CN105849921A - Wavelength conversion member and light emitting device using same - Google Patents

Wavelength conversion member and light emitting device using same Download PDF

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Publication number
CN105849921A
CN105849921A CN201580003341.7A CN201580003341A CN105849921A CN 105849921 A CN105849921 A CN 105849921A CN 201580003341 A CN201580003341 A CN 201580003341A CN 105849921 A CN105849921 A CN 105849921A
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wavelength conversion
conversion member
light
inorganic phosphor
glass matrix
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藤田直树
岩尾克
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Priority to CN201811358536.5A priority Critical patent/CN109301057B/en
Publication of CN105849921A publication Critical patent/CN105849921A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/006—Glass 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
    • F21V9/30—Elements containing photoluminescent material distinct from or spaced from the light source
    • 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
    • H01L33/48—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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/16—Microcrystallites, e.g. of optically or electrically active material

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Geochemistry & Mineralogy (AREA)
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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Glass Compositions (AREA)
  • Luminescent Compositions (AREA)
  • Led Device Packages (AREA)
  • Optical Filters (AREA)

Abstract

Provided are: a wavelength conversion member which is not susceptible to decrease of the luminous intensity over time in cases where the wavelength conversion member is irradiated with light from an LED or LD; and a light emitting device which uses this wavelength conversion member. A wavelength conversion member which is obtained by dispersing an inorganic phosphor in a glass matrix, and which is characterized in that: the glass matrix contains, in mol%, 40-60% of SiO2, 0.1-35% of B2O3, 0.1-10% of Al2O3, 0-10% of Li2O, 0-10% of Na2O, 0-10% of K2O, 0.1-10% of (Li2O + Na2O + K2O), 0-35% of MgO, 0-35% of CaO, 0-35% of SrO, 0-35% of BaO, 0.1-35% of (MgO + CaO + SrO + BaO) and 0-15% of ZnO; and the inorganic phosphor is composed of at least one phosphor selected from among oxide phosphors, nitride phosphors, oxynitride phosphors, chloride phosphors, oxychloride phosphors, halide phosphors, aluminate phosphors and halophosphate chloride phosphors.

Description

Wavelength conversion member and use the luminescent device of these parts
Technical field
The present invention relates to wavelength conversion member, its for by light emitting diode (LED:Light Emitting Diode), The wavelength conversion of the light that the light-emitting components such as laser diode (LD:Laser Diode) send becomes other wavelength.
Background technology
In recent years, the instead light source of future generation of fluorescent lamp, electric filament lamp, from consumption, electric power is low, small-size light-weight, readily From the viewpoint of light quantity regulation so, the concern to the light source using LED, LD is increased day by day.As this light source of future generation One example, such as, Patent Document 1 discloses a kind of light source, and it is configured with on the LED of injection blue light and absorbs the light from LED A part and be transformed into the wavelength conversion member of sodium yellow.This light source sends as the blue light penetrated from LED with from wavelength The white light of the synthesis light of the sodium yellow of transform component injection.
As wavelength conversion member, used the parts being dispersed with inorganic phosphor in resinous substrates in the past.But, make In the case of this wavelength conversion member, exist owing to causing resin to deteriorate from the light of LED, thus light-source brightness easily declines Problem.Being especially in the presence of the short wavelength hot, high-octane owing to LED sends (blue～ultraviolet) light causes resinous substrates bad Change, thus cause variable color, deform such problem.
Then, it is proposed that include replacing resin to disperse the complete inoganic solids of fixed inorganic fluorophor in glass matrix Wavelength conversion member (for example, referring to patent documentation 2 and 3).This wavelength conversion member has the feature that the glass becoming mother metal Glass is difficult to the heat due to LED chip, irradiates photoconduction deterioration, thus is not likely to produce variable color, deforms such problem.
But, the wavelength conversion member described in patent documentation 2 and 3 exists owing to firing when manufacturing causes inorganic fluorescent The problem that body deterioration and brightness easily deteriorate.In the purposes such as general lighting, special lighting, particularly require high colour rendering, Accordingly, it would be desirable to use such thermostability red, green than relatively low inorganic phosphor, thus there is the deterioration of inorganic phosphor Become significant trend.Then, it is proposed that a kind of wavelength conversion member, it is by making glass aoxidize containing alkali metal in forming Thing, reduces the softening point (for example, referring to patent documentation 4) of glass powder.This wavelength conversion member can be by compare low temperature Fire manufacture, therefore, it can suppress the deterioration of inorganic phosphor when firing.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-208815 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-258308 publication
Patent documentation 3: No. 4895541 publication of patent
Patent documentation 4: Japanese Unexamined Patent Publication 2007-302858 publication
Summary of the invention
Invent problem to be solved
The problem that wavelength conversion member described in patent documentation 4 declines with there is the easy time dependent of luminous intensity.Along with The light sources such as LED, LD in recent years further export increase, the decline by the time of luminous intensity is more and more significant.
Therefore, it is an object of the invention to, it is provided that a kind of irradiation LED, LD light in the case of, luminous strong by the time That spends declines few wavelength conversion member and uses the luminescent device of these parts.
For solving the scheme of problem
The wavelength conversion member of the present invention, it disperses inorganic phosphor to form in glass matrix, this wavelength conversion member Being characterised by, glass matrix contains 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 is Selected from oxide phosphor, nitride phosphor, nitrogen oxides fluorophor, chloride fluorophor, oxychloride fluorophor, halogenation At least one in thing fluorophor, chlorate MClO 3 fluorescent substance and halogen-phosphate compound fluorophor.
The present inventor etc. find, the decline by the time of the luminous intensity in wavelength conversion member is formed by glass especially Alkali metal component contained by, SiO2The impact of composition.This mechanism is presumed as follows.
If the glass matrix containing alkali metal in composition is irradiated exciting light, then by the energy of exciting light, exist The electronics of the outermost shell of the oxonium ion in glass matrix is excited, and separates from oxonium ion.In one part and glass matrix Alkali ion combines and forms paint centre (here, alkali ion forms room after departing from).On the other hand, electron detachment is passed through The hole generated is moved in glass matrix, and the room that a part is formed after being departed from by alkali ion traps, and forms paint centre. These paint centre being considered as forming in glass matrix become the absorption source of exciting light, fluorescence, thus wavelength conversion member Luminous intensity decline.(wavelength conversion loss becomes reason and produces to additionally, there are the heat owing to being produced by inorganic phosphor Heat) cause the trend that the electronics in glass matrix, hole, the movement of alkali ion come to life.Thus, paint centre is accelerated Being formed, luminous intensity easily declines.Then, in the present invention, as containing alkali metal by composition, while as above-mentioned Its content is limited on a small quantity, thus, the generation rising and suppressing paint centre of suppression softening point.
It addition, SiO in Zu Cheng2When content is many, the ratio combined as the Si-O-Si of network former in glass matrix Change is many, glass matrix structure stabilization.Therefore, the combination between Si and O in being combined by Si-O-Si is cut off and is formed Non-crosslinked oxygen is held stably, and this non-crosslinked oxygen becomes paint centre, and becomes the reason that luminous intensity declines.But, group SiO in one-tenth2When content is few, the content of other composition becomes many relatively, Si-O-Si combine beyond combination increase (such as, Ba, Other element such as Na enters between Si and O), thus, the stability of glass matrix structure declines.Form non-crosslinked in this condition During oxygen, the stability of the bonding state around Si element declines, and therefore, non-crosslinked oxygen is difficult to be held stably.Its result, can The formation of suppression paint centre.
Additionally, the glass matrix in the wavelength conversion member of the present invention contains alkaline-earth oxide (containing MgO) as required Composition.Alkaline-earth oxide hinders the movement of the alkali metal ion in glass matrix and other ion.Its result, paint centre is difficult to Formed, it is possible to the decline by the time of suppression luminous intensity.
In the wavelength conversion member of the present invention, preferably glass matrix contains the Li of respectively more than 0.1%2O、Na2O and K2O。
In the wavelength conversion member of the present invention, the preferably softening point of glass matrix is 400～800 DEG C.
The wavelength conversion member of the present invention preferably comprises the inorganic phosphor of 0.01～30 mass %.
The wavelength conversion member of the present invention is preferably made up of sintered powder.
The luminescent device of the present invention, it is characterised in that possess 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 of, by the time luminous intensity decline few Wavelength conversion member and use the luminescent device of these parts.
Accompanying drawing explanation
Fig. 1 is the schematic side view of the luminescent device of one embodiment of the present invention.
Detailed description of the invention
The wavelength conversion member of the present invention is to disperse the parts 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%.Following description so limits the reason of glass compositing range.
SiO2It it is the composition forming glass network.SiO2Content be 40～60%, preferably 45～55%.If SiO2's Content is very few, then there is weatherability, mechanical strength downward trend.But, if SiO2Content too much, then luminous intensity is easy Time dependent ground declines.It addition, when manufacturing wavelength conversion member, sintering temperature becomes high temperature, and inorganic phosphor easily deteriorates.
B2O3It is to reduce melt temperature and significantly improve the composition of meltbility.B2O3Content be 0.1～35%, preferably It is 1～30%.If B2O3Content very few, then be difficult to obtain the effect above.It addition, when manufacturing wavelength conversion member, sintering temperature Degree becomes high temperature, and inorganic phosphor easily deteriorates.But, if B2O3Content too much, then luminous intensity easy time dependent underground Fall.It addition, weatherability easily declines.
Additionally, SiO2And B2O3Ratio SiO2/B2O3The value of (mol ratio) is 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 excessive, then SiO2Ratio become big, easy shape Become and departed from, by O element, the paint centre caused, thus there is luminous intensity time dependent ground downward trend.But, if SiO2/ B2O3Value too small, then B2O3Ratio become big, weatherability easily declines.
Al2O3It is to improve weatherability, the composition of mechanical strength.Al2O3Content be 0.1～10%, preferably 2～8%. If Al2O3Content very few, be difficult to obtain the effect above.But, if Al2O3Content too much, then have that meltbility declines becomes Gesture.
Additionally, in order to realize high weatherability, preferably by SiO2+B2O3+Al2O3Content be set to more than 55%, more preferably It is set to more than 60%, is further preferably set to more than 65%, be particularly preferably set to more than 67%, be most preferably set to more than 70%. SiO2+B2O3+Al2O3The upper limit of content be not particularly limited, but time too much, meltbility easily declines, it is therefore preferable that be set to Less than 85%, more preferably it is set to less than 84%, is further preferably set to less than 83%.
Li2O、Na2O and K2O is to make melt temperature decline, improve meltbility and the composition making softening point decline.These become Point content be respectively 0～10%, preferably 0～5%, more preferably 0.1～2%.If the content of these compositions is too much, then deposit In weatherability downward trend.
Additionally, 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 is difficult to decline.But, if Li2O+Na2O+K2The content of O is too much, under weatherability is easy Fall, and decline with causing the easy time dependent of luminous intensity owing to the light of LED, LD irradiates.Li2O、Na2O and K2O is preferably mixing Use two or more, be particularly preferably used in mixed way 3 kinds.Specifically, the Li of respectively more than 0.1% is preferably comprised2O、Na2O And K2O.So set, then can pass through mixed base effect, reduce softening point efficiently.If it addition, by each basic anhydride When content is set to equal, it is readily obtained mixed base effect.
In order to realize high weatherability, preferably suitably adjust as the SiO contributing to the composition that weatherability improves2、B2O3And Al2O3Total amount and become the alkali metal oxide (Li of reason that weatherability declines2O, Na2O and K2The ratio of content O).Tool For body, (Li2O+Na2O+K2O)/(SiO2+B2O3+Al2O3) (mol ratio) preferably less than 0.2, more preferably less than 0.18, More preferably less than 0.15.
MgO, CaO, SrO and BaO are to make melt temperature decline, improve meltbility and the composition making softening point decline.Separately Outward, hinder owing to the light of LED, LD irradiates the movement of the ion becoming the reason that paint centre is formed caused, therefore, also have The effect declined by the time of suppression luminous intensity.The content of these compositions is respectively 0～45%, preferably 10～45%, Particularly preferably 15～35%.If the content of these compositions is too much, then there is weatherability downward trend.Additionally, mass number is big BaO hinder the effect of movement of the ion becoming the reason that paint centre is formed obvious, it is possible to effectively suppress luminous intensity Decline by the time.
Additionally, the content of MgO+CaO+SrO+BaO is 0.1～45%, preferably 0.1～40%, more preferably 0.1～ 35%, more preferably 1～30%, particularly preferably 5～25%.If the content of MgO+CaO+SrO+BaO is very few, then soften Point is difficult to decline, and is difficult to obtain the effect declined by the time of suppression luminous intensity.But, if MgO+CaO+SrO+ The content of BaO is too much, then weatherability easily declines.
ZnO is to make melt temperature decline and improve the composition of meltbility.The content of ZnO is 0～15%, preferably 0～ 12%, more preferably 0～10%, more preferably 1～7%.If the content of ZnO is too much, then there is becoming of weatherability decline Gesture.
It addition, in addition to mentioned component, it is also possible to do not affecting in the range of effect of the present invention containing various compositions.Example As, it is also possible to by P2O5、La2O3、Ta2O5、TeO2、TiO2、Nb2O5、Gd2O3、Y2O3、CeO2、Sb2O3、SnO2、Bi2O3And ZrO2Deng Contain less than 15% respectively, contain less than 10% further, especially with less than 5%, and with total amount for less than 30% Scope contains.Alternatively, it is also possible to containing F.F has the effect reducing softening point, and therefore, replacement is former as paint centre formation The alkali metal component of one of cause, containing F, thus can be when maintaining softening point, suppression luminous intensity is by the time 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, more preferably 450～750 DEG C, more preferably 500～ 700℃.If softening point is too low, then mechanical strength and weatherability easily decline.But, if softening point is too high, then time owing to manufacturing Fire and cause inorganic phosphor easily to deteriorate.
Additionally, it is said that in general, in most cases, the refractive index of the refractive index ratio glass of inorganic phosphor is high.Wavelength conversion In parts, if inorganic phosphor is big with the refractivity of glass matrix, then exciting light is on the boundary of inorganic phosphor Yu glass matrix Face is susceptible to scattering.Its result, exciting light uprises for the illumination efficiency of inorganic phosphor, and luminous efficiency easily improves.But It is that if inorganic phosphor is excessive with the refractivity of glass matrix, then exciting light too scatters, thus becomes scattering loss, instead And there is luminous efficiency downward trend.More than in view of, the refractivity of inorganic phosphor and glass matrix be preferably 0.001～ About 0.5.It addition, the refractive index of glass matrix (nd) preferably 1.45～1.8, more preferably 1.47～1.75, the most excellent Elect 1.48～1.6 as.
Inorganic phosphor in the present invention is (to comprise the garnet system fluorescence of YAG fluorophor etc. selected from oxide phosphor Body), nitride phosphor, nitrogen oxides fluorophor, chloride fluorophor, oxychloride fluorophor, halogenide fluorophor, aluminic acid At least one in salt fluorophor and halogen-phosphate compound fluorophor.In these inorganic phosphors, oxide phosphor, nitride The thermostability of fluorophor and nitrogen oxides fluorophor is higher, the less susceptible deterioration when firing, so preferably.Additionally, nitride Fluorophor and nitrogen oxides fluorophor have the feature that the exciting light of near ultraviolet～indigo plant is transformed into green～red such wide Wavelength region, and luminous intensity is the highest.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 suppress the heat transfer that produced by inorganic phosphor extremely Glass matrix, it is possible to use the coated inorganic phosphor processed.Thus, the electronics in suppression glass matrix, hole, alkali Property ion activeization of movement, as a result, it is possible to the formation of suppression paint centre.As covering material, it is preferably oxidation Thing.Additionally, as fluorophor other than the above, sulphide phosphor can be enumerated, but sulphide phosphor time dependent ground deteriorates, Or react with glass matrix, thus luminous intensity easily declines, and therefore, does not uses in the present invention.
As above-mentioned inorganic phosphor, can be set forth in wavelength 300～500nm there is excitation band and at wavelength 380～ 780nm has the fluorophor of glow peak, particularly send blueness (wavelength 440～480nm), green (wavelength 500～540nm), Yellow (wavelength 540～595nm), the fluorophor of light of red (wavelength 600～700nm).
The luminous inorganic glimmering of blueness is sent during as ultraviolet～the near ultraviolet exciting light of illumination wavelength 300～440nm Body of light, can enumerate (Sr, Ba) MgAl10O17: Eu2+, (Sr, Ba)3MgSi2O8: Eu2+Deng.
Fluorescence inorganic glimmering of green is sent during as ultraviolet～the near ultraviolet exciting light of illumination wavelength 300～440nm 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.
Send the inorganic phosphor of the fluorescence of green during as the exciting light of the blueness of illumination wavelength 440～480nm, can arrange Lift SrAl2O4: Eu2+、SrBaSiO4: Eu2+、Y3(Al、Gd)5O12: Ce3+, SrSiON:Eu2+, β-SiAlON:Eu2+Deng.
Fluorescence inorganic glimmering of yellow is sent during as ultraviolet～the near ultraviolet exciting light of illumination wavelength 300～440nm Body of light, can enumerate La3Si6N11: Ce3+Deng.
Send the inorganic phosphor of the fluorescence of yellow during as the exciting light of the blueness of illumination wavelength 440～480nm, can arrange Lift Y3(Al, Gd)5O12: Ce3+、Sr2SiO4: Eu2+。
Fluorescence inorganic glimmering of redness is sent during as ultraviolet～the near ultraviolet exciting light of illumination wavelength 300～440nm Body of light, can enumerate MgSr3Si2O8: Eu2+、Mn2+、Ca2MgSi2O7: Eu2+、Mn2+Deng.
Send the inorganic phosphor of the fluorescence of redness during as the exciting light of the blueness of illumination wavelength 440～480nm, can arrange Lift CaAlSiN3: Eu2+、CaSiN3: Eu2+、(Ca、Sr)2Si5N8: Eu2+, α-SiAlON:Eu2+Deng.
In addition it is also possible to coordinate exciting light and luminous wavelength domain, it is used in mixed way multiple inorganic phosphor.Such as, shining Penetrate in the case of the exciting light in ultraviolet territory obtains white light, be used in mixed way and send blueness, green, yellow, the nothing of red fluorescence Machine fluorophor.
The luminous efficiency (lm/W) of wavelength conversion member becomes according to the kind of inorganic phosphor and content and then according to wavelength Thickness changing parts etc. and change.The content of inorganic phosphor and the thickness of wavelength conversion member become optimal with luminous efficiency Mode suitably adjusts.If the content of inorganic phosphor is too much, then it may happen that be difficult to be sintered, or the porosity becomes Greatly, thus be difficult to make exciting light to expose to asking of degradation under inorganic phosphor, or the mechanical strength of wavelength conversion member efficiently Topic.But, if the content of inorganic phosphor is very few, then it is difficult to obtain required luminous intensity.From this point of view, this The content of the bright inorganic phosphor in wavelength conversion member is preferably 0.01～30 mass %, more preferably 0.05～25 matter Amount %, more preferably 0.08～20 mass %.
Additionally, the fluorescence produced in wavelength conversion member will be made to the reflection of exciting light light incident side thus mainly only to take fluorescence Send as in the wavelength conversion member of purpose to outside, not by above-mentioned restriction, it is possible to increase the content (example of inorganic phosphor As, 30～80 mass %, are 40～75 mass % further) so that luminous intensity becomes maximum.
In the wavelength conversion member of the present invention, in addition to inorganic phosphor, it is also possible to by aluminium oxide, silicon dioxide, oxygen The photodiffusion material changing magnesium etc. contains to being calculated as 30 mass % with total amount.
The wavelength conversion member of the present invention is preferably made up of sintered powder.Specifically, preferably by containing glass powder Constitute with the sintered body of the mixed-powder of inorganic phosphor powder.By so setting, it is possible to be easily produced on glass matrix In the dispersed wavelength conversion member having inorganic phosphor.
Maximum particle diameter D of glass powdermaxIt is preferably below 200 μm, below more preferably 150 μm, more preferably Below 105 μm.Mean diameter D of glass powder50It is preferably more than 0.1 μm, more than more preferably 1 μm, more preferably 2 μm Above.If maximum particle diameter D of glass powdermaxExcessive, then in obtained wavelength conversion member, exciting light is difficult to scattering, sends out Light efficiency easily declines.If it addition, mean diameter D of glass powder50Too small, then in obtained wavelength conversion member, swash Luminous undue scattering, luminous efficiency easily declines.
Additionally, in the present invention, maximum particle diameter DmaxWith mean diameter D50Refer to the value measured by laser diffractometry.
Firing temperature containing glass powder and the mixed-powder of inorganic phosphor be preferably the softening point of glass powder ± Within 150 DEG C, more preferably within softening point ± 100 DEG C of glass powder.If firing temperature is too low, then glass powder does not flows Dynamic, it is difficult to obtain the sintered body of densification.But, if firing temperature is too high, then there is following worry: inorganic phosphor composition exists Glass melts out, thus luminous intensity declines, or inorganic phosphor composition spreads in glass, glass coloration, thus luminous Intensity declines.
Preferably carry out in reduced pressure atmosphere it addition, fire.Specifically, the atmosphere in firing is preferably less than 1.013 × 105Pa, more preferably below 1000Pa, more preferably below 400Pa.Thereby, it is possible to reduce in wavelength conversion member The amount of the bubble of residual.It is as a result, it is possible to the dispersion factor that reduces in wavelength conversion member, it is possible to increase luminous efficiency.Additionally, Operation can be fired in reduced pressure atmosphere overall, such as, can also only be fired operation in reduced pressure atmosphere, and by it Heating process, cooling process front and back are carried out in the atmosphere (such as under atmospheric pressure) of non-reduced pressure atmosphere.
The shape of the wavelength conversion member of the present invention is not particularly limited, except such as tabular, column, hemispherical, hemisphere Dome-shaped etc., himself there are the parts of given shape, but also include the base material table being formed at glass substrate, ceramic substrate etc. The sintered body etc. being film-like in face.
Fig. 1 represents the embodiment of the luminescent device of the present invention.As it is shown in figure 1, luminescent device 1 possesses wavelength conversion section Part 2 and light source 3.Wavelength conversion member 2 is irradiated exciting light L1 by light source 3.It is incident to the exciting light L1 conversion of wavelength conversion member 2 Become the fluorescence L2 of other wavelength, penetrate from the opposition side with light source 3.At this time it is also possible to be set to as follows: injection is without wavelength conversion And the synthesis light of the exciting light L1 and fluorescence L2 of transmission.
Embodiment
Hereinafter, describe the present invention in detail based on embodiment, but the present invention is not limited to these embodiments.
(1) making of glass powder
Table 1 and 2 represents the glass powder (examination used in the glass powder (Sample A～M) and comparative example used in embodiment Sample N～P).
[table 1]
[table 2]
First, preparation raw material in the way of becoming the composition of the glass shown in table 1 and 2.Raw material utilizes platinum crucible with 800～ The temperature of 1500 DEG C melts 1～2 hour and carries out vitrification, flows out to melten glass, between a pair chill roll, thus, be shaped to film Shape.After film-like glass molded body utilizes ball mill pulverize, carry out classification, obtain mean diameter D50It it is the glass powder of 2.5 μm. For the glass powder obtained, measure softening point and weatherability by following method.
Softening point uses and utilizes elongate fiber method viscosity to become 107.6The temperature of dPa s.
Weatherability is evaluated as follows.Glass powder utilizes mould carry out extrusion forming, makes the cylindric preformation of diameter 1cm Type body, by being fired with the firing temperature described in table 1 and 2, obtains columned sintered body sample.The Pingshan Mountain is utilized to make Made HAST testing machine PC-242HSR2, by sample 121 DEG C, 95%RH, keep 300 hours under conditions of 2 atmospheric pressure, see Examine specimen surface, thus, evaluate weatherability.Specifically, by observation by light microscope (× 500), after before the test, examination The sample that sample surface is not changed in is as "○", at the sample that specimen surface separates out glass ingredient or gloss disappears as "×", It is evaluated.
(2) making of wavelength conversion member
Table 3～6 represents embodiments of the invention (sample 1～13,17～29) and comparative example (14～16,30～32).
[table 3]
[table 4]
[table 5]
[table 6]
With inorganic glimmering than shown in mixture table 3～6 of the quality of regulation in each glass powder sample described in table 1 and 2 Body of light powder, obtains mixed-powder.Mixed-powder is carried out in a mold extrusion forming, makes the cylindric preformation of diameter 1cm Type body.After preform is fired, the sintered body obtained is implemented processing, thus, obtains diameter 8mm, the disk of thickness 0.2mm The wavelength conversion member of shape.Additionally, firing temperature is according to the glass powder used, described in employing table 1 and 2, fire temperature Degree.The wavelength conversion member obtained is measured luminescent spectrum, calculates luminous efficiency.Result is represented in table 3～6.
Luminous efficiency is tried to achieve as follows.First, the light source of excitation wavelength 460nm arranges wavelength conversion member, measure The Energy distribution spectrum of the light sent above wavelength conversion member in integrating sphere.Then, it is relative that the spectrum obtained is multiplied by standard Visibility, calculates total light flux, and total light flux, divided by the power of light source, calculates luminous efficiency.
Then, above-mentioned wavelength conversion member is processed into 1.2mm square, obtains the wavelength conversion member of small pieces.By little The wavelength conversion member of sheet is positioned in and carries out in the LED chip of emission wavelength 445nm that is energized with 650mA, and carries out 100 hours Continuous light irradiates.Wavelength conversion member after irradiating 100 hours for light pre-irradiation and light, utilizes general luminescent spectrum to measure Device measures the Energy distribution spectrum of the light sent above wavelength conversion member in integrating sphere.The luminescent spectrum obtained is multiplied by Standard relatlve visibility, thus, calculates total light flux value.The rate of change of total light flux value uses up the total light after irradiating 100 hours Amount of flux is divided by the total light flux value of light pre-irradiation and is multiplied by 100 values obtained (%) and represents, and represents in table 3～6.
As knowable to table 3 and 4, in the case of using α-SiAlON as inorganic phosphor, as embodiment 1～ Total light flux value after the wavelength conversion member of 13 makes the light of 100 hours irradiate maintains more than the 98% of light pre-irradiation, relatively In this, the total light flux value after irradiating as the light of 100 hours of wavelength conversion member of 14～16 of comparative example declines to a great extent For light pre-irradiation less than 96.5%.
As knowable to table 5 and 6, in the case of using YAG as inorganic phosphor, as the ripple of 17～the 29 of embodiment Long transform component carry out 100 hours light irradiate after, the decline to total light flux value the most unconfirmed, in contrast, as than The 30 of relatively example～the light of 100 hours of the wavelength conversion member of 32 irradiate after total light flux value decline to a great extent as light pre-irradiation Less than 98.5%.
Industrial utilizability
The wavelength conversion member of the present invention is useful as the general lighting of White LED etc., special lighting (such as projector light Source, the headlamp light source of automobile) etc. component parts.
Reference
1 luminescent device
2 wavelength conversion member
3 light sources

Claims (6)

1. a wavelength conversion member, disperses inorganic phosphor to form in glass matrix, and the feature of this wavelength conversion member exists In:
Described glass matrix contains in terms of mole %: SiO240～60%, 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%,
Described inorganic phosphor is selected from oxide phosphor, nitride phosphor, nitrogen oxides fluorophor, chloride fluorescence At least one in body, oxychloride fluorophor, halogenide fluorophor, chlorate MClO 3 fluorescent substance and halogen-phosphate compound fluorophor.
2. wavelength conversion member as claimed in claim 1, it is characterised in that:
Described glass matrix contains the Li of respectively more than 0.1%2O、Na2O and K2O。
3. wavelength conversion member as claimed in claim 1 or 2, it is characterised in that:
The softening point of described glass matrix is 400～800 DEG C.
4. the wavelength conversion member as according to any one of claims 1 to 3, it is characterised in that:
Described inorganic phosphor containing 0.01～30 mass %.
5. the wavelength conversion member as according to any one of Claims 1 to 4, it is characterised in that:
It is made up of sintered powder.
6. a luminescent device, it is characterised in that:
Possess the wavelength conversion member according to any one of Claims 1 to 5 and described wavelength conversion member is irradiated exciting light Light source.
CN201580003341.7A 2014-04-01 2015-03-13 Wavelength conversion member and light emitting device using same Pending CN105849921A (en)

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