CN109301057A - Wavelength conversion member and use luminescent device made of the component - Google Patents

Wavelength conversion member and use luminescent device made of the component Download PDF

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Publication number
CN109301057A
CN109301057A CN201811358536.5A CN201811358536A CN109301057A CN 109301057 A CN109301057 A CN 109301057A CN 201811358536 A CN201811358536 A CN 201811358536A CN 109301057 A CN109301057 A CN 109301057A
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wavelength conversion
conversion member
fluorophor
light
inorganic phosphor
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CN109301057B (en
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藤田直树
岩尾克
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Nippon Electric Glass Co Ltd
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/006Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00Compositions for glass with special properties
    • C03C4/12Compositions for glass with special properties for luminescent glass; for fluorescent glass
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21VFUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V9/00Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
    • F21V9/30Elements containing photoluminescent material distinct from or spaced from the light source
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00Nature of the non-vitreous component
    • C03C2214/16Microcrystallites, e.g. of optically or electrically active material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502Wavelength conversion materials

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Abstract

The present invention provide it is a kind of irradiation LED, LD light in the case where, the few wavelength conversion member of decline of luminous intensity and use luminescent device made of the component by the time.A kind of wavelength conversion member is dispersed inorganic phosphor in glass matrix and is formed, which is characterized in that, glass matrix is contained in terms of mole %: SiO240~53%, B2O30.1~35%, Al2O30.1~10%, Li2O0~10%, Na2O0~10%, K2O0~10%, Li2O+Na2O+K2O0.1~10%, MgO0~35%, CaO0~35%, SrO0~35%, BaO0~35%, MgO+CaO+SrO+BaO0.1~35% and ZnO0~15%, inorganic phosphor are selected from least one of oxide phosphor, nitride phosphor, nitrogen oxides fluorophor, chloride fluorophor, oxychloride fluorophor, halide fluorophor, chlorate MClO 3 fluorescent substance and halogen-phosphate compound fluorophor.

Description

Wavelength conversion member and use luminescent device made of the component
This case isOn 03 13rd, 2015, application No. is201580003341.7, it is entitled "Wavelength becomes Change component and using luminescent device made of the component" divisional application
Technical field
The present invention relates to wavelength conversion member, be used for by light emitting diode (LED:Light Emitting Diode), The wavelength conversion for the light that the light-emitting components such as laser diode (LD:Laser Diode) issue is at other wavelength.
Background technique
In recent years, as the next-generation light source for replacing fluorescent lamp, incandescent lamp, electric power is low from consumption, small-size light-weight, readily From the perspective of light quantity is adjusted in this way, the concern for the light source for using LED, LD is increasingly increased.As this next-generation light source A kind of light source is disclosed in an example, such as patent document 1, configured with light of the absorption from LED on the LED for projecting blue light A part and be transformed into the wavelength conversion member of sodium yellow.The light source is issued as the blue light projected from LED and from wavelength The white light of the synthesis light for the sodium yellow that transform component projects.
It is previous to use the component that inorganic phosphor is dispersed in resinous substrates as wavelength conversion member.But make In the case where with the wavelength conversion member, exist since the light guide from LED causes resin deterioration, so that light-source brightness is easy decline The problem of.It is especially in the presence of the heat since LED is issued, short wavelength (blue~ultraviolet) light guide of high-energy causes resinous substrates bad Change, so as to cause discoloration, deformation such problems.
Then, the complete inoganic solids including dispersing fixed inorganic fluorophor in glass matrix instead of resin are proposed Wavelength conversion member (for example, referring to patent document 2 and 3).The wavelength conversion member has the feature that the glass as base material Glass is not easy the heat due to LED chip, irradiation light causes to deteriorate, to be not likely to produce discoloration, deformation such problems.
However, firing when wavelength conversion member documented by patent document 2 and 3 exists due to manufacture leads to inorganic fluorescent The problem of body deteriorates and brightness is easy deterioration.Especially in the demanding colour rendering on the way such as general illumination, special lighting, Therefore, it is necessary to use inorganic phosphor red, that heat resistance as green is relatively low, so that there are the deteriorations of inorganic phosphor Become significant trend.Then, a kind of wavelength conversion member is proposed, is aoxidized in glass composition containing alkali metal by making Object reduces the softening point of glass powder (for example, referring to patent document 4).The wavelength conversion member can be by compare low temperature Firing manufacture, therefore, can inhibit fire when inorganic phosphor deterioration.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2000-208815 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2003-258308 bulletin
Patent document 3: No. 4895541 bulletin of patent
Patent document 4: Japanese Unexamined Patent Publication 2007-302858 bulletin
Summary of the invention
Problems to be solved by the invention
Wavelength conversion member documented by patent document 4 has that luminous intensity declines with being easy time dependent.With The further output of the light sources such as LED, LD in recent years increases, and the decline by the time of luminous intensity is more and more significant.
Therefore, the object of the present invention is to provide it is a kind of irradiation LED, LD light in the case where, strong light by the time Degree declines few wavelength conversion member and using luminescent device made of the component.
Solution for solving the problem
Wavelength conversion member of the invention is dispersed inorganic phosphor in glass matrix and is formed, the wavelength conversion member It is characterized in that, glass matrix is contained in terms of mole %: SiO240~60%, B2O30.1~35%, Al2O30.1~10%, Li2O0~10%, Na2O0~10%, K2O0~10%, Li2O+Na2O+K2O0.1~10%, MgO0~45%, CaO0~ 45%, SrO0~45%, BaO0~45%, MgO+CaO+SrO+BaO0.1~45% and ZnO0~15%, inorganic phosphor are Selected from oxide phosphor, nitride phosphor, nitrogen oxides fluorophor, chloride fluorophor, oxychloride fluorophor, halogenation At least one of object fluorophor, chlorate MClO 3 fluorescent substance and halogen-phosphate compound fluorophor.
The inventors of the present invention have found that the decline by the time of the luminous intensity in wavelength conversion member is especially formed by glass Contained in alkali metal component, SiO2The influence of ingredient.The mechanism is presumed as follows.
If existing to the glass matrix irradiation exciting light in composition containing alkali metal element by the energy of exciting light The electronics of the outermost shell of oxonium ion in glass matrix is excited, and separates from oxonium ion.In part of it and glass matrix Alkali ion in conjunction with and form paint centre (here, alkali ion be detached from then form vacancy).On the other hand, pass through electron detachment The hole of generation is moved in glass matrix, and the vacancy trapping that a part is formed after being detached from by alkali ion forms paint centre. Being considered as forming these paint centres in glass matrix becomes the absorption source of exciting light, fluorescence, thus wavelength conversion member Luminous intensity decline.Additionally, there are the heat being generated by inorganic phosphor (to generate due to wavelength conversion loss becomes Heat) trend that causes the movement of electronics, hole, alkali ion in glass matrix to become active.Accelerate paint centre as a result, It is formed, luminous intensity is easy decline.Then, in the present invention, contain alkali metal element as an essential component on one side, on one side as above-mentioned Its content is limited on a small quantity, inhibit the rising of softening point as a result, and inhibits the generation of paint centre.
In addition, SiO in composition2Ratio when content is more, in glass matrix as the Si-O-Si combination of network former Become more, glass matrix structure stabilization.Therefore, by Si-O-Si combine in Si and O between combination cutting formed Non-crosslinked oxygen is held stably, which becomes paint centre, and becomes the reason of luminous intensity declines.However, group At middle SiO2When content is few, the content of other ingredients is opposite to become more, the combination other than Si-O-Si combination increase (for example, Ba, Other elements such as Na enter between Si and O), the stability decline of glass matrix structure as a result,.It is formed in this state non-crosslinked When oxygen, the stability of the bonding state around Si element declines, and therefore, non-crosslinked oxygen is not easy to be held stably.As a result, can Inhibit the formation of paint centre.
In addition, the glass matrix in wavelength conversion member of the invention contains alkaline-earth oxide (containing MgO) as required Ingredient.Alkaline-earth oxide hinders the movement of alkali metal ion and other ions in glass matrix.As a result, paint centre is not easy It is formed, is able to suppress the decline by the time of luminous intensity.
In wavelength conversion member of the invention, preferably glass matrix contains respectively 0.1% or more Li2O、Na2O and K2O。
In wavelength conversion member of the invention, preferably the softening point of glass matrix is 400~800 DEG C.
Wavelength conversion member of the invention preferably comprises the inorganic phosphor of 0.01~30 mass %.
Wavelength conversion member of the invention is preferably made of sintered powder.
Luminescent device of the invention, which is characterized in that have above-mentioned wavelength conversion member and wavelength conversion member is irradiated The light source of exciting light.
Invention effect
According to the present invention it is possible to provide irradiation LED, LD light in the case where, luminous intensity declines few by the time Wavelength conversion member and use luminescent device made of the component.
Detailed description of the invention
Fig. 1 is the schematical side view of the luminescent device of one embodiment of the present invention.
Specific embodiment
Wavelength conversion member of the invention is to disperse component made of inorganic phosphor in glass matrix.Glass matrix with Mole % meter contains: SiO240~60%, B2O30.1~35%, Al2O30.1~10%, Li2O0~10%, Na2O0~10%, K2O0~10%, Li2O+Na2O+K2O0.1~10%, MgO0~45%, CaO0~45%, SrO0~45%, BaO0~45%, MgO+CaO+SrO+BaO0.1~45% and ZnO0~15%.Explanation limits the reason of glass compositing range so below.
SiO2It is the ingredient to form glass network.SiO2Content be 40~60%, preferably 45~55%.If SiO2's Content is very few, then there is weatherability, mechanical strength downward trend.However, if SiO2Content it is excessive, then luminous intensity be easy Decline to time dependent.In addition, sintering temperature becomes high temperature when manufacturing wavelength conversion member, inorganic phosphor is easy deterioration.
B2O3It is the ingredient for reducing melting temperature and significantly improving meltbility.B2O3Content be 0.1~35%, preferably It is 1~30%.If B2O3Content it is very few, then be difficult to obtain said effect.In addition, when manufacturing wavelength conversion member, sintering temperature Degree becomes high temperature, and inorganic phosphor is easy deterioration.However, if B2O3Content it is excessive, then luminous intensity be easy time dependent underground Drop.In addition, weatherability is easy decline.
In addition, SiO2And B2O3Ratio SiO2/B2O3The value of (molar ratio) be 1~7,1~6.5,1.1~6,1.15~5, 1.2~4,1.5~3.5, particularly preferably 1.7~2.5.If SiO2/B2O3Value it is excessive, then SiO2Ratio become larger, be easy shape Paint centre caused by being detached from by O element, thus there are luminous intensity time dependent downward trend.However, if SiO2/ B2O3Value it is too small, then B2O3Ratio become larger, weatherability be easy decline.
Al2O3It is the ingredient for improving weatherability, mechanical strength.Al2O3Content be 0.1~10%, preferably 2~8%. If Al2O3Content it is very few, be difficult to obtain said effect.However, if Al2O3Content it is excessive, then exist meltbility decline become Gesture.
In addition, in order to realize high weatherability, preferably by SiO2+B2O3+Al2O3Content be set as 55% or more, more preferably It is set as 60% or more, is further preferably set as 65% or more, 67% or more is particularly preferably set as, is most preferably set as 70% or more. SiO2+B2O3+Al2O3The upper limit of content be not particularly limited, but it is excessive when, meltbility is easy decline, it is therefore preferable that being set as 85% hereinafter, be more preferably set as 84% hereinafter, being further preferably set as 83% or less.
Li2O、Na2O and K2O is the ingredient for making melting temperature decline, improving meltbility and declining softening point.These at The content divided is respectively 0~10%, and preferably 0~5%, more preferably 0.1~2%.If the content of these ingredients is excessive, deposit In weatherability downward trend.
In addition, Li2O+Na2O+K2The content of O is 0.1~10%, preferably 1~7%, more preferably 2~5%.If Li2O +Na2O+K2The content of O is very few, and softening point does not tend to decrease.However, if Li2O+Na2O+K2The content of O is excessive, under weatherability is easy Drop, and since the irradiation of the light of LED, LD causes luminous intensity to decline with being easy time dependent.Li2O、Na2O and K2O is preferably mixed Using two or more, it is particularly preferably used in mixed way 3 kinds.Specifically, it is preferable that containing the Li for being respectively 0.1% or more2O、Na2O And K2O.It sets in this way, then softening point can efficiently be reduced by mixed base effect.In addition, if by each basic anhydride When content is set as equal, it is easy to get mixed base effect.
In order to realize high weatherability, preferably SiO of the appropriate adjustment as the ingredient for contributing to weatherability raising2、B2O3And Al2O3Total amount with become weatherability decline the reason of alkali metal oxide (Li2O, Na2O and K2O the ratio of content).Tool For body, (Li2O+Na2O+K2O)/(SiO2+B2O3+Al2O3) (molar ratio) be preferably 0.2 hereinafter, more preferably 0.18 hereinafter, Further preferably 0.15 or less.
MgO, CaO, SrO and BaO are the ingredients for making melting temperature decline, improving meltbility and declining softening point.Separately Outside, the movement of the ion due to being formed caused by the light irradiation of LED, LD as paint centre is hindered, also have Inhibit the effect of luminous intensity declined by the time.The content of these ingredients is respectively 0~45%, and preferably 10~45%, Particularly preferably 15~35%.If the content of these ingredients is excessive, there are weatherability downward trends.In addition, mass number is big BaO hinder become paint centre formation the reason of ion movement effect it is obvious, luminous intensity can be effectively inhibited Decline by the time.
In addition, the content of MgO+CaO+SrO+BaO be 0.1~45%, preferably 0.1~40%, more preferably 0.1~ 35%, further preferably 1~30%, particularly preferably 5~25%.If the content of MgO+CaO+SrO+BaO is very few, soften Point does not tend to decrease, and is difficult to obtain the effect declined by the time for inhibiting luminous intensity.However, if MgO+CaO+SrO+ The content of BaO is excessive, then weatherability is easy decline.
ZnO is the ingredient for declining melting temperature and improving meltbility.The content of ZnO be 0~15%, preferably 0~ 12%, more preferably 0~10%, further preferably 1~7%.If the content of ZnO is excessive, there are becoming for weatherability decline Gesture.
In addition, in addition to the above ingredients, various composition can also be contained in the range of not influencing effect of the present invention.Example It such as, can also be by P2O5、La2O3、Ta2O5、TeO2、TiO2、Nb2O5、Gd2O3、Y2O3、CeO2、Sb2O3、SnO2、Bi2O3And ZrO2Deng Contain 15% respectively hereinafter, further containing 10% hereinafter, especially containing 5% hereinafter, and being 30% below with total amount Range contains.Alternatively, it is also possible to contain F.F has the effect of reducing softening point, therefore, instead of the original formed as paint centre The alkali metal component of one of cause, containing F, it is possible thereby to inhibit luminous intensity by the time in the state of maintaining softening point Decline.The content of F is calculated as 0~20%, preferably 0~10%, particularly preferably 0.1~5% with anion %.
The softening point of glass matrix is preferably 400~800 DEG C, and more preferably 450~750 DEG C, further preferably 500~ 700℃.If softening point is too low, mechanical strength and weatherability are easy decline.However, if softening point is excessively high, when due to manufacture Firing cause inorganic phosphor be easy deterioration.
In addition, in general, in most cases, the refractive index of inorganic phosphor is higher than the refractive index of glass.Wavelength conversion In component, if the refringence of inorganic phosphor and glass matrix is big, exciting light is on the boundary of inorganic phosphor and glass matrix Face is easy to happen scattering.As a result, exciting light gets higher the illumination efficiency of inorganic phosphor, luminous efficiency is easy to improve.But It is that, if the refringence of inorganic phosphor and glass matrix is excessive, exciting light excessively scatters, to become scattering loss, instead And there are luminous efficiency downward trends.In view of above, the refringence of inorganic phosphor and glass matrix is preferably 0.001~ 0.5 or so.In addition, the refractive index (nd) of glass matrix is preferably 1.45~1.8, and more preferably 1.47~1.75, it is further excellent It is selected as 1.48~1.6.
Inorganic phosphor in the present invention is selected from oxide phosphor (the garnet system fluorescence comprising YAG fluorophor etc. Body), nitride phosphor, nitrogen oxides fluorophor, chloride fluorophor, oxychloride fluorophor, halide fluorophor, aluminic acid At least one of salt fluorophor and halogen-phosphate compound fluorophor.In these inorganic phosphors, oxide phosphor, nitride The heat resistance of fluorophor and nitrogen oxides fluorophor is higher, the less susceptible deterioration when firing, so it is preferred that.In addition, nitride Fluorophor and nitrogen oxides fluorophor have the feature that near ultraviolet~indigo plant exciting light is transformed into it is green~red such wide Wavelength region, and luminous intensity is also high.Therefore, nitride phosphor and nitrogen oxides fluorophor are especially as white The inorganic phosphor of LED element wavelength conversion member is effective.In order to inhibit the heat generated by inorganic phosphor to be transferred to Glass matrix also can be used and be coated processed inorganic phosphor.Electronics in inhibition glass matrix, hole, alkali as a result, Activeization of the movement of property ion, as a result, being able to suppress the formation of paint centre.As covering material, preferably aoxidize Object.In addition, as fluorophor other than the above, sulphide phosphor can be enumerated, but sulphide phosphor time dependent deteriorate, Or reacted with glass matrix, so that luminous intensity is easy decline, therefore, do not used in the present invention.
As above-mentioned inorganic phosphor, can enumerate 300~500nm of wavelength have excitation band and wavelength 380~ 780nm has the fluorophor of glow peak, especially issue blue (440~480nm of wavelength), green (500~540nm of wavelength), The fluorophor of the light of yellow (540~595nm of wavelength), red (600~700nm of wavelength).
The luminous inorganic glimmering of blue is issued when exciting light as ultraviolet~near ultraviolet of 300~440nm of illumination wavelength Body of light can enumerate (Sr, Ba) MgAl10O17: Eu2+, (Sr, Ba)3MgSi2O8: Eu2+Deng.
The inorganic glimmering of the fluorescence of green is issued when exciting light as ultraviolet~near ultraviolet of 300~440nm of illumination wavelength Body of light can enumerate SrAl2O4: Eu2+、SrBaSiO4: Eu2+、Y3(Al、Gd)5O12: Ce3+, SrSiON:Eu2+、BaMgAl10O17: Eu2 +、Mn2+、Ba2MgSi2O7: Eu2+、Ba2SiO4: Eu2+、Ba2Li2Si2O7: Eu2+、BaAl2O4: Eu2+Deng.
As 440~480nm of illumination wavelength blue exciting light when issue green fluorescence inorganic phosphor, can arrange Lift SrAl2O4: Eu2+、SrBaSiO4: Eu2+、Y3(Al、Gd)5O12: Ce3+, SrSiON:Eu2+, β-SiAlON:Eu2+Deng.
The inorganic glimmering of the fluorescence of yellow is issued when exciting light as ultraviolet~near ultraviolet of 300~440nm of illumination wavelength Body of light can enumerate La3Si6N11: Ce3+Deng.
As 440~480nm of illumination wavelength blue exciting light when issue yellow fluorescence inorganic phosphor, can arrange Lift Y3(Al, Gd)5O12: Ce3+、Sr2SiO4: Eu2+
The inorganic glimmering of red fluorescence is issued when exciting light as ultraviolet~near ultraviolet of 300~440nm of illumination wavelength Body of light can enumerate MgSr3Si2O8: Eu2+、Mn2+、Ca2MgSi2O7: Eu2+、Mn2+Deng.
The inorganic phosphor that red fluorescence is issued when exciting light as the blue of 440~480nm of illumination wavelength, can arrange Lift CaAlSiN3: Eu2+、CaSiN3: Eu2+、(Ca、Sr)2Si5N8: Eu2+, α-SiAlON:Eu2+Deng.
In addition it is also possible to cooperate exciting light and luminous wavelength domain, it is used in mixed way multiple inorganic phosphors.For example, shining Penetrate ultraviolet range exciting light obtain white light in the case where, be used in mixed way issue blue, green, yellow, red fluorescence nothing Machine fluorophor.
The luminous efficiency (lm/W) of wavelength conversion member becomes according to the type and content of inorganic phosphor, in turn according to wavelength It changes thickness of component etc. and changes.The content of inorganic phosphor and the thickness of wavelength conversion member become optimal with luminous efficiency Mode carries out appropriate adjustment.If the content of inorganic phosphor is excessive, it may be not easy to be sintered or the porosity becomes Greatly, to be not easy asking for mechanical strength decline for making exciting light efficiently expose to inorganic phosphor or wavelength conversion member etc. Topic.However, being difficult to obtain required luminous intensity if the content of inorganic phosphor is very few.From this point of view, this hair The content of inorganic phosphor in bright wavelength conversion member is preferably 0.01~30 mass %, more preferably 0.05~25 matter Measure %, further preferably 0.08~20 mass %.
In addition, will make the fluorescence generated in wavelength conversion member to the reflection of excitation light incident side to mainly only take fluorescence Into the external wavelength conversion member issued as a purpose, not by above-mentioned restriction, the content (example of inorganic phosphor can be increased Such as, 30~80 mass % is further 40~75 mass %), so that luminous intensity becomes maximum.
It, can also be by aluminium oxide, silica, oxygen other than inorganic phosphor in wavelength conversion member of the invention The photodiffusion material for changing magnesium etc. contains until being in the total amount 30 mass %.
Wavelength conversion member of the invention is preferably made of sintered powder.Specifically, it is preferable that by containing glass powder It is constituted with the sintered body of the mixed-powder of inorganic phosphor powder.It sets in this way, can easily be produced on glass matrix In the evenly dispersed wavelength conversion member for having inorganic phosphor.
The maximum particle diameter D of glass powdermaxPreferably 200 μm hereinafter, more preferably 150 μm hereinafter, further preferably 105 μm or less.The average grain diameter D of glass powder50Preferably 0.1 μm or more, more preferably 1 μm or more, further preferably 2 μm More than.If the maximum particle diameter D of glass powdermaxExcessive, then in obtained wavelength conversion member, exciting light is not easy to scatter, hair Light efficiency is easy decline.In addition, if the average grain diameter D of glass powder50It is too small, then in obtained wavelength conversion member, swash Shine excessively scattering, and luminous efficiency is easy decline.
In addition, in the present invention, maximum particle diameter DmaxWith average grain diameter D50Refer to the value measured by laser diffractometry.
The firing temperature of mixed-powder containing glass powder and inorganic phosphor be preferably glass powder softening point ± Within 150 DEG C, more preferably within softening point ± 100 DEG C of glass powder.If firing temperature is too low, glass powder does not flow It is dynamic, it is difficult to obtain fine and close sintered body.However, there are following worries if firing temperature is excessively high: inorganic phosphor ingredient exists It is melted out in glass, so that luminous intensity decline or inorganic phosphor ingredient are spread in glass, glass coloration, to shine Intensity decline.
It is carried out preferably in reduced pressure atmosphere in addition, firing.Specifically, the atmosphere in firing be preferably less than 1.013 × 105Pa, more preferably 1000Pa are hereinafter, further preferably 400Pa or less.Thereby, it is possible to reduce in wavelength conversion member The amount of remaining bubble.As a result, it is possible to reduce the dispersion factor in wavelength conversion member, luminous efficiency can be improved.In addition, Process entirety can be fired in reduced pressure atmosphere, such as can also only be fired process in reduced pressure atmosphere, and by its Heating process, the cooling process of front and back carry out in the atmosphere (such as under atmospheric pressure) of non-reduced pressure atmosphere.
The shape of wavelength conversion member of the invention is not particularly limited, in addition to such as plate, column, hemispherical, hemisphere It is dome-shaped etc., its own component with specific shape, but also the substrate table including being formed in glass substrate, ceramic substrate etc. The sintered body being film-like in face etc..
The embodiment of luminescent device of the invention is indicated in Fig. 1.As shown in Figure 1, luminescent device 1 has wavelength conversion section Part 2 and light source 3.Light source 3 irradiates exciting light L1 to wavelength conversion member 2.It is incident to the exciting light L1 transformation of wavelength conversion member 2 At the fluorescence L2 of other wavelength, projected from the opposite side of light source 3.At this point, also can be set to as follows: projecting without wavelength conversion And the synthesis light of the exciting light L1 and fluorescence L2 transmitted.
Embodiment
Hereinafter, based on embodiment, the present invention will be described in detail, but the present invention is not limited to these embodiments.
(1) production of glass powder
Table 1 and 2 indicates the (examination of glass powder used in glass powder (Sample A~M) used in embodiment and comparative example Sample N~P).
[table 1]
[table 2]
Firstly, the preparation raw material in the way of becoming glass shown in table 1 and 2 and form.By raw material using platinum crucible with 800~ 1500 DEG C of temperature melts progress vitrifying in 1~2 hour, and melten glass is flowed out between a pair of of chill roll, is shaped to film as a result, Shape.After film-like glass formed body is crushed using ball mill, it is classified, obtains average grain diameter D50For 2.5 μm of glass powder. For obtained glass powder, softening point and weatherability are measured by following methods.
Softening point, which is used, becomes 10 using elongate fiber method viscosity7.6The temperature of dPas.
Weatherability is evaluated as follows.Glass powder is press-formed using mold, production diameter 1cm it is cylindric it is pre- at Type body obtains columned sintered body sample by being fired with firing temperature documented by table 1 and 2.It is made using the Pingshan Mountain Made HAST testing machine PC-242HSR2 keeps sample 300 hours under conditions of 121 DEG C, 95%RH, 2 atmospheric pressure, sees Specimen surface is examined, evaluates weatherability as a result,.Specifically, will be tried before and after the test by optical microphotograph sem observation (× 500) As "○", in specimen surface sample that glass ingredient or gloss disappear is precipitated as "×" in the sample that sample surface does not change, It is evaluated.
(2) production of wavelength conversion member
Table 3~6 indicates the embodiment of the present invention (sample 1~13,17~29) and comparative example (14~16,30~32).
[table 3]
[table 4]
[table 5]
[table 6]
It is inorganic more glimmering than shown in mixture table 3~6 with defined quality into each glass powder sample documented by table 1 and 2 Body of light powder, obtains mixed-powder.Mixed-powder is press-formed in a mold, production diameter 1cm it is cylindric it is pre- at Type body.After preform is fired, processing is implemented to obtained sintered body, obtains the disk of diameter 8mm, thickness 0.2mm as a result, The wavelength conversion member of shape.In addition, firing temperature is according to used glass powder, it is warm using being fired documented by table 1 and 2 Degree.Luminescent spectrum is measured to obtained wavelength conversion member, calculates luminous efficiency.Result is indicated in table 3~6.
Luminous efficiency acquires as follows.Firstly, wavelength conversion member is arranged on the light source of excitation wavelength 460nm, measurement exists The Energy distribution spectrum of the light issued above wavelength conversion member in integrating sphere.Then, the spectrum obtained is opposite multiplied by standard Visibility, calculates total light flux, and total light flux calculates luminous efficiency divided by the power of light source.
Then, above-mentioned wavelength conversion member is processed into 1.2mm square, obtains the wavelength conversion member of small pieces.It will be small The wavelength conversion member of piece is positioned in on the LED chip of the 650mA emission wavelength 445nm being powered, and is carried out 100 hours Continuous illumination is penetrated.For the wavelength conversion member before light irradiation and after light irradiation 100 hours, general luminescent spectrum is utilized to measure The Energy distribution spectrum for the light that device measurement issues above wavelength conversion member in integrating sphere.Obtained luminescent spectrum multiplied by Standard relatlve visibility calculates total light flux value as a result,.The change rate of total light flux value uses up total light after irradiation 100 hours Amount of flux irradiated divided by light before total light flux value and indicated multiplied by 100 obtained values (%), and indicated in table 3~6.
Such as from table 3 and 4 it is found that in the case where using α-SiAlON as inorganic phosphor, as embodiment 1~ 13 wavelength conversion member makes the total light flux value after light irradiation in 100 hours maintain 98% or more before light irradiation, relatively In this, the total light flux value after the 100 hours light irradiation of 14~16 wavelength conversion member as comparative example declines to a great extent For 96.5% or less before light irradiation.
Such as from table 5 and 6 it is found that 17~29 wave in the case where using YAG as inorganic phosphor, as embodiment Long transform component carry out 100 hours light irradiation after, do not confirm the decline of total light flux value yet, in contrast, as than It declines to a great extent compared with the total light flux value after the 100 hours light irradiation of 30~32 wavelength conversion member of example as before light irradiation 98.5% or less.
Industrial utilizability
Wavelength conversion member of the invention is suitable for the general illumination of White LED etc., special lighting (such as projector light Source, automobile headlamp light source) etc. component parts.
Appended drawing reference
1 luminescent device
2 wavelength conversion members
3 light sources

Claims (6)

1. a kind of wavelength conversion member is dispersed inorganic phosphor in glass matrix and formed, the feature of the wavelength conversion member exists In:
The glass matrix is contained in terms of mole %: SiO240~53%, B2O30.1~35%, Al2O30.1~10%, Li2O 0~10%, Na2O 0~10%, K2O 0~10%, Li2O+Na2O+K2O 0.1~10%, MgO 0~45%, CaO 0 ~45%, SrO 0~45%, BaO 0~45%, MgO+CaO+SrO+BaO 0.1~45% and ZnO 0~15%,
The inorganic phosphor is selected from oxide phosphor, nitride phosphor, nitrogen oxides fluorophor, chloride fluorescence At least one of body, oxychloride fluorophor, halide fluorophor, chlorate MClO 3 fluorescent substance and halogen-phosphate compound fluorophor.
2. wavelength conversion member as described in claim 1, it is characterised in that:
The glass matrix contains respectively 0.1% or more Li2O、Na2O and K2O。
3. wavelength conversion member as claimed in claim 1 or 2, it is characterised in that:
The softening point of the glass matrix is 400~800 DEG C.
4. wavelength conversion member as claimed in claim 1 or 2, it is characterised in that:
The inorganic phosphor containing 0.01~30 mass %.
5. wavelength conversion member as claimed in claim 1 or 2, it is characterised in that:
It is made of sintered powder.
6. a kind of luminescent device, it is characterised in that:
Have wavelength conversion member according to any one of claims 1 to 5 and exciting light is irradiated to the wavelength conversion member Light source.
CN201811358536.5A 2014-04-01 2015-03-13 Wavelength conversion member and light emitting device using the same Active CN109301057B (en)

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