence body, absorb the wavelength 450nm of semiconductor light-emitting elements, these two kinds of semiconductor microactuator particles of the second semiconductor microactuator particle that the first semiconductor microactuator particle that is 530nm by for example peak wavelength and fluorescent peak wavelength are 620nm form.
(embodiment 1)
(structure)
The schematic configuration of the semiconductor light-emitting elements 1 related to for embodiments of the invention 1, utilize Fig. 1 to Fig. 3 to describe.Fig. 1 is the sectional view of the semiconductor light-emitting elements that relates to of embodiments of the invention 1.And Fig. 2 and Fig. 3 are the a-quadrant of the semiconductor light-emitting elements that relates to of embodiments of the invention 1 and the enlarged drawing in B zone.
As Fig. 1 illustrates, the semiconductor light-emitting elements 1 that embodiment 1 relates to is, for example, in the upper formation of substrate 10 (sapphire substrate), for example comprises as the semiconductor layer lit-par-lit structure body of the active layer 13 of InGaN/GaN Multiple Quantum Well.On this semiconductor layer lit-par-lit structure body, form the first metal layer 16 as the p electrode.Semiconductor layer lit-par-lit structure body is, for example stack gradually as the resilient coating 11 of Si Doped GaN layer, for example as the active layer 13 of the first cover layer 12 of Si doped with Al GaN layer, Multiple Quantum Well structure, for example, as the second cover layer 14 of Mg doped with Al GaN layer and as the contact layer 15 of Mg Doped GaN layer.
The first metal layer 16 on contact layer 15 is to make the transparency electrode from the light transmission of active layer 13.In the present embodiment, this transparency electrode is the indium oxide (ITO) that has been added tin.
Mode with the top and side of the top that covers this first metal layer 16 and semiconductor layer lit-par-lit structure body, form for example as silicon oxide layer (SiO 2), silicon nitride film (Si 1-xn x), pellumina (Al 2o 3) such the first dielectric film 18 with oxygen barrier.
And, on the first dielectric film 18, form the second dielectric film 20.This second dielectric film 20 is, for example, in silicones, the luminescent coating that the quantum dot fluorescence body that these two kinds of semiconductor microactuator particles of the second semiconductor microactuator particle 25b that the first semiconductor microactuator particle 25a that will be 530nm by the fluorescent peak wavelength and fluorescent peak wavelength are 620nm form disperses.
And the 3rd dielectric film 21 is formed the surface that covers the second dielectric film 20.The 3rd dielectric film 21, for example, by picture aluminium nitride film, silicon nitride film (Si 1-xn x), pellumina (Al 2o 3), silicon oxide layer (SiO 2), or oxygen silicon nitride membrane (SiO 1-xn 1-x-y) such dielectric film formation with oxygen barrier.That is to say, covered the surface of the second dielectric film 20 by the oxygen-proof membrane of the first dielectric film 18 and the 3rd dielectric film 21, thereby can suppress oxygen, enter into the second dielectric film 20.
And, in the regional A of Fig. 1, the first dielectric film 18 on the first metal layer 16 tops, form peristome, at this peristome, in the mode that is connected in the first metal layer 16, forms the second metal level 19a.
And, in regional B, form n electrode 17 on resilient coating 11, further, form the second metal level 19b on it.
Fig. 2 and Fig. 3 illustrate, position relationship in this zone A and regional B, the first dielectric film 18, the second dielectric film 20 and the 3rd dielectric film 21.
As Fig. 2 and Fig. 3 illustrate, the second dielectric film 20, be formed on than the first dielectric film 18 inboards.The 3rd dielectric film 21, be formed on than the first dielectric film 18 inboards and than second dielectric film 20 outsides.
So, the first dielectric film 18 consisted of the dielectric film with oxygen barrier and the 3rd dielectric film 21 cover the second dielectric film 20 of containing quantum dot phosphors, thereby can suppress seeing through to the oxygen of the second dielectric film 20.Therefore, can suppress contacting of semiconductor microactuator particle (quantum dot fluorescence body) and oxygen.Accordingly, can suppress the oxidation of semiconductor microactuator particle, therefore can reduce the reduction of the luminous efficiency of semiconductor light-emitting elements.
Then, for the effect of the oxygen-proof membrane specifically utilized in the present embodiment, utilize Fig. 4 and Fig. 5 to describe.Fig. 4 is the figure that the oxygen permeability of the dielectric film consisted of resin material is shown.Fig. 5 illustrates, and utilizes CVD (Chemical Vapor Deposition) method, electron magnetic resonance (Electron Cyclotron Resonance:ECR) sputtering method, electron beam (EB:Electron Beam) vapour deposition method to carry out the figure of oxygen permeability of the dielectric film of film forming.
As Fig. 4 illustrates, for semiconductor light-emitting elements contain fluorophor the time resin that utilizes oxygen permeability (situation that the resin thickness is 0.1mm), silicon is 460000cc/m 2day, epoxy is 50cc/m 2day, propylene is 657ccg/m 2day.
On the other hand, by the CVD method, the oxygen permeability of the aluminium nitride film (more than 8nm) of film forming, compare 0.4cc/m 2day (33 ℃ of temperature, humidity 0%) is low.And by the ECR sputter, the oxygen permeability of the aluminium oxide (17nm) of film forming is, 1.45cc/m 2day (30 ℃ of temperature, humidity 70%), also can make oxygen permeability step-down in humidity under high condition.Therefore, by the film by such, become the 3rd dielectric film 21, thereby can reduce the oxygen amount that reaches the quantum dot fluorescence body.And silicon oxide film (>15nm), oxygen silicon nitride membrane (24nm), also obtain 0.4cc/m 2the low like this value of day (33 ℃ of temperature, humidity 0%, 40 ℃ of temperature, humidity 0%), also can make oxygen permeability step-down in humidity under high condition.And then, in the situation that carry out film forming by the electron beam evaporation plating method, the density step-down of crystallization, therefore, in the situation that silicon oxide film at least becomes than 50nm thick-film, and, in the situation that pellumina becomes than 25nm thick-film, thereby can make oxygen permeability step-down.
And, in the present embodiment, the first metal layer 16 has been utilized to the indium oxide (ITO) that has been added tin, still, also can utilize the tin oxide that has been added antimony or zinc oxide etc.
And, utilized the silicones as the second dielectric film 20, but, for the second dielectric film 20, the transparent material that can easily mix the first semiconductor microactuator particle 25a and the second semiconductor microactuator particle 25b gets final product, for example, also can utilize epoxy resin, fluoride resin, the thermosetting resin of allyl resin etc., transparent polyimide resin, polyarylate resin, polyethylene terephthalate resin, polysulfone resin, the Parylene resin, the organic material of the thermoplastic resin of polyparabanic acid resin etc. etc., the unorganic glass perhaps formed by sol-gal process.
And, for the 3rd dielectric film 21, utilized aluminium nitride, still, be not limited only to this.For the 3rd dielectric film, also can utilize silicon nitride, silica nitrogen, Si oxide, zinc oxide, aluminum oxide or indium oxide.
And, for the structure of the quantum dot fluorescence body of the second dielectric film 20, can enumerate hud typed, quantum well type etc., still, in the present embodiment, can be suitable for which structure.
And, for the core that forms the quantum dot fluorescence body and the material of shell, for example, situation for the II-VI compounds of group, can enumerate from CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnZe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnZeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgSeTe, CdHgSTe, HgZnSS, HgZnSeTe, at least one that select in HgZnSTe etc.
And, example for the III-V compounds of group, can enumerate from GaN, GaP, GaAs, GaSb, AlN, AlGaN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, InGaN, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, InAlNP, InAlNAs, InAlNSb, InAlPAs, at least one that select in InAlPSb etc.
And, for substrate 10, utilized sapphire substrate, still, also can utilize GaN, SiC, Si, graphite, ZnO, AlN.And semiconductor light-emitting elements 1, can be also to have removed the structure of substrate 10 by laser lift-off etc.
(manufacture method)
Then, the manufacture method of the semiconductor light-emitting elements 1 related to for embodiments of the invention 1, below, utilize Fig. 6 to describe.Fig. 6 is the figure that the manufacture method of the semiconductor light-emitting elements that embodiments of the invention 1 relate to is shown.
As (a) of Fig. 6 illustrates, at first, by the organic metal vapour deposition process, upper at substrate 10 (sapphire substrate), the resilient coating 11 that deposition for example consists of the N-shaped GaN after the Si doping successively, the first cover layer 12 for example formed by the N-shaped AlGaN after the Si doping, the active layer 13, the second cover layer 14 for example formed by the p-type AlGaN after the Mg doping that for example by the Multiple Quantum Well of InGaN and GaN, are formed and the contact layer 15 for example formed by the p-type GaN after the Mg doping.
Then, on contact layer 15 surface, form not illustrated diaphragm pattern, by for example having utilized the dry ecthing of chlorine, as (b) of Fig. 6 illustrates, form the peristome 30 that reaches resilient coating 11.
Then, as (c) of Fig. 6 illustrates, by electron beam evaporation plating method or sputtering method, on the top of contact layer 15, for example, the transparency electrode consisted of ITO is carried out to film forming, using as the first metal layer 16.
Then, utilize plasma CVD method, preferably utilize the ECR sputtering method, will be as for example SiO of the first dielectric film 18 2, Si 2n 3, or Al 2o 3, be formed on each side of top and resilient coating 11, the first cover layer 12, active layer 13, the second cover layer 14, contact layer 15 and the first metal layer 16 of resilient coating 11 and the first metal layer 16.
Then; utilize photoetching; formation is equivalent to be used to form the peristome 35 of n electrode 17 and the second metal level 19a and 19b and 36 not illustrated diaphragm pattern; remove first dielectric film 18 at the position of opening by dry ecthing; accordingly; as (d) of Fig. 6 illustrates, form peristome 35 and 36.
Then, at the peristome 36 of the resilient coating 11 exposed, utilize photoetching and electron beam evaporation plating method, for example, form the n electrode 17 (Fig. 6 (d)) formed by Ti/Al/Ti/Au.
Then, as (e) of Fig. 6 illustrates, on the top of the first metal layer 16 exposed and n electrode 17, for example, form the second metal level 19a and the 19b formed by Cr/Au.Particularly, utilize photoetching to form not illustrated diaphragm pattern, utilize the electron beam evaporation plating method to carry out film forming to Cr/Au, by stripping method, form the second metal level 19a and 19b.
Then, for example, by rotary coating, spraying process or bar type rubbing method, for example, second dielectric film 20 that will consist of the silicones comprised as the semiconductor microactuator particle of core-shell type quantum point fluorophor is coated on comprehensively.At this, the semiconductor microactuator particle is, the second semiconductor microactuator particle 25b that the first semiconductor microactuator particle 25a that the fluorescent peak wavelength is 530nm and fluorescent peak wavelength are 620nm is mixed, is all the semiconductor microactuator particle of core material by the core-shell type quantum point fluorophor that CdSe or InP form, sheathing material consists of ZnS.Now, also can be by SiO 2film covers the semiconductor microactuator particle.
Then, utilize photoetching to form Etching mask, as (f) of Fig. 6 illustrates, the second dielectric film 20 that utilizes aqueous slkali to remove to comprise unwanted semiconductor microactuator particle.Now, as Fig. 2 and Fig. 3 illustrate, with the end of the second dielectric film 20 of comprising the semiconductor microactuator particle, be positioned at than the mode of the first dielectric film 18 inboards and carry out opening.
Then, for example, utilize electron beam evaporation plating method, plasma CVD method, preferably utilize the ECR sputtering method, for example, with the thick thickness than 50nm at least, silicon nitride film is carried out to film forming, using as the 3rd dielectric film 21.Then, utilize photoetching to form Etching mask, as (g) of Fig. 6 illustrates, by dry ecthing, remove unwanted the 3rd dielectric film 21.Now, as Fig. 2 and Fig. 3 illustrate, with the end of the 3rd dielectric film 21, be positioned at than the mode of the first dielectric film 18 inboards and carry out opening.
And, then, by cutting, carry out the element separation, thereby can access semiconductor light-emitting elements 1.
Above, as to relate to according to embodiments of the invention 1 semiconductor light-emitting elements 1, by oxygen barrier, high the first dielectric film 18 and the 3rd dielectric film 21 cover the second dielectric film 20 of containing quantum dot phosphors, therefore, can suppress the oxidation of quantum dot phosphor.Accordingly, can realize the semiconductor light-emitting elements that quantum efficiency is high and the quantum efficiency quantum dot fluorescence body can not reduce of quantum dot fluorescence body.
(variation of embodiment 1)
The variation of the semiconductor light-emitting elements that embodiments of the invention 1 relate to then, is described.
(structure)
Fig. 7 is the sectional view that the variation of the semiconductor light-emitting elements that embodiments of the invention 1 relate to is shown.
As Fig. 7 illustrates, the semiconductor light-emitting elements 101 that this variation relates to, the semiconductor light-emitting elements 1 related to respect to embodiment 1, alternately form the second dielectric film 20b of the second semiconductor microactuator particle 25b of the second dielectric film 20a of the first semiconductor microactuator particle 25a of the quantum dot fluorescence body that to comprise as the fluorescent peak wavelength be 530nm and the quantum dot fluorescence body that to comprise as the fluorescent peak wavelength be 620nm, thereby form the second dielectric film 20.
By the second dielectric film 20 is become to such structure, with the situation of mixing two kinds of quantum dot fluorescence bodies, compare, can more suppress irregular colour even.
(manufacture method)
Then, the manufacture method of the semiconductor light-emitting elements 101 related to for this variation, below, describe.
At first, same with the manufacture method of explanation in embodiment 1, till being fabricated onto (e) of Fig. 6.
Then, in the film formation process of the second dielectric film 20 illustrated at Fig. 6 (f), as Fig. 7 illustrates, alternately the second dielectric film 20a and the second dielectric film 20b are carried out to film forming, thereby form the second dielectric film 20.Particularly, be provided with on the fluororesin mask of recess, such as the second dielectric film 20a coating of the quantum dot fluorescence body that utilizes ink-jet method, silk screen print method etc., will contain as emission wavelength the first semiconductor microactuator particle 25a that is 530nm, and thermmohardening.Equally, for example utilize ink-jet method, the second dielectric film 20b coating of the quantum dot fluorescence body of the second semiconductor microactuator particle 25b that will to contain as emission wavelength be 620nm, and thermmohardening.
Then, same with Fig. 6 (g), for example, utilize electron beam evaporation plating method, plasma CVD method, preferably utilize the ECR sputtering method, for example, with the thick thickness than 8nm at least, silicon nitride is carried out to film forming, using as the 3rd dielectric film 21.Then, utilize photoetching to form Etching mask, by dry ecthing, remove unwanted the 3rd dielectric film 21.Now, in this variation, as Fig. 2 and Fig. 3 illustrate, also with the end of the 3rd dielectric film 21, be positioned at than the mode of the first dielectric film 18 inboards and carry out opening.Then, carry out the element separation by cutting.
Above, as to relate to according to this variation semiconductor light-emitting elements 101, by oxygen barrier, high the first dielectric film 18 and the 3rd dielectric film 21 cover the second dielectric film 20 of containing quantum dot phosphors, therefore, can suppress the oxidation of quantum dot phosphor.And then, in this variation, the second dielectric film 20 consists of the second dielectric film 20a that comprises the first semiconductor microactuator particle 25a and the second dielectric film 20b that comprises the second semiconductor microactuator particle 25b, therefore with the situation of mixing two kinds of semiconductor microactuator particles, compares, and can more suppress irregular colour even.Accordingly, can realize quantum efficiency and colorrendering quality good, can more suppress the even semiconductor light-emitting elements of irregular colour.
(embodiment 2)
Then, the semiconductor light-emitting elements 2 that embodiments of the invention 2 relate to is described.The structure of the semiconductor light-emitting elements 2 related to for the present embodiment, because the structure of the semiconductor light-emitting elements related to embodiment 1 is roughly the same, therefore only illustrate different parts.
(structure)
At first, the schematic configuration of the semiconductor light-emitting elements 2 related to for embodiments of the invention 2, utilize Fig. 8 to Figure 10 to describe.Fig. 8 is the sectional view of the semiconductor light-emitting elements that relates to of embodiments of the invention 2.And Fig. 9 and Figure 10 are the C zone of the semiconductor light-emitting elements 2 that relates to of embodiments of the invention 2 and the enlarged drawing in D zone.
As Fig. 8 to Figure 10 illustrate, the semiconductor light-emitting elements 2 that the present embodiment relates to, the semiconductor light-emitting elements 1 related to respect to embodiment 1 possesses the 4th dielectric film 22 between the second dielectric film 20 and the 3rd dielectric film 21.
And, cover the second dielectric film 20 fully by the first dielectric film 18 and the 4th dielectric film 22.And then, there is the structure that is covered the second dielectric film 20 and the 4th dielectric film 22 by the first dielectric film 18 and the 3rd dielectric film 21 fully.Now, for the 4th dielectric film 22, preferably, by the electron beam evaporation plating that can hang down the film forming of damaging to resin bed, carry out film forming, the material for the 4th such dielectric film, can utilize silicon nitride, silica, silicon oxynitride, aluminium oxide etc.
So, covered the second dielectric film 20 of containing quantum dot phosphor by the first dielectric film 18, the 3rd dielectric film 21 and the 4th dielectric film 22, therefore, can suppress the oxidation of quantum dot phosphor.Accordingly, can realize that quantum efficiency is good and the second dielectric film 20 be there is no to the semiconductor light-emitting elements damaged.
(manufacture method)
Then, the manufacture method of the semiconductor light-emitting elements related to for embodiment 2, below, utilize Figure 11 to describe.Figure 11 is the figure that the manufacture method of the semiconductor light-emitting elements that embodiments of the invention 2 relate to is shown.
As (a) of Figure 11 illustrates, at first, by the organic metal vapour deposition process, upper at substrate 10 (sapphire substrate), the resilient coating 11 that deposition for example consists of N-shaped GaN successively, the first cover layer 12 for example formed by N-shaped AlGaN, the active layer 13, the second cover layer 14 for example formed by p-type AlGaN and the contact layer 15 formed by p-type GaN that for example by the Multiple Quantum Well of InGaN and GaN, are formed.
Then, utilize photoetching to form the not illustrated diaphragm pattern corresponding with the shape of peristome 30.Then, utilize dry ecthing, till etching into the part of resilient coating 11, as (b) of Figure 11 illustrates, form peristome 30.Then, although do not illustrate,, by electron beam evaporation plating method or sputtering method, on the top of contact layer 15, for example, the transparency electrode consisted of ITO is carried out to film forming, using as the first metal layer 16.
Then, utilize plasma CVD method, preferably utilize the ECR sputtering method, will be as for example SiO of the first dielectric film 18 2, Si 2n 3, Al 2o 3, be formed on each side of top and resilient coating 11, the first cover layer 12, active layer 13, the second cover layer 14, contact layer 15 and the first metal layer 16 of resilient coating 11 and the first metal layer 16.Then, as (c) of Figure 11 illustrates, in order to form n electrode 17 and the second metal level 19a and 19b, utilize photoetching, at the first dielectric film 18, form peristomes 35 and 36.
Then, at the peristome 36 of the resilient coating 11 exposed, utilize photoetching and electron beam evaporation plating method, for example, form the n electrode 17 (Figure 11 (c)) formed by Ti/Al/Ti/Au.
Then, as (d) of Figure 11 illustrates, on the top of the first metal layer 16 exposed and n electrode 17, by peeling off of combination photoetching process and electron beam evaporation plating method, form the second metal level 19a and the 19b formed by Cr/Au.
Then, for example, by rotary coating or spraying process, for example, second dielectric film 20 that will consist of the silicones comprised as the semiconductor microactuator particle of core-shell type quantum point fluorophor is coated on comprehensively.At this, the semiconductor microactuator particle is, the second semiconductor microactuator particle 25b that the first semiconductor microactuator particle 25a that the fluorescent peak wavelength is 530nm and fluorescent peak wavelength are 620nm is mixed, is all the semiconductor microactuator particle of core material by the core-shell type quantum point fluorophor that CdSe or InP form, sheathing material consists of ZnS.Now, also can be by SiO 2film covers the semiconductor microactuator particle.
Then, utilize photoetching to form Etching mask, as (e) of Figure 11 illustrates, the second dielectric film 20 that utilizes aqueous slkali to remove to comprise unwanted semiconductor microactuator particle.Now, as Fig. 9 and Figure 10 illustrate, with the end of the second dielectric film 20 of comprising the semiconductor microactuator particle, be positioned at than the mode of the first dielectric film 18 inboards and carry out opening.
Then, utilize photoetching to form Etching mask, for example, by the electron beam evaporation plating method, as (f) of Figure 11 illustrates, for example, to cover the comprehensive mode of the second dielectric film 20, with the thick thickness than 10nm at least, silicon nitride film is carried out to film forming, using as the 4th dielectric film 22.Now, as Fig. 9 and Figure 10 illustrate, with the end of the 4th dielectric film 22, be positioned at than the mode of the first dielectric film 18 inboards and carry out opening.
Then, for example, utilize plasma CVD method, preferably utilize the ECR sputtering method, for example, with the thick thickness than 8nm at least, silicon nitride film is carried out to film forming, using as the 3rd dielectric film 21.Then, utilize photoetching to form Etching mask, as (g) of Figure 11 illustrates, by dry ecthing, remove unwanted the 3rd dielectric film 21.Now, as Fig. 9 and Figure 10 illustrate, with the end of the 3rd dielectric film 21, be positioned at than the mode of the first dielectric film 18 inboards and carry out opening.
And, then, by cutting, carry out the element separation, thereby can access semiconductor light-emitting elements 2.
Above, the semiconductor light-emitting elements 2 related to according to embodiments of the invention 2, form the 4th dielectric film 22 on the second dielectric film 20, therefore, when utilizing ECR sputtering method and CVD method that fine and close crystallization is formed to the 3rd dielectric film 21, can suppress the damage brought to the second dielectric film 20 that comprises semiconductor microactuator particle (quantum dot fluorescence body).Its result is, can reduce the reduction of the quantum efficiency that the oxidation because of the quantum dot fluorescence body causes, and, can reduce that the damage accepted when forming the 3rd dielectric film 21 causes the reduction of quantum efficiency.Accordingly, can realize the high semiconductor light-emitting elements of quantum efficiency of quantum dot fluorescence body.
And, for the quantum dot fluorescence body, the material that embodiment 1 puts down in writing gets final product.And, for the structure of quantum dot fluorescence body, utilized hud typedly, still, can be also the quantum well type.And, for the second dielectric film 20, the material that embodiment 1 puts down in writing gets final product.And, for the 3rd dielectric film 21, the material that embodiment 1 puts down in writing gets final product.
(variation of embodiment 2)
The variation of the semiconductor light-emitting elements that embodiments of the invention 2 relate to then, is described.
(structure)
Figure 12 is the sectional view that the variation of the semiconductor light-emitting elements that embodiments of the invention 2 relate to is shown.
As Figure 12 illustrates, the semiconductor light-emitting elements 201 that this variation relates to, the semiconductor light-emitting elements 2 related to respect to embodiment 2, alternately form the second dielectric film 20b of the second semiconductor microactuator particle 25b of the second dielectric film 20a of the first semiconductor microactuator particle 25a of the quantum dot fluorescence body that to comprise as the fluorescent peak wavelength be 530nm and the quantum dot fluorescence body that to comprise as the fluorescent peak wavelength be 620nm, thereby form the second dielectric film 20.
By the second dielectric film 20 is become to such structure, with the situation of mixing two kinds of quantum dot fluorescence bodies, compare, can more suppress irregular colour even.And the semiconductor light-emitting elements that this variation relates to is that same method can be manufactured by the variation with embodiment 1.
(embodiment 3)
Then, the light-emitting device that embodiments of the invention 3 relate to is described.
(structure)
Figure 13 is the sectional view of the light-emitting device that relates to of embodiments of the invention 3.
As Figure 13 illustrates, the light-emitting device 3 that embodiments of the invention 3 relate to possesses: packaging body 50 consists of the resin 51 with recess and two lead frames 52,53 of exposing in the bottom surface of recess; Semiconductor light-emitting elements 1, be arranged on the lead frame 52 in recess; Article two, wire 55,56, connect semiconductor light-emitting elements 1 and two lead frames 52,53; And resin bed 60, be formed in recess and cover on semiconductor light-emitting elements 1.In the present embodiment, utilize the semiconductor light-emitting elements 1 that embodiment 1 relates to be illustrated, still, also can be suitable for the semiconductor light-emitting elements that variation, embodiment 2 or this variation of embodiment 1 relate to.
Being configured to of packaging body 50, in the resin 51 formed at for example polyamide with recess, imbed the first electrode of becoming packaging body 50 and the second electrode, for example surface is by silver-plated two lead frames 52,53 that copper formed.
For the part of this lead frame 52,53, the bottom surface sections in the recess of resin 51 is exposed, and by two wires 55,56, with the second metal level 19a, the 19b of semiconductor light-emitting elements 1, is electrically connected to, and usings as the first electrode and the second electrode.
And, be configured in the semiconductor light-emitting elements 1 of bottom surface sections of recess and the mode of the lead frame 52,53 that exposes in recess with covering, form resin bed 60.In resin bed 60, for example, the particulate that the aluminium nitride that to have disperseed by thermal conductivity be 200W/mK forms, using as high heat conduction particulate 61.
In the present embodiment, the lead frame 52,53 that resin bed 60 is high with thermal conductance contacts, and therefore, the heat occurred at the second dielectric film 20, via the 3rd dielectric film 21 and disperseed the resin bed 60 of high heat conduction particulate 61 to dispel the heat.The temperature that therefore, can suppress the second dielectric film 20 rises.According to this structure, can suppress the oxidation of quantum dot phosphor, the luminous efficiency that can also suppress to cause because of heating reduces.
(manufacture method)
Then, the manufacture method of the light-emitting device 3 related to for embodiment 3, below, utilize Figure 13 to describe.
At first, by the manufacture method of explanation in embodiment 1, manufacture semiconductor light-emitting elements 1.
Then, at packaging body 50, this semiconductor light-emitting elements 1 is installed.Then, to packaging body 50, the aqueous resin that perfusion contains high heat conduction particulate 61.Then, under 160 ℃ of conditions, by resin thermmohardening 30 minutes, thereby form resin bed 60.
And, for high heat conduction particulate 61, utilized the aluminium nitride that thermal conductivity is 200W/mK.And, in the present embodiment, for high heat conduction particulate 61, utilized aluminium nitride, but be not limited only to this.For high heat conduction particulate 61, do not absorb from the luminous of semiconductor element and from the luminous material of quantum dot fluorescence body and material with high heat conductance and get final product, can utilize silicon nitride, silica nitrogen, Si oxide, zinc oxide, aluminum oxide, indium oxide, carborundum or diamond.
And, in the present embodiment, for packaging body 50, utilized the packaging body with the resin filling lead frame, still, be not limited only to this, also can utilize the ceramic packaging body that thermal conductivity is higher.
(embodiment 4)
Then, the semiconductor light-emitting elements 4 that embodiments of the invention 4 relate to is described.The structure of the semiconductor light-emitting elements 4 related to for the present embodiment, because the structure of the semiconductor light-emitting elements related to embodiment 1 and 2 is roughly the same, therefore only illustrate different parts.
(structure)
At first, the schematic configuration of the semiconductor light-emitting elements 4 related to for embodiments of the invention 4, utilize Figure 14 to describe.Figure 14 is the sectional view of the semiconductor light-emitting elements that relates to of embodiments of the invention 4.
As Figure 14 illustrates, the feature of the semiconductor light-emitting elements 4 that the present embodiment relates to is, the face of the contrary side of face that n electrode 17 is formed on the back side of substrate 10, be formed with active layer, the second dielectric film 20 is sealed between the first dielectric film 18 and the 3rd dielectric film 21.
Now, for the 3rd dielectric film 21, for example, utilize as epoxy resin, easily thickness is adjusted into to thickness and the oxygen barrier high resin of several 10 μ m to several 100 μ m.
Accordingly, by manufacture method described later, the film high by oxygen barrier easily covers the second dielectric film 20 that comprises semiconductor microactuator particle (quantum dot fluorescence body).
(manufacture method)
Then, the manufacture method of the semiconductor light-emitting elements 4 related to for embodiment 4, below, utilize Figure 15 to describe.Figure 15 is the figure that the manufacture method of the semiconductor light-emitting elements 4 that embodiments of the invention 4 relate to is shown.
As (a) of Figure 15 illustrates, at first, by the organic metal vapour deposition process, in the conduct as conductive board for example on the substrate 10 of N-shaped GaN substrate or SiC substrate, the resilient coating 11 that deposition for example consists of N-shaped GaN successively, the first cover layer 12 for example formed by N-shaped AlGaN, the active layer 13, the second cover layer 14 for example formed by p-type AlGaN and the contact layer 15 for example formed by p-type GaN that for example by the Multiple Quantum Well of InGaN and GaN, are formed.Then, form peristome 30 by photoetching and dry ecthing.Then, on the top of contact layer 15, form the first metal layer 16 for example formed by ITO.Then, for example, will be by SiO 2, Si 2n 3, Al 2o 3the first dielectric film 18 of forming of at least more than one film, for example, utilize plasma CVD method, preferably utilize the ECR sputtering method, be formed on each side of top and resilient coating 11, the first cover layer 12, active layer 13, the second cover layer 14, contact layer 15 and the first metal layer 16 of resilient coating 11 and the first metal layer 16.Then, utilize photoetching, at the first dielectric film 18, peristome is set, and, for example, form the second metal level 19 formed by Cr/Au.
Then, as Figure 15 (b) illustrates, for example, by rotary coating or spraying process, for example, second dielectric film 20 that will consist of the silicones comprised as the semiconductor microactuator particle of core-shell type quantum point fluorophor is coated on comprehensively.At this, the semiconductor microactuator particle is, the second semiconductor microactuator particle that the first semiconductor microactuator particle that the fluorescent peak wavelength is 530nm and fluorescent peak wavelength are 620nm is mixed, is all the semiconductor microactuator particle of core material by the core-shell type quantum point fluorophor that CdSe or InP form, sheathing material consists of ZnS.
Then, as Figure 15 (c) illustrates, utilize photoetching to form Etching mask, utilize top that aqueous slkali removes the second metal level 19 with and the second dielectric film 20 on every side.
Then, as Figure 15 (d) illustrates, utilize cutter 91, near the central portion of peristome 30, the second dielectric film 20, the first dielectric film 18 and resilient coating 11 cut, and excavates substrate 10, forms groove 31.
Then, for example, in the mode of covering groove 31 and the second dielectric film 20, form the 3rd dielectric film 21 with oxygen barrier of the thickness of the regulation as epoxy resin.Then, utilize photoetching to form Etching mask, as (e) of Figure 15 illustrates, so that near the mode of openings the second metal level 19 forms peristome 35.Now, be positioned at than the mode of the second dielectric film 20 inboards and carry out opening with the end of the 3rd dielectric film 21.
Finally, as (f) of Figure 15 illustrates, after the back side of substrate 10 forms the n electrode 17 as for example Ti/Au, near the central authorities for groove 31, adopt for example laser cutting technique, utilize laser 92 to carry out the element separation.Accordingly, can access semiconductor light-emitting elements 4.
Above, as to relate to according to embodiments of the invention 4 semiconductor light-emitting elements 4, the second dielectric film 20 by the first dielectric film 18 and the 3rd dielectric film 21 covering containing quantum dot phosphors, therefore, can suppress the oxidation of quantum dot phosphor.Accordingly, can realize the semiconductor light-emitting elements that quantum efficiency is good.
And, for the quantum dot fluorescence body, the material that embodiment 1 and embodiment 2 put down in writing gets final product.And, for the structure of quantum dot fluorescence body, utilized hud typedly, still, can be also the quantum well type.And, for the second dielectric film 20, the material that embodiment 1 puts down in writing gets final product.And, for the 3rd dielectric film 21, the material that embodiment 1 puts down in writing gets final product.
(embodiment 5)
Then, the light-emitting device that embodiments of the invention 5 relate to is described.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 5, utilize Figure 16 to describe.Figure 16 is the sectional view of the light-emitting device that relates to of embodiments of the invention 5.
As Figure 16 illustrates, packaging body 70 is that the structure with recess consisted of resin, in the bottom surface sections of recess, imbed the lead frame 71 consisted of the conductor with the first electrode and second electrode.
For the part of this lead frame 71, the bottom surface sections in the recess of packaging body 70 is exposed, and for example, with the semiconductor light-emitting elements 72 luminous with 450nm, is electrically connected to, and usings as the first electrode and the second electrode.And, be configured in the semiconductor light-emitting elements 72 of bottom surface sections of recess and the mode of the lead frame 71 that exposes in recess with covering, form wavelength converter section 73.
Wavelength converter section 73 (the first resin portion) is, in resin 74a, the quantum dot fluorescence body 75 that contains the following peak wavelength with 530nm and 620nm of particle diameter 20nm for example and as the titanium oxide (TiO of for example average grain diameter 50nm of the absorbing particle 77a (the first absorbing particle) of adsorb oxygen x: x>0) form.So, the absorbing particle 77a of the interior scattered adsorption oxygen of wavelength converter section 73, thus can suppress the oxidation of quantum dot phosphor 75.
For the absorbing particle 77a (titanium oxide) utilized in the present embodiment, average grain diameter is 50nm, and size is similar to the particle diameter of quantum dot fluorescence body 75, therefore, and can be dispersed together with quantum dot fluorescence body 75 in resin 74a.Accordingly, the luminous efficiency that can suppress the quantum dot fluorescence body 75 that causes because of oxidation reduces, and can realize the light-emitting device of high reliability.
At this, consider to see through the oxygen amount of resin 74a.The oxygen amount that sees through resin 74a is that the oxygen transmission coefficient had according to resin 74a can calculate.For example, in the situation that utilize the epoxy resin (100 μ m) as resin 74a, the oxygen transmission coefficient is 52cc/m 2day, be for example angle type packaging body of vertical 3.5mm, horizontal 3.5mm if be considered as the size of LED packaging body, and the oxygen amount seen through to epoxy resin from air layer is 1.97 * 10 11individual/s.Generally speaking, the LED illumination need to have the long products life-span of so-called 40,000 hours.That is to say, the oxidation of needs inhibition quantum dot phosphor 75 40,000 hours, oxygen transit dose now is 2.84 * 10 19individual.And oxygen also sees through from lead frame 71 and the gap of packaging body 70.Its transit dose is 2.7 * 10 8individual/s (is 3.99 * 10 after 40,000 hours 16individual).And then oxygen also sees through from packaging body 70.Its transit dose is 5.3 * 10 8individual/s (is 7.7 * 10 after 40,000 hours 16individual).Considering for an oxygen molecule, adsorb in the situation of an absorbing particle, in order to adsorb all oxygen seen through, need the amount that will be placed in the absorbing particle 77a in resin 74a at least to become 2.86 * 10 19more than individual.
And, in the present embodiment, for resin, 74a has utilized epoxy resin, still, resin 74a is, resin silicones, fluoride resin, allyl resin etc., that the emission wavelength from semiconductor light-emitting elements and quantum dot fluorescence body is had to a high permeability gets final product.
And, in the present embodiment, for absorbing particle 77a, utilized titanium oxide, still, be not limited only to this.For example, the candidate of absorbing particle 77a has, metal oxide and porous material.
For the absorbing particle 77a of metal oxide, can enumerate for example titanium oxide (TiO x), niobium oxide (NbO x), hafnium oxide (HfO x), indium oxide (In 2o x), tungsten oxide (WO x), tin-oxide (SnO x), zinc oxide (ZnO x), Zirconium oxide (ZrO x), magnesium oxide (MgO), sb oxide (SbO x), aluminum oxide (Al 2o x) etc.For the absorbing particle 77a of porous material, can enumerate for example silicon dioxide (SiO x), silica nitrogen (SiON) etc. (still, X>0).
For the structure of quantum dot fluorescence body 75, can enumerate hud typed, quantum well type etc., still, in the present embodiment, can be suitable for which structure.
And, for the core that forms quantum dot fluorescence body 75 and the material of shell, for example, situation for the II-VI compounds of group, can enumerate from CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnZe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnZeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgSeTe, CdHgSTe, HgZnSS, HgZnSeTe, at least one that select in HgZnSTe etc.
And, example for the III-V compounds of group, can enumerate from GaN, GaP, GaAs, GaSb, AlN, AlGaN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, InGaN, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, InAlNP, InAlNAs, InAlNSb, InAlPAs, at least one that select in InAlPSb etc.
(manufacture method)
Then, the manufacture method of the light-emitting device related to for embodiments of the invention 5, below describe.
At first, the packaging body 70 be mounted to semiconductor light-emitting elements 72, perfusion has disperseed the resin 74a of quantum dot fluorescence body 75 and absorbing particle 77a (TiOx:x>0), forms wavelength converter section 73.Now, with the bottom surface of covering packaging body 70 and the mode of lead frame 71, form wavelength converter section 73.This wavelength converter section 73 is, contains quantum dot phosphor 75 and absorbing particle 77a in resin 74a.Quantum dot fluorescence body 75 is, for take emission wavelength as 530nm and 620nm luminous, and for example core has been utilized CdSe, shell has been utilized to the particulate below the particle diameter 20nm of ZnS.Absorbing particle 77a, by for example adsorb oxygen and for example do not absorb with the 450nm emission wavelength of luminous semiconductor light-emitting elements 72 and consist of the material of the wavelength of quantum dot fluorescence body 75 conversions.Such absorbing particle 77a has, for example the titanium oxide of average grain diameter 50nm.Then, for example, once, under 160 ℃ of conditions, by resin 74a thermmohardening 30 minutes.
Above, what according to embodiments of the invention 5, relate to partly leads device, due to the many oxygen that see through in resin 74a, by absorbing particle 77a absorption, therefore can suppress the oxidation of quantum dot phosphor 75.Therefore, can reduce the oxidation of quantum dot fluorescence body 75.Accordingly, can realize the light-emitting device that luminous efficiency is high, colorrendering quality is good.
(embodiment 6)
Then, the light-emitting device that embodiments of the invention 6 relate to is described.The basic structure of the light-emitting device that the present embodiment relates to is identical with embodiment 5.The present embodiment, the structures different from embodiment 5 are, between the inwall in the recess of wavelength converter section and packaging body, the layer that adsorb oxygen is set or does not make oxygen see through.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 6, utilize Figure 17 to describe.Figure 17 is the sectional view of the light-emitting device that relates to of embodiments of the invention 6.
As Figure 17 illustrates, packaging body 70 is that the structure with recess consisted of resin, in the bottom surface sections of recess, imbed the lead frame 71 consisted of the conductor with the first electrode and second electrode.
For the part of this lead frame 71, the bottom surface sections in the recess of packaging body 70 is exposed, and for example, with the semiconductor light-emitting elements 72 luminous with 450nm, is electrically connected to, and usings as the first electrode and the second electrode.And, inwall in the recess of packaging body 70, formation as adsorb oxygen or do not make oxygen see through the layer oxidation prevention layer 78, and then, be configured in the semiconductor light-emitting elements 72 of bottom surface sections of recess and the mode of the lead frame 71 exposed and oxidation prevention layer 78 with covering in recess, form wavelength converter section 73.
Wavelength converter section 73 is, in resin 74a, and the quantum dot fluorescence body 75 that contains the following peak wavelength with 530nm and 620nm of particle diameter 20nm for example and as the titanium oxide (TiO of for example average grain diameter 50nm of the absorbing particle 77a of adsorb oxygen x: x>0) form.
For the absorbing particle 77a (titanium oxide) utilized in the present embodiment, average grain diameter is 50nm, and size is similar to the particle diameter of quantum dot fluorescence body 75, therefore, and can be dispersed together with quantum dot fluorescence body 75 in resin 74a.
And oxidation prevention layer 78 is, the above silver of thickness 10nm for example.For silver, thermal conductance is high, also has radiating effect.Accordingly, oxidation prevention layer 78, also can suppress the promotion of the oxidation reaction that the heating because of quantum dot fluorescence body 75 causes.
And in the present embodiment, the material for oxidation prevention layer 78, utilized silver, still, is not limited only to this.For the material of oxidation prevention layer 78, the material that utilizes adsorb oxygen or do not make oxygen see through gets final product, for example, if metal, metal oxide, Porous particle have no particular limits.If metal, can enumerate such as gold, silver, aluminium, titanium, magnesium, nickel etc.If metal oxide, can enumerate such as titanium oxide, niobium oxide, hafnium oxide, indium oxide, tungsten oxide, tin-oxide, zinc oxide, Zirconium oxide, magnesium oxide, sb oxide etc.In the situation that the Porous particle can be enumerated such as silicon dioxide, silica nitrogen, zeolite etc.
Now, the oxygen amount seen through from the inwall of packaging body 70 is, 5.3 * 10 8individual/s (is 7.7 * 10 after 40,000 hours 16individual).Therefore, in the situation that utilize for example silver as oxidation prevention layer 78, need at least above thickness of 10nm.And, in the situation that utilize for example epoxy resin as resin 74a, from the oxygen transit dose of air layer, be 2.84 * 10 19individual (after 40,000 hours).Considering for an oxygen molecule, adsorb in the situation of an absorbing particle, in order to adsorb all oxygen seen through, need the amount that will be placed in the absorbing particle 77a in wavelength converter section 73 to become 2.85 * 10 19more than individual (thering is the needed amount of life-span of 40,000 hours).
Above, as to relate to according to embodiments of the invention 6 light-emitting device, not only, at the absorbing particle 77a of the interior scattered adsorption oxygen of wavelength converter section 73, the oxygen also seen through from packaging body 70, by oxidation prevention layer 78 absorption, therefore, can suppress to see through to the oxygen of wavelength converter section 73.And, even oxygen sees through in resin 74a, the many oxygen that also see through, by absorbing particle 77a absorption, therefore, can suppress the oxidation of quantum dot phosphor 75.Therefore, can reduce the oxidation of quantum dot fluorescence body 75.Accordingly, can realize the light-emitting device that luminous efficiency is high, colorrendering quality is good.
(manufacture method)
Then, the manufacture method of the light-emitting device related to for embodiments of the invention 6, below describe.
At first, with the bottom surface of the recess that covers packaging body 70 and the mode of lead frame 71, form for example Etching mask.Then, utilize evaporation or sputter etc., for example, the silver that the light by luminous reflects, thermal conductivity is high is carried out to film forming, using as oxidation prevention layer 78.Then, carry out removing of Etching mask.
Then, at packaging body 70, semiconductor light-emitting elements 72 is installed.Then, the packaging body 70 be mounted to semiconductor light-emitting elements 72, perfusion has disperseed quantum dot fluorescence body 75 and absorbing particle 77a (TiO x: resin 74a x>0) forms wavelength converter section 73.Now, the mode with the bottom surface, lead frame 71 and the oxidation prevention layer 78 that cover packaging body 70, form wavelength converter section 73.This wavelength converter section 73 is, contains quantum dot phosphor 75 and absorbing particle 77a in resin 74a.Quantum dot fluorescence body 75 is, for take emission wavelength as 530nm and 620nm luminous, and for example core has been utilized CdSe, shell has been utilized to the particulate below the particle diameter 20nm of ZnS.Absorbing particle 77a, by for example adsorb oxygen and for example do not absorb with the 450nm emission wavelength of luminous semiconductor light-emitting elements 72 and consist of the material of the wavelength of quantum dot fluorescence body 75 conversions.Such absorbing particle 77a has, for example the titanium oxide of average grain diameter 50nm.Then, for example, once, under 160 ℃ of conditions, by resin 74a thermmohardening 30 minutes.
And, for quantum dot fluorescence body 75, the material that embodiment 5 puts down in writing gets final product.And, for the structure of quantum dot fluorescence body 75, utilized hud typedly, still, can be also the quantum well type.And, for the material of absorbing particle 77a, the material that embodiment 5 puts down in writing gets final product.And, for the material of resin 74a, the material that embodiment 5 puts down in writing gets final product.
(embodiment 7)
Then, the light-emitting device that embodiments of the invention 7 relate to is described.The basic structure of the light-emitting device that the present embodiment relates to is identical with embodiment 5.The present embodiment, the structures different from embodiment 5 are to be covered the top of wavelength converter section by glass cover.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 7, utilize Figure 18 to describe.Figure 18 is the sectional view of the light-emitting device that relates to of embodiments of the invention 7.
As Figure 18 illustrates, packaging body 70 is that the structure with recess consisted of resin, in the bottom surface sections of recess, imbed the lead frame 71 consisted of the conductor with the first electrode and second electrode.
For the part of this lead frame 71, the bottom surface sections in the recess of packaging body 70 is exposed, and for example, with the semiconductor light-emitting elements 72 luminous with 450nm, is electrically connected to, and usings as the first electrode and the second electrode.And, be configured in the semiconductor light-emitting elements 72 of bottom surface sections of recess and the mode of the lead frame 71 that exposes in recess with covering, form wavelength converter section 73.Be provided with glass cover 79 on the top of wavelength converter section 73, accordingly, wavelength converter section 73 is by glass cover 79 gas-tight seals.
Wavelength converter section 73 is, in resin 74a, and the quantum dot fluorescence body 75 that contains the following peak wavelength with 530nm and 620nm of particle diameter 20nm for example and as the titanium oxide (TiO of for example average grain diameter 50nm of the absorbing particle 77a of adsorb oxygen x: x>0) form.
So, the absorbing particle 77a of adsorb oxygen is placed in wavelength converter section 73, and, by glass cover, the top of this wavelength converter section 73 and packaging body 70 are bonding by bonding agent, accordingly, can suppress significantly to see through from the oxygen of air layer.The luminous efficiency that accordingly, can suppress significantly the quantum dot fluorescence body 75 that causes because of oxidation reduces.
At this, consider to sneak into the amount of the absorbing particle 77a in wavelength converter section 73.The path that oxygen sees through to wavelength converter section 73 is, the position that the gap of packaging body 70, packaging body 70 and lead frame 71 and packaging body 70 and glass cover 79 are bonding by bonding agent 80.In the situation that utilize for example as the epoxy resin of resin 74a and bonding agent 80, the oxygen amount (40,000 hours) seen through from these three positions is 7.8 * 10 16individual.Considering for an oxygen molecule, adsorb in the situation of an absorbing particle, in order to adsorb all oxygen seen through, need the amount that will be placed in the absorbing particle 77a in wavelength converter section 73 to become 7.8 * 10 16more than individual.
(manufacture method)
Then, the manufacture method of the light-emitting device related to for embodiments of the invention 7, below describe.
At first, the packaging body 70 be mounted to semiconductor light-emitting elements 72, perfusion has disperseed quantum dot fluorescence body 75 and absorbing particle 77a (TiO x: resin x>0) forms wavelength converter section 73.Now, with the bottom surface of covering packaging body and the mode of lead frame 71, form wavelength converter section 73.Wavelength converter section 73 is, contains quantum dot phosphor 75 and absorbing particle 77a in resin 74a.Quantum dot fluorescence body 75 is, for take emission wavelength as 530nm and 620nm luminous, and for example core has been utilized CdSe, shell has been utilized to the particulate below the particle diameter 20nm of ZnS.Absorbing particle 77a, by for example adsorb oxygen and for example do not absorb with the 450nm emission wavelength of luminous semiconductor light-emitting elements 72 and consist of the material of the wavelength of quantum dot fluorescence body 75 conversions.Such absorbing particle 77a has, for example the titanium oxide of average grain diameter 50nm.Now, utilize scraper, the resin 74a by after perfusion, become the plane same with the protuberance of packaging body 70, for example, under 160 ℃ of conditions, thermmohardening 30 minutes, thus form wavelength converter section 73.
Then, at the thin resin 74a of glass cover 79 coating, the mode contacted with wavelength converter section 73 with resin 74a, by the bonding agent 80 for example formed by epoxy adhesive, that packaging body 70 and glass cover 79 is bonding, and gas-tight seal.Accordingly, can suppress significantly to see through to the oxygen of wavelength converter section 73.
And, for quantum dot fluorescence body 75, the material that embodiment 5 puts down in writing gets final product.And, for the structure of quantum dot fluorescence body 75, utilized hud typedly, still, can be also the quantum well type.And, for the material of absorbing particle 77a, the material that embodiment 5 puts down in writing gets final product.And, for the material of resin 74a, the material that embodiment 5 puts down in writing gets final product.
And, by absorbing particle 77a also is placed in bonding agent 80, thereby can more suppress to see through to the oxygen of wavelength converter section 73.
(embodiment 8)
Then, the light-emitting device that embodiments of the invention 8 relate to is described.The basic structure of the light-emitting device that the present embodiment relates to is identical with embodiment 1.The present embodiment, the structures different from embodiment 5 are, between the inwall of the recess of wavelength converter section and packaging body, are provided with as adsorb oxygen or the oxidation prevention layer of the layer that do not make oxygen see through, also on the top of wavelength converter section and oxidation prevention layer, are provided with glass cover.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 8, utilize Figure 19 to describe.Figure 19 is the sectional view of the light-emitting device that relates to of embodiments of the invention 8.
As Figure 19 illustrates, packaging body 70 is that the structure with recess consisted of resin, in the bottom surface sections of recess, imbed the lead frame 71 consisted of the conductor with the first electrode and second electrode.
For the part of this lead frame 71, the bottom surface sections in the recess of packaging body 70 is exposed, and for example, with the semiconductor light-emitting elements 72 luminous with 450nm, is electrically connected to, and usings as the first electrode and the second electrode.And, inwall in the recess of packaging body 70, formation as adsorb oxygen or do not make oxygen see through the layer oxidation prevention layer 78, and then, be configured in the semiconductor light-emitting elements 72 of bottom surface sections of recess and the mode of the lead frame 71 exposed and oxidation prevention layer 78 with covering in recess, form wavelength converter section 73.
Wavelength converter section 73 is, in resin 74a, and the quantum dot fluorescence body 75 that contains the following peak wavelength with 530nm and 620nm of particle diameter 20nm for example and as the titanium oxide (TiO of for example average grain diameter 50nm of the absorbing particle 77a of adsorb oxygen x: x>0) form.
Oxidation prevention layer 78 is, for example the above silver of thickness 10nm.And then, be provided with glass cover 79 on the top of wavelength converter section 73 and oxidation prevention layer 78.Glass cover 79 and packaging body 70 are bonding by bonding agent 80, and accordingly, wavelength converter section 73 is hermetically sealed.
At this, consider to sneak into the amount of the absorbing particle 77a in wavelength converter section 73.The path that oxygen sees through to wavelength converter section 73 is, the position that the gap of packaging body 70 and lead frame 71 and packaging body 70 and glass cover 79 are bonding by bonding agent 80.In the situation that utilize for example as the epoxy resin of resin 74a and bonding agent 80, the oxygen amount seen through from two positions (40,000 hours) is 4.1 * 10 16individual.Considering for an oxygen molecule, adsorb in the situation of an absorbing particle, in order to adsorb all oxygen seen through, need the amount that will be placed in the absorbing particle 77a in wavelength converter section 73 to become 4.1 * 10 16more than individual.
And, in the situation that utilize for example silver as oxidation prevention layer 78, and preferably, more than the thickness of oxidation prevention layer 78 is at least become to 10nm.
Above, as to relate to according to embodiments of the invention 8 light-emitting device, can reduce the oxygen transit dose from air layer, and, can reduce significantly from the oxygen of packaging body 70 and see through.For silver, thermal conductance is high, also has radiating effect.Accordingly, by utilizing the silver as oxidation prevention layer 78, thereby also can suppress the promotion of the oxidation reaction that the heating because of quantum dot fluorescence body 75 causes.
(manufacture method)
Then, the manufacture method of the light-emitting device related to for embodiments of the invention 8, below describe.
At first, with the bottom surface of the recess that covers packaging body 70 and the mode of lead frame 71, form for example Etching mask.Then, utilize evaporation or sputter etc., for example, the reflection of the light by luminous and the high silver of thermal conductivity are carried out to film forming, using as oxidation prevention layer 78.Then, carry out removing of Etching mask.
Then, at packaging body 70, semiconductor light-emitting elements 72 is installed.Then, the packaging body 70 be mounted to semiconductor light-emitting elements 72, perfusion has disperseed quantum dot fluorescence body 75 and absorbing particle 77a (TiO x: resin x>0) forms wavelength converter section 73.Now, the mode with the bottom surface, lead frame 71 and the oxidation prevention layer 78 that cover packaging body 70, form wavelength converter section 73.This wavelength converter section 73 is, contains quantum dot phosphor 75 and absorbing particle 77a in resin 74a.Quantum dot fluorescence body 75 is, for take emission wavelength as 530nm and 620nm luminous, and for example core has been utilized CdSe, shell has been utilized to the particulate below the particle diameter 20nm of ZnS.Absorbing particle 77a, by for example adsorb oxygen and for example do not absorb with the 450nm emission wavelength of luminous semiconductor light-emitting elements 72 and consist of the material of the wavelength of quantum dot fluorescence body 75 conversions.Such absorbing particle 77a has, for example the titanium oxide of average grain diameter 50nm.Now, utilize scraper, the resin 74a by after perfusion, become the plane same with the protuberance of packaging body 70, for example, under 160 ℃ of conditions, thermmohardening 30 minutes, thus form wavelength converter section 73.
Then, at the thin resin 74a of glass cover 79 coating, the mode contacted with wavelength converter section 73 with resin 74a, by the bonding agent 80 for example formed by epoxy adhesive, that packaging body 70 and glass cover 79 is bonding, and gas-tight seal.Accordingly, can suppress significantly to see through to the oxygen of wavelength converter section 73.
And, for quantum dot fluorescence body 75, the material that embodiment 5 puts down in writing gets final product.And, for the structure of quantum dot fluorescence body 75, utilized hud typedly, still, can be also the quantum well type.And, for the material of absorbing particle 77a, the material that embodiment 5 puts down in writing gets final product.And, for the material of resin 74a, the material that embodiment 5 puts down in writing gets final product.
And, by absorbing particle 77a also is placed in bonding agent 80, thereby can more suppress to see through to the oxygen of wavelength converter section 73.
And, utilized the silver as the material of oxidation prevention layer 78, still, be not limited only to this, the material that embodiment 6 puts down in writing gets final product.
(embodiment 9)
Then, the light-emitting device that embodiments of the invention 9 relate to is described.The basic structure of the light-emitting device that the present embodiment relates to is identical with embodiment 5.The present embodiment, the structures different from embodiment 5 are to form the oxygen absorbed layer on the top of wavelength converter section.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 9, utilize Figure 20 to describe.Figure 20 is the sectional view of the light-emitting device that relates to of embodiments of the invention 9.
As Figure 20 illustrates, packaging body 70 is that the structure with recess consisted of resin, in the bottom surface sections of recess, imbed the lead frame 71 consisted of the conductor with the first electrode and second electrode.
For the part of this lead frame 71, the bottom surface sections in the recess of packaging body 70 is exposed, and for example, with the semiconductor light-emitting elements 72 luminous with 450nm, is electrically connected to, and usings as the first electrode and the second electrode.And, be configured in the semiconductor light-emitting elements 72 of bottom surface sections of recess and the mode of the lead frame 71 that exposes in recess with covering, form wavelength converter section 73.
Wavelength converter section 73 is, in resin 74a, and the quantum dot fluorescence body 75 that contains the following peak wavelength with 530nm and 620nm of particle diameter 20nm for example and as the titanium oxide (TiO of for example average grain diameter 50nm of the absorbing particle 77a of adsorb oxygen x: x>0) form.
And, to cover the mode of wavelength converter section 73, form oxygen absorbed layer 76 (the second resin portion).Oxygen absorbed layer 76 is, in resin 74b, contains the absorbing particle 77b (the second absorbing particle) for example consisted of the zeolite (aluminosilicate) below particle diameter 100 μ m and forms.Zeolite (aluminosilicate) is a kind of regular porous body, has four oxygen (O) crystal structure that three-dimensional connects regularly around silicon (Si) and aluminium (Al).
And zeolite is, at the Si with tetravalence, the structure of the Al of trivalent is put in identical position, and therefore, Al is negative charging, in order to keep electric neutrality, puts into cation in pore.For example, if put into potassium (K), fine pore can be changed to the 0.3nm of the size roughly the same with oxygen molecule, be placed in the oxygen in pore, because cationic electrostatic field is adsorbed.Particle diameter for zeolite now, be preferably 1 μ m to 100 μ m, more preferably 1 μ m to 20 μ m.This is because if particle diameter is too large, do not can be uniformly dispersed zeolite in resin, the cause that the oxygen adsorption effect reduces.
So, form oxygen absorbed layer 76 by the upper strata at wavelength converter section 73, thereby the oxygen that can suppress significantly from air layer to wavelength converter section 73 sees through.And even, oxygen absorbed layer 76 adsorb oxygen fully, and oxygen enters into wavelength converter section 73, the oxygen entered is also by the absorbing particle 77a absorption of wavelength converter section 73 interior mixing.
And, for the absorbing particle 77a (titanium oxide) utilized in the present embodiment, average grain diameter is 50nm, size is similar to the particle diameter of quantum dot fluorescence body 75.Accordingly, can be dispersed together with quantum dot fluorescence body 75 in resin 74a.Its result is, can effectively suppress the oxidation of quantum dot phosphor 75, and the light-emitting device that obtains high efficiency light-emitting, high reliability can be provided.
At this, for the amount that is placed in the absorbing particle 77a in wavelength converter section 73, if resin 74a is for example epoxy resin, according to the path seen through to wavelength converter section 73 from oxygen (packaging body 70, the gap of lead frame 71 and packaging body 70), the oxygen amount (4 * 10 seen through to epoxy resin 14individual: as the oxygen amount after 40,000 hours), need to become 4 * 10 14more than individual.
And, for the amount that is placed in the absorbing particle 77b in oxygen absorbed layer 76, considering for an oxygen molecule, adsorb in the situation of an absorbing particle, in order to adsorb all oxygen seen through, for example, according to the oxygen amount (2.84 * 10 that (epoxy resin) sees through from air layer to resin 74b 19individual: as the oxygen transit dose after 40,000 hours), need to become 2.85 * 10 19more than individual.
And, in the present embodiment, for absorbing particle 77b, utilized zeolite (aluminosilicate), still, be not limited only to this.For example, the candidate of absorbing particle 77b has, metal oxide and porous material.For the absorbing particle 77b of metal oxide, can enumerate for example titanium oxide (TiO x), niobium oxide (NbO x), hafnium oxide (HfO x), indium oxide (In 2o x), tungsten oxide (WO x), tin-oxide (SnO x), zinc oxide (ZnO x), Zirconium oxide (ZrO x), magnesium oxide (MgO), sb oxide (SbO x), aluminum oxide (Al 2o x) etc.For the absorbing particle 77b of porous material, can enumerate for example silicon dioxide (SiO x), silica nitrogen (SiON) etc. (still, X>0).
And 74b has utilized epoxy resin for resin, still, silicones, fluoride resin, allyl resin etc., the resin that the emission wavelength from semiconductor light-emitting elements and quantum dot fluorescence body is had to a high permeability get final product.
(manufacture method)
Then, the manufacture method of the light-emitting device related to for embodiments of the invention 9, below describe.
At first, the packaging body 70 be mounted to semiconductor light-emitting elements 72, perfusion has disperseed quantum dot fluorescence body 75 and absorbing particle 77a (TiO x: resin 74a x>0) forms wavelength converter section 73.Now, with the bottom surface of covering packaging body and the mode of lead frame 71, form wavelength converter section 73.This wavelength converter section 73 is, contains quantum dot phosphor 75 and absorbing particle 77a in resin 74a.Quantum dot fluorescence body 75 is, for take emission wavelength as 530nm and 620nm luminous, and for example core has been utilized CdSe, shell has been utilized to the particulate below the particle diameter 20nm of ZnS.Absorbing particle 77a, by for example adsorb oxygen and for example do not absorb with the 450nm emission wavelength of luminous semiconductor light-emitting elements 72 and consist of the material of the wavelength of quantum dot fluorescence body 75 conversions.Such absorbing particle 77a has, for example the titanium oxide of average grain diameter 50nm.
Then, for example, once, with under 160 ℃ of conditions, by resin 74a thermmohardening 30 minutes.Then, perfusion has disperseed the resin 74b of absorbing particle 77b, forms oxygen absorbed layer 76.Now, the mode with the recess that covers wavelength converter section 73 and packaging body 70, form oxygen absorbed layer 76.This oxygen absorbed layer 76 is to contain absorbing particle 77b's in the resin 74b for example consisted of epoxy.This absorbing particle 77b is, the zeolite (aluminosilicate) that particle diameter 100 μ m are following.Then, for example, under 160 ℃ of conditions, by resin 74b thermmohardening 30 minutes.
Above, as to relate to according to embodiments of the invention 9 light-emitting device,, therefore can suppress to see through to the oxygen of wavelength converter section 73 by absorbing particle 77b absorption due to the many oxygen that see through in the resin 74a forming oxygen absorbed layer 76.Its result is, can suppress the oxidation of quantum dot phosphor 75, can realize the light-emitting device that luminous efficiency is high, colorrendering quality is good.
And, for quantum dot fluorescence body 75, the material that embodiment 5 puts down in writing gets final product.And, for the structure of quantum dot fluorescence body 75, utilized hud typedly, still, can be also the quantum well type.And, for the material of absorbing particle 77a, the material that embodiment 5 puts down in writing gets final product.And, for the material of resin 74a, the material that embodiment 5 puts down in writing gets final product.
(embodiment 10)
Then, the light-emitting device that embodiments of the invention 10 relate to is described.The basic structure of the light-emitting device that the present embodiment relates to is identical with embodiment 9.The present embodiment, the structures different from embodiment 9 are, between the inwall of the recess of wavelength converter section and oxygen absorbed layer and packaging body, form as adsorb oxygen or the oxidation prevention layer of the layer that do not make oxygen see through.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 10, utilize Figure 21 to describe.Figure 21 is the sectional view of the light-emitting device that relates to of embodiments of the invention 10.
As Figure 21 illustrates, packaging body 70 is that the structure with recess consisted of resin, in the bottom surface sections of recess, imbed the lead frame 71 consisted of the conductor with the first electrode and second electrode.
For the part of this lead frame 71, the bottom surface sections in the recess of packaging body 70 is exposed, and for example, with the semiconductor light-emitting elements 72 luminous with 450nm, is electrically connected to, and usings as the first electrode and the second electrode.And, be configured in the semiconductor light-emitting elements 72 of bottom surface sections of recess and the mode of the lead frame 71 that exposes in recess with covering, form wavelength converter section 73.
Wavelength converter section 73, in resin 74a, the quantum dot fluorescence body 75 that contains the following peak wavelength with 530nm and 620nm of particle diameter 20nm for example and as the titanium oxide (TiO of for example average grain diameter 50nm of the absorbing particle 77a of adsorb oxygen x: x>0).
And, to cover the mode of wavelength converter section 73, form oxygen absorbed layer 76.Oxygen absorbed layer 76 is, in resin 74b, contains the following zeolite (aluminosilicate) of particle diameter 100 μ m for example and can form.
Between the inwall of the recess of wavelength converter section 73 and packaging body 70, and, between the inwall of the recess of oxygen absorbed layer 76 and packaging body 70, form oxidation prevention layer 78.Oxidation prevention layer 78 is, for example silver (Ag) film forming at least 10nm to come up, can form.For silver, thermal conductance is high, also has radiating effect.Accordingly, oxidation prevention layer 78, also can suppress the promotion of the oxidation reaction that the heating because of quantum dot fluorescence body 75 causes.
At this, for the amount that is placed in the absorbing particle 77a in wavelength converter section 73, if resin 74a is for example epoxy resin, according to the path seen through to wavelength converter section 73 from oxygen (packaging body 70, the gap of lead frame 71 and packaging body 70), the oxygen amount (2.84 * 10 seen through to epoxy resin 19individual: as the oxygen amount after 40,000 hours), need to become 2.85 * 10 19more than individual.
And, for the amount that is placed in the absorbing particle 77b in oxygen absorbed layer 76, according to the oxygen amount (2.84 * 10 for example, seen through from bonding agent 80 (epoxy resin) 19individual: as the oxygen transit dose after 40,000 hours), need to become 2.84 * 10 19more than individual.
Above, as to relate to according to embodiments of the invention 10 light-emitting device, the oxygen seen through from packaging body 70, by oxidation prevention layer 78 (silver) absorption, therefore can more suppress to see through to the oxygen of wavelength converter section 73.
(manufacture method)
Then, the manufacture method of the light-emitting device related to for embodiments of the invention 10, below describe.
At first, with the bottom surface of the recess that covers packaging body 70 and the mode of lead frame 71, form for example Etching mask.Then, utilize evaporation or sputter etc., for example, the reflection of the light by luminous and the high silver of thermal conductivity are carried out to film forming, using as oxidation prevention layer 78.Then, carry out removing of Etching mask.
Then, at packaging body 70, semiconductor light-emitting elements 72 is installed.Then, the packaging body 70 be mounted to semiconductor light-emitting elements 72, perfusion has disperseed quantum dot fluorescence body 75 and absorbing particle 77a (TiO x: resin 74a x>0) forms wavelength converter section 73.Now, with the bottom surface of covering packaging body 70 and the mode of lead frame 71, form wavelength converter section 73.This wavelength converter section 73 is, contains quantum dot phosphor 75 and absorbing particle 77a in resin 74a.Quantum dot fluorescence body 75 is, for take emission wavelength as 530nm and 620nm luminous, and for example core has been utilized CdSe, shell has been utilized to the particulate below the particle diameter 20nm of ZnS.Absorbing particle 77b, by for example adsorb oxygen and for example do not absorb with the 450nm emission wavelength of luminous semiconductor light-emitting elements 72 and consist of the material of the wavelength of quantum dot fluorescence body 75 conversions.Such absorbing particle 77a has, for example the titanium oxide of average grain diameter 50nm.Then, for example, once, under 160 ℃ of conditions, by resin 74a thermmohardening 30 minutes.
Then, perfusion has disperseed the resin 74b of absorbing particle 77b, forms oxygen absorbed layer 76.Now, the mode with the recess that covers wavelength converter section 73 and packaging body 70, form oxygen absorbed layer 76.This oxygen absorbed layer 76 is to contain absorbing particle 77b's in the resin 74b for example consisted of epoxy resin.This absorbing particle 77b is, for example the following zeolite (aluminosilicate) of particle diameter 100 μ m.Then, for example, under 160 ℃ of conditions, by resin 74b thermmohardening 30 minutes.
Above, as to relate to according to embodiments of the invention 10 light-emitting device,, therefore can suppress to see through to the oxygen of wavelength converter section 73 by absorbing particle 77b absorption due to the many oxygen that see through in the resin 74a forming oxygen absorbed layer 76.Its result is, can more suppress the oxidation of quantum dot phosphor 75, can realize the light-emitting device that luminous efficiency is high, colorrendering quality is good.
And, for quantum dot fluorescence body 75, the material that embodiment 5 puts down in writing gets final product.And, for the structure of quantum dot fluorescence body 75, utilized hud typedly, still, can be also the quantum well type.And, for the material of absorbing particle 77a, the material that embodiment 5 puts down in writing gets final product.And, for the material of absorbing particle 77b, the material that embodiment 9 puts down in writing gets final product.And, for the material of resin 74a, the material that embodiment 5 puts down in writing gets final product.And, for the material of resin 74b, the material that embodiment 9 puts down in writing gets final product.
(embodiment 11)
Then, the light-emitting device that embodiments of the invention 11 relate to is described.The basic structure of the light-emitting device that the present embodiment relates to is identical with embodiment 9.The present embodiment, the structures different from embodiment 9 are to form the oxygen absorbed layer on the top of wavelength converter section.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 11, utilize Figure 22 to describe.Figure 22 is the sectional view of the light-emitting device that relates to of embodiments of the invention 11.
As Figure 22 illustrates, packaging body 70 is that the structure with recess consisted of resin, in the bottom surface sections of recess, imbed the lead frame 71 consisted of the conductor with the first electrode and second electrode.
For the part of this lead frame 71, the bottom surface sections in the recess of packaging body 70 is exposed, and for example, with the semiconductor light-emitting elements 72 luminous with 450nm, is electrically connected to, and usings as the first electrode and the second electrode.And, be configured in the semiconductor light-emitting elements 72 of bottom surface sections of recess and the mode of the lead frame 71 that exposes in recess with covering, form wavelength converter section 73.
Wavelength converter section 73 is, in resin 74a, the quantum dot fluorescence body 75 that contains the following peak wavelength with 530nm and 620nm of particle diameter 20nm for example and form as the titanium oxide (TiOx:x>0) of for example average grain diameter 50nm of the absorbing particle 77a of adsorb oxygen.
And, to cover the mode of wavelength converter section 73, form oxygen absorbed layer 76.Oxygen absorbed layer 76 is, in resin 74b, contains the following zeolite (aluminosilicate) of particle diameter 100 μ m for example and forms.To be covered the mode on the top of this oxygen absorbed layer 76 by glass cover 79, glass cover 79 is bonding by bonding agent 80 with packaging body 70.
Zeolite (aluminosilicate) is a kind of regular porous body, has four oxygen (O) crystal structure that three-dimensional connects regularly around silicon (Si) and aluminium (Al).
And zeolite is, at the Si with tetravalence, the structure of the Al of trivalent is put in identical position, and therefore, Al is negative charging, in order to keep electric neutrality, puts into cation in pore.For example, if put into potassium (K), fine pore can be changed to the 0.3nm of the size roughly the same with oxygen molecule, be placed in the oxygen in pore, because cationic electrostatic field is adsorbed.Particle diameter for zeolite now, be preferably 1 μ m to 100 μ m, more preferably 1 μ m to 20 μ m.This is because if particle diameter is too large, do not can be uniformly dispersed zeolite in resin, the cause that the oxygen adsorption effect reduces.
So, form oxygen absorbed layer 76 by the upper strata at wavelength converter section 73, thereby a large amount of oxygen that can suppress from air layer to wavelength converter section 73 sees through.And, even oxygen absorbed layer 76 adsorb oxygen fully, also by the absorbing particle 77a absorption of wavelength converter section 73 interior mixing.
And, for the absorbing particle 77a (titanium oxide) utilized in the present embodiment, average grain diameter is 50nm, size is similar to the particle diameter of quantum dot fluorescence body 75, therefore, and can be dispersed together with quantum dot fluorescence body 75 in resin 74a.
And then, by by glass cover 79, covering oxygen absorbed layer 76, thereby can reduce significantly to the oxygen of the oxygen absorbed layer 76 contacted most with oxygen, see through.
At this, for the amount that is placed in the absorbing particle 77a in wavelength converter section 73, according to the path seen through to wavelength converter section 73 from oxygen (packaging body 70, the gap of lead frame 71 and packaging body 70), to resin 74a(epoxy resin for example) the oxygen amount (1.1 * 10 that sees through 17individual: as the oxygen amount after 40,000 hours), need to become 1.2 * 10 17more than individual.
And, for the amount that is placed in the absorbing particle 77b in oxygen absorbed layer 76, according to the oxygen amount (7.6 * 10 for example, seen through to bonding agent 80 (epoxy resin) 14individual: as the oxygen transit dose after 40,000 hours), need to become 7.7 * 10 14more than individual.
According to such structure, can suppress the oxidation of quantum dot phosphor 75, the light-emitting device that obtains high efficiency light-emitting, high reliability can be provided.
(manufacture method)
Then, the manufacture method of the light-emitting device related to for embodiments of the invention 11, below describe.
At first, the packaging body 70 be mounted to semiconductor light-emitting elements 72, perfusion has disperseed quantum dot fluorescence body 75 and absorbing particle 77a (TiO x: resin 74a x>0) forms wavelength converter section 73.Now, with the bottom surface of covering packaging body 70 and the mode of lead frame 71, form wavelength converter section 73.This wavelength converter section 73 is, contains quantum dot phosphor 75 and absorbing particle 77a in resin 74a.Quantum dot fluorescence body 75 is, for take emission wavelength as 530nm and 620nm luminous, and for example core has been utilized CdSe, shell has been utilized to the particulate below the particle diameter 20nm of ZnS.Absorbing particle 77a, by for example adsorb oxygen and for example do not absorb with the 450nm emission wavelength of luminous semiconductor light-emitting elements 72 and consist of the material of the wavelength of quantum dot fluorescence body 75 conversions.Such absorbing particle 77a has, for example the titanium oxide of average grain diameter 50nm.Then, for example, once, under 160 ℃ of conditions, by resin 74a thermmohardening 30 minutes.
Then, perfusion has disperseed the resin 74b of absorbing particle 77b, forms oxygen absorbed layer 76.Now, the mode with the recess that covers wavelength converter section 73 and packaging body 70, form oxygen absorbed layer 76.This oxygen absorbed layer 76 is to contain absorbing particle 77b's in the resin 74b for example consisted of epoxy.Such absorbing particle 77b has, for example the following zeolite (aluminosilicate) of particle diameter 100 μ m.Now, utilize scraper, the resin 74b by after perfusion, become the plane same with the protuberance of packaging body 70, for example, with under 160 ℃ of conditions, thermmohardening 30 minutes, thus form oxygen absorbed layer 76.
Then, at the thin resin 74b of glass cover 79 coating, the mode contacted with oxygen absorbed layer 76 with resin 74b, by the bonding agent 80 for example formed by epoxy adhesive, that packaging body 70 and glass cover 79 is bonding, and gas-tight seal.Accordingly, can suppress significantly to see through to the oxygen of wavelength converter section 73.
Above, as to relate to according to embodiments of the invention 11 light-emitting device, can reduce the oxygen amount seen through to wavelength converter section 73 significantly, therefore can suppress significantly the oxidation of quantum dot phosphor 75.Its result is to realize the light-emitting device that luminous efficiency is high, colorrendering quality is good.
And, for quantum dot fluorescence body 75, the material that embodiment 5 puts down in writing gets final product.And, for the structure of quantum dot fluorescence body 75, utilized hud typedly, still, can be also the quantum well type.And, for the material of absorbing particle 77a, the material that embodiment 5 puts down in writing gets final product.And, for the material of absorbing particle 77b, the material that embodiment 9 puts down in writing gets final product.And, for the material of resin 74a, the material that embodiment 5 puts down in writing gets final product.And, for the material of resin 74b, the material that embodiment 9 puts down in writing gets final product.
(embodiment 12)
Then, the light-emitting device that embodiments of the invention 12 relate to is described.The basic structure of the light-emitting device that the present embodiment relates to is identical with embodiment 10.The present embodiment, the structures different from embodiment 10 are to form glass cover on the top of oxygen absorbed layer.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 12, utilize Figure 23 to describe.Figure 23 is the sectional view of the light-emitting device that relates to of embodiments of the invention 12.
As Figure 23 illustrates, packaging body 70 is that the structure with recess consisted of resin, in the bottom surface sections of recess, imbed the lead frame 71 consisted of the conductor with the first electrode and second electrode.
For the part of this lead frame 71, the bottom surface sections in the recess of packaging body 70 is exposed, and for example, with the semiconductor light-emitting elements 72 luminous with 450nm, is electrically connected to, and usings as the first electrode and the second electrode.And, be configured in the semiconductor light-emitting elements 72 of bottom surface sections of recess and the mode of the lead frame 71 that exposes in recess with covering, form wavelength converter section 73.
Wavelength converter section 73 is, in resin 74a, the quantum dot fluorescence body 75 that contains the following peak wavelength with 530nm and 620nm of particle diameter 20nm for example and form as the titanium oxide (TiOx:x>0) of for example average grain diameter 50nm of the absorbing particle 77a of adsorb oxygen.
And, to cover the mode of wavelength converter section 73, form oxygen absorbed layer 76.Oxygen absorbed layer 76 is, in resin 74b, contains the following zeolite (aluminosilicate) of particle diameter 100 μ m for example and forms.
Between the inwall of the recess of wavelength converter section 73 and packaging body 70, and, between the inwall of the recess of oxygen absorbed layer 76 and packaging body 70, form oxidation prevention layer 78.Oxidation prevention layer 78 is, for example silver (Ag) film forming at least 10nm to come up, can form.For silver, thermal conductance is high, also has radiating effect.Accordingly, oxidation prevention layer 78, adsorb oxygen or do not make oxygen see through not only, also can suppress the promotion of the oxidation reaction that the heating because of quantum dot fluorescence body 75 causes.
To be covered the mode on the top of this oxygen absorbed layer 76 and oxidation prevention layer 78 by glass cover 79, glass cover 79 is bonding by bonding agent 80 with packaging body 70.
At this, for the amount that is placed in the absorbing particle 77a in wavelength converter section 73, if resin 74a is for example epoxy resin, according to the path seen through to wavelength converter section 73 from oxygen (packaging body 70, the gap of lead frame 71 and packaging body 70), the oxygen amount (1.2 * 10 seen through to epoxy resin 17individual: as the oxygen amount after 40,000 hours), need to become 1.3 * 10 17more than individual.
And, for the amount that is placed in the absorbing particle 77b in oxygen absorbed layer 76, according to the oxygen amount (7.7 * 10 for example, seen through from bonding agent 80 (epoxy resin) 14individual: as the oxygen transit dose after 40,000 hours), need to become 7.7 * 10 14more than individual.
Above, as to relate to according to embodiments of the invention 12 light-emitting device, the oxygen seen through from packaging body 70, by oxidation prevention layer 78 (silver) absorption, therefore can more suppress to see through to the oxygen of wavelength converter section 73.
(manufacture method)
Then, the manufacture method of the light-emitting device related to for embodiments of the invention 12, below describe.
At first, with the bottom surface of the recess that covers packaging body 70 and the mode of lead frame 71, form for example Etching mask.Then, utilize evaporation or sputter etc., for example, the reflection of the light by luminous and the high silver of thermal conductivity are carried out to film forming, using as oxidation prevention layer 78.Then, carry out removing of Etching mask.
Then, at packaging body 70, semiconductor light-emitting elements 72 is installed.Then, the packaging body 70 be mounted to semiconductor light-emitting elements 72, perfusion has disperseed quantum dot fluorescence body 75 and absorbing particle 77a (TiO x: resin 74a x>0) forms wavelength converter section 73.Now, with the bottom surface of covering packaging body 70 and the mode of lead frame 71, form wavelength converter section 73.This wavelength converter section 73 is, contains quantum dot phosphor 75 and absorbing particle 77a in resin 74a.Quantum dot fluorescence body 75 is, for take emission wavelength as 530nm and 620nm luminous, and for example core has been utilized CdSe, shell has been utilized to the particulate below the particle diameter 20nm of ZnS.Absorbing particle 77a, by for example adsorb oxygen and for example do not absorb with the 450nm emission wavelength of luminous semiconductor light-emitting elements 72 and consist of the material of the wavelength of quantum dot fluorescence body 75 conversions.Such absorbing particle 77a has, for example the titanium oxide of average grain diameter 50nm.Then, for example, once, under 160 ℃ of conditions, by resin 74a thermmohardening 30 minutes.
Then, perfusion has disperseed the resin 74b of absorbing particle 77b, forms oxygen absorbed layer 76.Now, the mode with the recess that covers wavelength converter section 73 and packaging body 70, form oxygen absorbed layer 76.This oxygen absorbed layer 76 is to contain absorbing particle 77b's in the resin 74b for example consisted of epoxy resin.This absorbing particle 77b is, for example the following zeolite (aluminosilicate) of particle diameter 100 μ m.Now, utilize scraper, the resin 74b by after perfusion, become the plane same with the protuberance of packaging body 70, for example, under 160 ℃ of conditions, thermmohardening 30 minutes, thus form the second oxygen absorbed layer.Then, for example, under 160 ℃ of conditions, by resin 74b thermmohardening 30 minutes.
Then, at the thin resin 74b of glass cover 79 coating, the mode contacted with oxygen absorbed layer 76 with resin 74b, by the bonding agent 80 for example formed by epoxy adhesive, that packaging body 70 and glass cover 79 is bonding, and gas-tight seal.Accordingly, can suppress significantly to see through to the oxygen of wavelength converter section 73.And, can suppress significantly the oxidation of quantum dot phosphor 75.Its result is to realize the light-emitting device that luminous efficiency is high, colorrendering quality is good.
And, for quantum dot fluorescence body 75, the material that embodiment 5 puts down in writing gets final product.And, for the structure of quantum dot fluorescence body 75, utilized hud typedly, still, can be also the quantum well type.And, for the material of absorbing particle 77a, the material that embodiment 5 puts down in writing gets final product.And, for the material of absorbing particle 77b, the material that embodiment 9 puts down in writing gets final product.And, for the material of resin 74a, the material that embodiment 5 puts down in writing gets final product.And, for the material of resin 74b, the material that embodiment 9 puts down in writing gets final product.
(embodiment 13)
Then, the light-emitting device that embodiments of the invention 13 relate to is described.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 13, utilize Figure 24 to describe.Figure 24 is the sectional view of the light-emitting device that relates to of embodiments of the invention 13.
As Figure 24 illustrates, the light-emitting device that embodiments of the invention 13 relate to possesses: packaging body 70 has recess; Lead frame 71, expose in the bottom surface of recess; The first oxygen absorbed layer 76a, be formed and cover the lead frame exposed; Quantum dot fluorescence body layer 75a, be formed on the first oxygen absorbed layer 76a; And the second oxygen absorbed layer 76b, be formed and cover quantum dot phosphor layer 75a.
Packaging body 70 is that the structure with recess consisted of resin, in the bottom surface sections of recess, imbed the lead frame 71 consisted of the conductor with the first electrode and second electrode.
For the part of this lead frame 71, the bottom surface sections in the recess of packaging body 70 is exposed, and for example, with the semiconductor light-emitting elements 72 luminous with 450nm, is electrically connected to, and usings as the first electrode and the second electrode.
And, be configured in the semiconductor light-emitting elements 72 of bottom surface sections of recess and the mode of the lead frame 71 that exposes in recess with covering, form the first oxygen absorbed layer 76a.The first oxygen absorbed layer 76a is, in resin 74a, contains and forms as for example zeolite (aluminosilicate) of the absorbing particle 77 of adsorb oxygen.
And, on the first oxygen absorbed layer 76a in recess, form, in resin 74b, for example disperseed to have the quantum dot fluorescence body layer 75a of quantum dot fluorescence body 75 of the peak wavelength of 530nm and 620nm.This quantum dot fluorescence body layer 75a, can contact with packaging body 70, also can not contact with packaging body 70.
And, on quantum dot fluorescence body layer 75a, to cover the mode of the quantum dot fluorescence body layer 75a exposed in recess, form the second oxygen absorbed layer 76b.The second oxygen absorbed layer 76b is, in resin 74c, contains and forms as for example zeolite (aluminosilicate) of the absorbing particle 77 of adsorb oxygen.
So, by the resin portion of the first oxygen absorbed layer 76a, the second oxygen absorbed layer 76b and packaging body 70, cover quantum dot phosphor layer 75a, therefore can suppress the oxidation of the quantum dot fluorescence body 75 that the oxygen because of the top from packaging body 70 and bottom surface sections intrusion causes.
And, even in the situation that only by the resin bed that comprises the oxygen absorbent as absorbing particle 77 of the first oxygen absorbed layer 76a and the second oxygen absorbed layer 76b etc., cover quantum dot phosphor layer 75a, also can suppress the oxidation of the quantum dot fluorescence body 75 that the oxygen because of the top from packaging body 70 and bottom surface sections intrusion causes.
At this, the zeolite (aluminosilicate) utilized as absorbing particle 77 is a kind of regular porous body, has four oxygen (O) crystal structure that three-dimensional connects regularly around silicon (Si) and aluminium (Al).
And zeolite is, at the Si with tetravalence, the structure of the Al of trivalent is put in identical position, and therefore, Al is negative charging, in order to keep electric neutrality, puts into cation in pore.For example, if put into potassium (K), fine pore can be changed to the 0.3nm of the size roughly the same with oxygen molecule, be placed in the oxygen in pore, because cationic electrostatic field is adsorbed.Particle diameter for zeolite now, be preferably 1 μ m to 100 μ m, more preferably 1 μ m to 20 μ m.This is because if particle diameter is too large, do not can be uniformly dispersed zeolite in resin, the cause that the oxygen adsorption effect reduces.
Above, as to relate to according to embodiments of the invention 13 light-emitting device, can access following action effect.
The position that the oxygen of the reason reduced as the luminous efficiency of quantum dot fluorescence body 75 is invaded is, the gap of packaging body 70 and lead frame 71 and the face contacted with top air.
In the present embodiment, top and the bottom of quantum dot fluorescence body layer 75a, covered by the first oxygen absorbed layer 76a and the second oxygen absorbed layer 76b, therefore, can suppress oxygen and enter into quantum dot fluorescence body layer 75a.Accordingly, the luminous efficiency that can suppress the quantum dot fluorescence body 75 that causes because of oxidation reduces, and therefore can realize the light-emitting device of high reliability.
At this, consider to see through the oxygen amount of resin.The oxygen amount that sees through resin is that the oxygen transmission coefficient that can have according to resin calculates.For example, in the situation that utilize the epoxy resin (100 μ m) as resin 74a and resin 74c, the oxygen transmission coefficient is 52cc/m 2day, the oxygen amount seen through to epoxy resin from air layer is 1.97 * 10 11individual/s.
Generally speaking, the LED illumination need to have the long products life-span of so-called 40,000 hours.That is to say, the oxidation of needs inhibition quantum dot phosphor 75 40,000 hours, oxygen transit dose now is 2.84 * 10 19individual.Considering for an oxygen molecule, adsorb in the situation of a zeolite particles, in order to adsorb all oxygen seen through, need 2.85 * 10 19individual above zeolite.And, from the oxygen transit dose in the gap of lead frame 71 and packaging body 70, be 8.1 * 10 8individual/s (is 1.2 * 10 after 40,000 hours 17individual).Therefore, need to be placed in the interior zeolite of oxygen absorbed layer of the bottom that is arranged on quantum dot fluorescence body layer 75a, become 1.3 * 10 17more than individual.
And, in the present embodiment, for resin 74a and resin 74c, utilized epoxy resin, but, resin 74a and resin 74c be, silicones, fluoride resin, allyl resin etc., the resin that the emission wavelength from semiconductor light-emitting elements and quantum dot fluorescence body is had to a high permeability get final product.
And, in the present embodiment, for absorbing particle 77, utilized zeolite (aluminosilicate), still, be not limited only to this.For example, the candidate of absorbing particle 77 has, metal oxide and porous material.
For the absorbing particle 77 of metal oxide, can enumerate for example titanium oxide (TiO x), niobium oxide (NbO x), hafnium oxide (HfO x), indium oxide (In 2o x), tungsten oxide (WO x), tin-oxide (SnO x), zinc oxide (ZnO x), Zirconium oxide (ZrO x), magnesium oxide (MgO), sb oxide (SbO x) etc.For the absorbing particle 77 of porous material, can enumerate for example silicon dioxide (SiO x), silica nitrogen (SiON) etc. (still, 0<X).
For the structure of quantum dot fluorescence body 75, can enumerate hud typed, quantum well type etc., still, in the present embodiment, can be suitable for which structure.
And, for the core that forms quantum dot fluorescence body 75 and the material of shell, for example, situation for the II-VI compounds of group, can enumerate from CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnZe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnZeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgSeTe, CdHgSTe, HgZnSS, HgZnSeTe, at least one that select in HgZnSTe etc.
And, example for the III-V compounds of group, can enumerate from GaN, GaP, GaAs, GaSb, AlN, AlGaN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, InGaN, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, InAlNP, InAlNAs, InAlNSb, InAlPAs, at least one that select in InAlPSb etc.
(manufacture method)
Then, the manufacture method of the light-emitting device related to for embodiments of the invention 13, below describe.
At first, the packaging body 70 be mounted to semiconductor light-emitting elements 72, perfusion has disperseed the resin 74a of absorbing particle 77 (zeolite).Now, with at least a portion of the bottom surface that covers packaging body 70 and the mode of lead frame 71, form resin 74a.This resin 74a, contain adsorb oxygen for example and for example do not absorb with the 450nm emission wavelength of luminous semiconductor light-emitting elements 72 and by the absorbing particle 77 of the wavelength of quantum dot fluorescence body 75 conversions.Such absorbing particle 77 has, the zeolite that the grain size with fine pore equal with oxygen molecule diameter 0.3nm is 5 to 20 μ m left and right.
Then, for example, under 160 ℃ of conditions, by resin 74a thermmohardening 30 minutes, thereby form the first oxygen absorbed layer 76a.
Then, on the first oxygen absorbed layer 76a in recess, perfusion has for example utilized CdSe, shell has been utilized to the resin 74b of the quantum dot fluorescence body 75 of the peak wavelength that has 530nm and 620nm for example having disperseed below the particle diameter 20nm of ZnS core.And, under 160 ℃ of conditions, by resin 74b thermmohardening 30 minutes, thereby form quantum dot phosphor layer 75a.
And, on quantum dot fluorescence body layer 75a, in the mode on the top that covers the quantum dot fluorescence body layer 75a in recess, perfusion has disperseed the resin 74c of absorbing particle 77 (zeolite), for example, and under 160 ℃ of conditions, thermmohardening 30 minutes, thus the second oxygen absorbed layer 76b formed.
(embodiment 14)
Then, the light-emitting device that embodiments of the invention 14 relate to is described.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 14, utilize Figure 25 to describe.Figure 25 is the sectional view of the light-emitting device that relates to of embodiments of the invention 14.
As Figure 25 illustrates, the structure of the light-emitting device that embodiments of the invention 14 relate to is, covered the top of the light-emitting device that embodiment 13 relate to by glass cover 79.So, cover the position contacted most with oxygen on the top of packaging body 70 by glass cover 79, thereby can suppress significantly the amount through the oxygen of the second oxygen absorbed layer 76b.Accordingly, can prevent the reduction of the luminous efficiency of the quantum dot fluorescence body 75 that causes because of oxidation.
(manufacture method)
The manufacture method of the light-emitting device that embodiments of the invention 14 relate to then, is described.
At first, the packaging body 70 be mounted to semiconductor light-emitting elements 72, perfusion has disperseed the resin 74a of absorbing particle 77 (zeolite).Now, with at least a portion of the bottom surface that covers packaging body 70 and the mode of lead frame 71, form resin 74a.This resin 74a, contain adsorb oxygen for example and for example do not absorb with the 450nm emission wavelength of luminous semiconductor light-emitting elements 72 and by the absorbing particle 77 of the wavelength of quantum dot fluorescence body 75 conversions.Such absorbing particle 77 has, the zeolite that the grain size with fine pore equal with oxygen molecule diameter 0.3nm is 5 to 20 μ m left and right.
Then, for example, under 160 ℃ of conditions, by resin 74a thermmohardening 30 minutes, thereby form the first oxygen absorbed layer 76a.
Then, on the first oxygen absorbed layer 76a in recess, perfusion has for example utilized CdSe, shell has been utilized to the resin 74b of the quantum dot fluorescence body 75 of the peak wavelength that has 530nm and 620nm for example having disperseed below the particle diameter 20nm of ZnS core.And, under 160 ℃ of conditions, by resin 74b thermmohardening 30 minutes, thereby form quantum dot phosphor layer 75a.And, on quantum dot fluorescence body layer 75a, in the mode on the top that covers the quantum dot fluorescence body layer 75a in recess, perfusion has disperseed the resin 74c of absorbing particle 77 (zeolite).Now, utilize scraper, the resin 74c by after perfusion, become the plane same with the protuberance of packaging body 70, for example, under 160 ℃ of conditions, thermmohardening 30 minutes, thus form the second oxygen absorbed layer 76b.
Then, at the thin resin 74c of glass cover 79 coating, with resin 74c and the mode that the second oxygen absorbed layer 76b contacts, utilize organic polymer bonding agent (for example epoxy resin), glass cover 79 and packaging body 70 is bonding.
Above, as to relate to according to embodiments of the invention 14 light-emitting device, cover the position contacted most with oxygen on the top of packaging body 70 by glass cover 79, thereby can suppress significantly the amount through the oxygen of the second oxygen absorbed layer 76b.Accordingly, can prevent the reduction of the luminous efficiency of the quantum dot fluorescence body 75 that causes because of oxidation.
And in the present embodiment, the transit dose of the oxygen seen through from the organic polymer bonding agent between packaging body 70 and glass cover 79 is, 5.4 * 10 8individual/s (is 7.8 * 10 after 40,000 hours 16individual).For the amount of sneaking into the absorbing particle 77 in the second oxygen absorbed layer 76b on the top that is arranged on quantum dot fluorescence body layer 75a, considering for an oxygen molecule, adsorb in the situation of a zeolite particles, in order to adsorb all oxygen seen through, need to become 7.9 * 10 16more than individual.And, for the zeolite in the oxygen absorbed layer that is placed in the bottom that is arranged on quantum dot fluorescence body layer 75a, put into the amount that the manufacture method of embodiment 13 illustrates and get final product.
And, in the present embodiment, for absorbing particle 77, utilized zeolite (aluminosilicate), still, be not limited only to this.The candidate of absorbing particle 77 has, metal oxide and porous material, and this material is that the material of enumerating in embodiment 13 gets final product.And, for the structure of quantum dot fluorescence body 75, utilized hud typedly, still, can be also the quantum well type.And the material that forms quantum dot fluorescence body 75 is that the material of enumerating in embodiment 13 gets final product.And the material of resin 74a, resin 74b is that the material of enumerating in embodiment 13 gets final product.
And, in the present embodiment, on packaging body 70 and glass cover 79 bonding, utilized the organic polymer bonding agent, still, also can in this bonding agent, put into absorbing particle 77.Accordingly, can suppress to see through from the oxygen of bonding plane.
(embodiment 15)
Then, the light-emitting device that embodiments of the invention 15 relate to is described.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 15, utilize Figure 26 to describe.Figure 26 is the sectional view of the light-emitting device that relates to of embodiments of the invention 15.
As Figure 26 illustrates, similarly to Example 13, the light-emitting device that embodiments of the invention 15 relate to possesses, packaging body 70, lead frame 71, the first oxygen absorbed layer 76a, quantum dot fluorescence body layer 75a and the second oxygen absorbed layer 76b.And then the light-emitting device that the present embodiment relates to possesses, oxidation prevention layer 78.
Packaging body 70 is that the structure with recess consisted of resin, in the bottom surface sections of recess, imbed the lead frame 71 consisted of the conductor with the first electrode and second electrode.
For the part of this lead frame 71, the bottom surface sections in the recess of packaging body 70 is exposed, and for example, with the semiconductor light-emitting elements 72 luminous with 450nm, is electrically connected to, and usings as the first electrode and the second electrode.
And, be configured in the semiconductor light-emitting elements 72 of bottom surface sections of recess and the mode of the lead frame 71 that exposes in recess with covering, form the first oxygen absorbed layer 76a.The first oxygen absorbed layer 76a is, in resin 74a, for example contains and to form as for example zeolite (aluminosilicate) of the absorbing particle 77 of adsorb oxygen.
And, on the first oxygen absorbed layer 76a in recess, form, in resin 74b, for example disperseed to have the quantum dot fluorescence body layer 75a of quantum dot fluorescence body 75 of the peak wavelength of 530nm and 620nm.This quantum dot fluorescence body layer 75a, can contact with packaging body 70, also can not contact with packaging body 70.
And, on quantum dot fluorescence body layer 75a, to cover the mode of the quantum dot fluorescence body layer 75a exposed in recess, form the second oxygen absorbed layer 76b.The second oxygen absorbed layer 76b is, in resin 74c, contains and forms as for example zeolite (aluminosilicate) of the absorbing particle 77 of adsorb oxygen.
Between the sidewall (inwall of recess) of the first oxygen absorbed layer 76a, quantum dot fluorescence body layer 75a and the second oxygen absorbed layer 76b and packaging body 70, form as adsorb oxygen or the oxidation prevention layer 78 of the layer that do not make oxygen see through.For this oxidation prevention layer 78, preferably, utilize for example reflecting metallic film (for example silver) or Porous particle membrane (for example zeolite).
According to this structure, can suppress to see through the oxygen of trace of the sidewall of packaging body 70.Accordingly, can suppress the oxidation with the quantum dot fluorescence body 75 of the contacts side surfaces of packaging body 70, can prevent that irregular colour is even, the reduction of luminous efficiency.
(manufacture method)
The manufacture method of the light-emitting device that embodiments of the invention 15 relate to then, is described.And, in the manufacture method of the present embodiment, centered by the part that embodiment 13 is appended, describe.
For example, at the inwall of packaging body 70, utilize evaporation, sputter, gold-plated, electrodeposition process etc., the reflecting metallic film for example consisted of silver (Ag) is carried out to film forming, using as oxidation prevention layer 78.
Then, semiconductor light-emitting elements 72 is installed to packaging body.Then, same with the manufacture method of embodiment 13, by covered top and the bottom of quantum dot phosphor layer 75a by the oxygen absorbed layer, thereby can manufacture light-emitting device.
Above, as to relate to according to embodiments of the invention 15 light-emitting device, except the action effect of embodiment 13, can also obtain following action effect.
Packaging body 70 is formed by resin, therefore from packaging body 70, also sees through micro-oxygen.In embodiment 13 and embodiment 14, the position contacted with quantum dot fluorescence body layer 75a in the packaging body side, the oxidation that produces quantum dot phosphor 75, and not luminous, it is even therefore irregular colour to occur.
But, as the present embodiment, by oxidation prevention layer 78 is set, can suppress from the seeing through of the oxygen of packaging body 70, therefore, can suppress the oxidation of quantum dot fluorescence body 75 at the position of quantum dot phosphor layer 75a and packaging body 70 contacts side surfaces.Its result is, can suppress the reduction of the even and luminous efficiency of irregular colour.
And in the present embodiment, the material for oxidation prevention layer 78, utilized silver, still, is not limited only to this.For the material of oxidation prevention layer 78, the material that utilizes adsorb oxygen or do not make oxygen see through gets final product, for example, if metal, metal oxide, Porous particle have no particular limits.If metal, can enumerate such as gold, silver, aluminium, titanium, magnesium, nickel etc.If metal oxide, can enumerate such as titanium oxide, niobium oxide, hafnium oxide, indium oxide, tungsten oxide, tin-oxide, zinc oxide, Zirconium oxide, magnesium oxide, sb oxide etc.In the situation that the Porous particle can be enumerated such as silicon dioxide, silica nitrogen, zeolite etc.
Now, the oxygen amount seen through from the sidewall of packaging body 70 is, 5.3 * 10 8individual/s (is 7.7 * 10 after 40,000 hours 16individual).Now, in the side of packaging body 70, in the situation that utilize for example silver of oxidation prevention layer 78, thickness needs at least more than 10nm.
And, for the zeolite (absorbing particle 77) in the oxygen absorbed layer that is placed in the top that is arranged on quantum dot fluorescence body layer 75a and bottom, put into the amount that the manufacture method of embodiment 13 illustrates and get final product.
And, in the present embodiment, for absorbing particle 77, utilized zeolite (aluminosilicate), still, be not limited only to this.The candidate of absorbing particle 77 has, metal oxide and porous material, and this material is that the material of enumerating in embodiment 13 gets final product.And, for the structure of quantum dot fluorescence body 75, utilized hud typedly, still, can be also the quantum well type.And the material that forms quantum dot fluorescence body 75 is that the material of enumerating in embodiment 13 gets final product.And the material of resin 74a, resin 74b is that the material of enumerating in embodiment 13 gets final product.
(embodiment 16)
Then, the light-emitting device that embodiments of the invention 16 relate to is described.
(structure)
At first, the schematic configuration of the light-emitting device related to for embodiments of the invention 16, utilize Figure 27 to describe.Figure 27 is the sectional view of the light-emitting device that relates to of embodiments of the invention 16.
As Figure 27 illustrates, the structure of the light-emitting device that embodiments of the invention 16 relate to is, covered the top of the light-emitting device that embodiment 15 relate to by glass cover 79.So, cover the position contacted most with oxygen on the top of packaging body 70 by glass cover 79, thereby can suppress significantly the amount through the oxygen of the second oxygen absorbed layer 76b.Accordingly, can prevent the reduction of the luminous efficiency of quantum dot fluorescence body 75.
Above, as to relate to according to embodiments of the invention 16 light-emitting device, can suppress to see through the oxygen of trace of the sidewall of packaging body 70.Accordingly, can suppress the oxidation with the quantum dot fluorescence body 75 of the contacts side surfaces of packaging body 70.Can prevent that irregular colour is even, the reduction of luminous efficiency.
(manufacture method)
The manufacture method of the light-emitting device that embodiments of the invention 16 relate to then, is described.
At first, with the bottom surface of the recess that covers packaging body 70 and the mode of lead frame 71, form for example Etching mask.
Then, utilize evaporation or sputter etc., at the sidewall (inwall of recess) of the recess of packaging body 70, for example, the reflection of the light by luminous, silver that thermal conductivity is high are carried out to film forming, using as oxidation prevention layer 78.Then, carry out removing of Etching mask.Then, at packaging body 70, semiconductor light-emitting elements 72 is installed.
Then, the packaging body 70 be mounted to semiconductor light-emitting elements 72, perfusion has disperseed the resin 74a of quantum dot fluorescence body 75 and absorbing particle 77 (zeolite).Now, with the bottom surface of covering packaging body 70 and the mode of at least a portion and lead frame 71, form resin 74a.This resin 74a, contain adsorb oxygen for example and for example do not absorb with the 450nm emission wavelength of luminous semiconductor light-emitting elements 72 and by the absorbing particle 77 of the wavelength of quantum dot fluorescence body 75 conversions.Such absorbing particle 77 has, the zeolite that the grain size with fine pore equal with oxygen molecule diameter 0.3nm is 5 to 20 μ m left and right.Then, for example, under 160 ℃ of conditions, by resin 74a thermmohardening 30 minutes, thereby form the first oxygen absorbed layer 76a.
Then, on the first oxygen absorbed layer 76a in recess, perfusion has for example utilized CdSe, shell has been utilized to the resin 74b of the quantum dot fluorescence body 75 of the peak wavelength that has 530nm and 620nm for example having disperseed below the particle diameter 20nm of ZnS core.And, under 160 ℃ of conditions, by resin 74b thermmohardening 30 minutes, thereby form quantum dot phosphor layer 75a.
And, on quantum dot fluorescence body layer 75a, in the mode on the top that covers the quantum dot fluorescence body layer 75a in recess, perfusion has disperseed the resin 74c of absorbing particle 77 (zeolite).Now, utilize scraper, the resin 74c by after perfusion, become the plane same with the protuberance of packaging body 70, for example, under 160 ℃ of conditions, thermmohardening 30 minutes, thus form the second oxygen absorbed layer 76b.
Then, at the thin resin 74c of glass cover 79 coating, with resin 74c and the mode that the second oxygen absorbed layer 76b contacts, utilize bonding agent (for example epoxy resin), glass cover 79 and packaging body 70 is bonding.
And in the present embodiment, for quantum dot fluorescence body 75, the material that embodiment 13 puts down in writing gets final product.And, for the structure of quantum dot fluorescence body 75, utilized hud typedly, still, can be also the quantum well type.And, for the material of absorbing particle 77, the material that embodiment 13 puts down in writing gets final product.And, for the material of resin 74a, resin 74c, the material that embodiment 13 puts down in writing gets final product.
And, in the present embodiment, for oxidation prevention layer 78, utilized silver, but, being not limited only to this, the material that utilizes adsorb oxygen or do not make oxygen see through gets final product, for example, if metal, metal oxide, Porous particle, have no particular limits, the material of enumerating in embodiment 15 gets final product.
And, covered the position contacted most with oxygen by glass cover 79, thereby can be suppressed at that the oxygen absorbed layer can not adsorb and the oxygen that sees through to quantum dot phosphor layer 75a.Accordingly, the oxygen transit dose can be more reduced, the reduction of the luminous efficiency of the quantum dot fluorescence body 75 that causes because of oxidation can be prevented.
And in the present embodiment, the transit dose of the oxygen for example, seen through from organic polymer bonding agent (epoxy) is, 5.3 * 10 6individual/s (is 7.7 * 10 after 40,000 hours 14individual), for the amount of sneaking into the absorbing particle 77 in the first oxygen absorbed layer 76a of the bottom that is arranged on quantum dot fluorescence body layer 75a, considering for an oxygen molecule, adsorb in the situation of a zeolite particles, in order to adsorb all oxygen seen through, need 7.8 * 10 14more than individual.And, for the zeolite in the first oxygen absorbed layer 76a that is placed in the bottom that is arranged on quantum dot fluorescence body layer 75a, put into the amount that the manufacture method of embodiment 13 illustrates and get final product.And, for the zeolite in the second oxygen absorbed layer 76b that is placed in the top that is arranged on quantum dot fluorescence body layer 75a, put into the amount that the manufacture method of embodiment 13 illustrates and get final product.And, in the situation that utilize the silver as oxidation prevention layer 78, thickness needs at least more than 10nm.
And, in the present embodiment, for absorbing particle 77, utilized zeolite (aluminosilicate), still, be not limited only to this.The candidate of absorbing particle 77 has, metal oxide and porous material, and this material is that the material of enumerating in embodiment 13 gets final product.And, for the structure of quantum dot fluorescence body 75, utilized hud typedly, still, can be also the quantum well type.
And, in the present embodiment, on packaging body 70 and glass cover 79 bonding, utilized the organic polymer bonding agent, still, also can in this bonding agent, put into absorbing particle 77.Accordingly, can suppress to see through from the oxygen of bonding plane.
Above, for the present invention, according to embodiment and variation, be illustrated, still, the present invention, be not limited only to such embodiment and variation.The form of for example, the present embodiment having been carried out to the various distortion that those skilled in the art expects in the scope that does not break away from aim of the present invention is also contained in scope of the present invention.And, in the scope that does not break away from aim of the present invention, each inscape in can a plurality of embodiment of combination in any.
Industrial applicibility
The present invention, can suppress to be formed on the oxidation of the fluorophor on semiconductor light-emitting elements, can suppress the reduction of quantum efficiency, therefore, be useful on and realize having utilized semiconductor light-emitting elements quantum dot fluorescence body and organic fluorescent, that there is high-luminous-efficiency and the technology of light-emitting device.
symbol description
1,101,2,201,4 semiconductor light-emitting elements
3 light-emitting devices
10 substrates
11 resilient coatings
12 first cover layers
13 active layers
14 second cover layers
15 contact layers
16 the first metal layers
17 n electrodes
18 first dielectric films
19,19a, 19b the second metal level
20,20a, 20b the second dielectric film
21 the 3rd dielectric films
22 the 4th dielectric films
25a the first semiconductor microactuator particle
25b the second semiconductor microactuator particle
30,35,36 peristomes
31 grooves
50 packaging bodies
51 resins
52,53 lead frames
55,56 wires
60 resin beds
61 high heat conduction particulates
70 packaging bodies
71 lead frames
72 semiconductor light-emitting elements
73 wavelength converter sections
74a, 74b, 74c resin
75 quantum dot fluorescence bodies
75a quantum dot fluorescence body layer
76 oxygen absorbed layers
76a the first oxygen absorbed layer
76b the second oxygen absorbed layer
77,77a, 77b absorbing particle
78 oxidation prevention layers
79 glass covers
80 bonding agents
91 cutter
92 laser

Claims (20)

1. a semiconductor light-emitting elements possesses:
Semiconductor layer, comprise active layer;
The first metal layer, be formed on described semiconductor layer;
The first dielectric film, be formed on described the first metal layer, and in the mode of the top and side that covers described semiconductor layer and be formed;
The second dielectric film, be formed on described the first dielectric film and comprise the semiconductor microactuator particle; And
The 3rd dielectric film, be formed on described the second dielectric film,
Described the second dielectric film is covered by the first dielectric film and the 3rd dielectric film.
2. semiconductor light-emitting elements as claimed in claim 1,
Described the first dielectric film on described the first metal layer is formed with peristome.
3. semiconductor light-emitting elements as claimed in claim 2,
Be formed with the second metal level at described peristome, this second metal level is connected with described the first metal layer.
4. semiconductor light-emitting elements as claimed in claim 1,
Described the first metal layer is transparency electrode,
The material of described transparency electrode is, has been added some among the indium oxide of tin, the tin oxide that has been added antimony and zinc oxide.
5. semiconductor light-emitting elements as claimed in claim 1,
Described semiconductor microactuator particle is the quantum dot fluorescence body, and described semiconductor microactuator particle is constituted as and absorbs luminous from described active layer, and sends the luminous different light from described active layer.
6. semiconductor light-emitting elements as claimed in claim 1,
Described the 3rd dielectric film is film and the high film of thermal conductivity that does not at least make oxygen see through, and described the 3rd dielectric film is some among aluminium nitride, silicon nitride, silica nitrogen, Si oxide, zinc oxide, aluminum oxide and indium oxide.
7. semiconductor light-emitting elements as described as any one of claim 1 to 6,
Possess the 4th dielectric film between described the second dielectric film and described the 3rd dielectric film,
Described the second dielectric film is covered by described the 4th dielectric film,
Described the 4th dielectric film is covered by described the 3rd dielectric film.
8. a light-emitting device, be the light-emitting device that possesses the described semiconductor light-emitting elements of any one of claim 1 to 7, and this light-emitting device possesses:
Packaging body, consist of resin, and have recess;
Lead frame, expose in the bottom surface of described recess;
Described semiconductor light-emitting elements, be arranged on the lead frame in described recess; And
Resin portion is formed to cover the mode on described semiconductor light-emitting elements in described recess,
Described resin portion comprises heat conduction particulate.
9. a light-emitting device possesses:
Packaging body, consist of resin, and have recess;
Lead frame, expose in the bottom surface of described recess;
Semiconductor light-emitting elements, be arranged on the lead frame in described recess; And
The first resin portion is formed in the mode that covers described semiconductor light-emitting elements in described recess,
Described the first resin portion consists of the first absorbing particle of quantum dot fluorescence body and adsorb oxygen.
10. light-emitting device as claimed in claim 9,
The particle diameter of described the first absorbing particle is below 100nm.
11. light-emitting device as claimed in claim 9,
Described light-emitting device also possesses the second resin portion, and this second resin portion is formed in the mode that covers described the first resin portion of exposing in described recess,
Described the second resin portion, the second absorbing particle with adsorb oxygen.
12. light-emitting device as claimed in claim 11,
The particle diameter of described the first absorbing particle is below 100nm,
The particle diameter of described the second absorbing particle is below 100 μ m.
13. light-emitting device as described as claim 9 or 11,
On the surface of described recess, the layer that is provided with adsorb oxygen or does not make oxygen see through.
14. light-emitting device as described as claim 9 or 11,
Described the first absorbing particle and described the second absorbing particle, do not absorb from the light wavelength of described semiconductor light-emitting elements radiation and the light wavelength of radiating from the quantum dot fluorescence body.
15. light-emitting device as described as claim 9 or 11,
Top in described the second resin portion is provided with glass cover,
Described glass cover and described packaging body are bonding.
16. a light-emitting device possesses:
Packaging body, consist of resin, and have recess;
Lead frame, expose in the bottom surface of described recess;
The first oxygen absorbed layer, be formed in the mode that at least covers the lead frame exposed described bottom surface;
Quantum dot fluorescence body layer, be formed on described the first oxygen absorbed layer; And
The second oxygen absorbed layer, be formed in the mode that covers described quantum dot fluorescence body layer.
17. light-emitting device as claimed in claim 16,
Top at described the second oxygen absorbed layer is provided with glass cover.
18. light-emitting device as described as claim 16 or 17,
At the inwall of described recess, the reflective metal layer that is provided with adsorb oxygen or does not make oxygen see through or the Porous particle layer of adsorb oxygen.
19. light-emitting device as described as any one of claim 16 to 18,
The absorbing particle comprised in described the first oxygen absorbed layer and the second oxygen absorbed layer comprises the some of titanium oxide, niobium oxide, hafnium oxide, indium oxide, tungsten oxide, tin-oxide, zinc oxide, Zirconium oxide, magnesium oxide, sb oxide, silicon dioxide, silica nitrogen.
20. light-emitting device as described as any one of claim 16 to 19,
Described quantum dot fluorescence body layer comprises CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnZe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnZeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, CdHgSeTe, CdHgSTe, HgZnSS, HgZnSeTe, HgZnSTe, GaN, GaP, GaAs, GaSb, AlN, AlGaN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, InGaN, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb.
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