CN105621886A - Phosphor-dispersed glass - Google Patents
Phosphor-dispersed glass Download PDFInfo
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- CN105621886A CN105621886A CN201510844963.4A CN201510844963A CN105621886A CN 105621886 A CN105621886 A CN 105621886A CN 201510844963 A CN201510844963 A CN 201510844963A CN 105621886 A CN105621886 A CN 105621886A
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- Prior art keywords
- fluorophor
- glass
- phosphor
- powder
- dispersing
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
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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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
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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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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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
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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
- H01L33/48—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
Abstract
The purpose of the invention is to provide phosphor-dispersed glass with excellent wet resistance and increasing an effect suppressing inactivation of phosphor. The phosphor-dispersed glass is phosphor-dispersed glass that phosphor is dispersed in glass and is characterized in that the glass comprises, by mass, 1 to 20% of SiO2, 10 to 40% of B2O3, 1 to 45% of ZnO, 1 to 50% of RO (selected from at least one in a group composed of MgO, CaO, SrO, and BaO) in the total, 0 to 20% of R2O (selected from at least one in a group composed of Li2O, Na2O, K2O) in the total, 0.1 to 30% of at least one selected from a group composed of Nb2O5, TiO2, and La2O3 in the total, and 0.1 to 15% of at least one selected from a group composed of antimony oxides and stannic oxide in the total.
Description
Technical field
The present invention relates to the fluorophor dispersing glass being dispersed with the fluorophor as luminescent material in glass.
Background technology
In the past, it is known that using light emitting diode (LED), laser diode (LD) etc. as light source, the light sent by this light source converts wavelength through fluorophor, obtain the light-emitting device (such as, patent documentation 1��4) of the light of desired color, wavelength.
In recent years, various exploitation has been carried out for the light-emitting device that LED, LD are used as light source. As one of such light-emitting device, for instance carried out LED is used as light source to obtain the exploitation of white light, it is achieved that the white light source of power saving and high color rendering. Now, for commercially available white light source, using blueness GaN LED as light source, use the yellow fluorophor that the part from this LED blue light sent is transformed to yellow, make the blue light of light source mix with the sodium yellow being transformed into through fluorophor, become near-white light. As above-mentioned fluorophor, it is widely used the YAG oxide phosphor that with the addition of cerium.
This existing blue led with in the combination of YAG oxide phosphor that with the addition of cerium, cyan (��500nm), red (600nm) composition few, therefore, it is possible to obtain the high white light of colour temperature (color of sunshine), but the low white light of colour temperature (incandescent light color) can not be obtained. Therefore, by adding multiple fluorophor with the red equiwavelength's composition covered the shortage, realize height and drill the white light source of color.
In recent years, as the known nitride phosphor of high efficiency red-emitting phosphors, for instance patent documentation 4 has made the CaAlSiN with Eu activation3Fluorophor powder. During the structure that the mixture making above-mentioned nitride phosphor and resin is coated on LED light source, it is possible to obtain sending the white light source of the color close to natural light.
When being used with LED light source, LD light source by fluorophor, it is common to use epoxy resin, organic siliconresin or fluoroplast etc., make above-mentioned fluorophor and resin-coating such construction packages on this light source. But, have because the heat release of LED, LD or the ultraviolet sent by LED, LD, blue light make the problems such as resin deterioration, variable color, light transmission reduction. It addition, there is situation about damaging because of moisture according to fluorophor difference, when the moisture in environment passes through the resin as encapsulating material, the problem having fluorophor generation inactivation etc.
Therefore, the glass that durability is high, water barrier is high of heat, light is received publicity by the resin being used for package parts. Such as, as shown in patent documentation 5,6, the powder being used in glass powder mixing phosphor and the sintered body making this mixture sintering (following, to be sometimes designated as " fluorophor dispersing glass ") encapsulation LED. Patent documentation 5 reports oxide phosphor and SnO-P2O5The white light source that the powder of-ZnO system glass mixes and sinters and obtain; Patent documentation 6 reports by having the softening point of less than 650 DEG C, being substantially free of the SiO of PbO2-TiO2-Nb2O5-R2O (R is Li, Na, K) is the illuminant color coversion material possessing weatherability that glass is made.
As the method using glass powder as described above and fluorophor powder to encapsulate LED, such as Patent Document 5 discloses the mixture of sintered glass powder and fluorophor powder, form fluorophor dispersing glass, it is made to soften flowing after being placed on LED by this fluorophor dispersing glass, the method thus encapsulating LED; It is coated with LED closely with the powder of mixing, hereafter makes powder softening flowing, the method thus simultaneously carrying out the encapsulation of LED and the formation of fluorophor dispersing glass. It addition, Patent Document 6 discloses mixing formation pastes such as glass powder, fluorophor powder, bonding agent, solvents, this paste is coated after on LED and burns till, the method simultaneously carrying out fluorophor dispersing glass and the encapsulation of LED; The material identical with aforesaid paste is used to form green compact, the method carrying out after stacking thermo-compressed burning till on LED by these green compact.
It addition, the moisture-proof that patent documentation 7 describes sulphide phosphor, chlorate MClO 3 fluorescent substance and silicate phosphor is poor. When manufacturing fluorophor dispersing glass not to use the sol-gal process of water to manufacture in the document, but obtain fluorophor dispersing glass solve when the fluorophor dispersing glass that manufacture is above-mentioned fluorophor because of the problem of moisture damaged by mixing/burn till glass powder and fluorophor powder.
As mentioned above, use the fluorophor dispersing glass being dispersed with fluorophor in glass, encapsulate LED, LD as light source, it is possible to the light-emitting device realizing improving the durability to the moisture in heat, light, air becoming problem in based on conventional resin-encapsulated, but when manufacturing fluorophor dispersing glass actually or encapsulate this light source, the mixture that must make fluorophor powder and glass powder rises to the temperature of more than glass transition point and is sintered, the probability that there is the heat because now applying and make fluorophor inactivate.
Report when nitride phosphor is heated under the environment that there is oxygen, fluorophor inactivation (non-patent literature 1). Non-patent literature 1 reports Sr2-xSi5N8:Eu2+If fluorophor exists oxygen when heating, then the Eu of divalent is oxidized to 3 valencys. That is, when mixed nitride thing fluorophor is sintered with the oxygen containing glass of bag, the luminous efficiency of nitride phosphor is likely to be greatly reduced.
It addition, patent documentation 8 reports use oxonitride phosphor, melts, the scopes of 900 DEG C to 1200 DEG C, the R used2O-R��O-B2O3-TeO2It it is fluorophor dispersing glass. Above-mentioned R2O-R��O-B2O3-TeO2Be glass can control heat time the reaction with oxonitride phosphor.
It addition, except above-mentioned oxonitride phosphor, sulphide phosphor, halogenide fluorophor, chlorate MClO 3 fluorescent substance etc. are likely to luminous efficiency is greatly reduced because of heat when burning till glass powder with fluorophor powder. Such as, patent documentation 9 reports and makes fluorophor powder that thermostability as described above is low and softening point is 600 DEG C neighbouring ZnO-B2O3-SiO2Glass frit end mixing/sintering, it is suppressed that the fluorophor dispersing glass of fluorophor inactivation.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-277516 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2012-155003 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2003-258308 publication
Patent documentation 4: No. 5045432 publication of Japanese Patent
Patent documentation 5: Japanese Unexamined Patent Publication 2005-11933 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2007-302858 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2009-177131 publication
Patent documentation 8: Japanese Unexamined Patent Publication 2011-162398 publication
Patent documentation 9: Japanese Unexamined Patent Publication 2007-191702 publication
Non-patent literature
Non-patent literature 1:YehCWetal. " OriginofthermaldegradationofSr (2-x) Si5N8:Eu (x) phosphorsinairforlight-emittingdiodes; " J.Am.Chem.Soc., 134,14108-14117 (2012).
Summary of the invention
The problem that invention to solve
As mentioned earlier, as the material of the encapsulation light source such as LED, LD and when using fluorophor dispersing glass, during the sintering of fluorophor powder and glass powder, when heating fluorophor dispersing glass to encapsulate this light source, fluorophor is likely to inactivate because of heat. Especially, when nitride phosphor, the rare earth ion in fluorophor is reactive high with glass, therefore easily caused by the inactivation of fluorophor, it is difficult to exploitation overcomes the glass of this problem.
It addition, in order to suppress as described above because of the inactivation of thermally-induced fluorophor, suppress the heat applied when sintering with doing one's utmost, it is therefore desirable for use the glass that softening point is low, but then, the weatherability of the glass that softening point is low, especially moisture-proof reduce, and are chemically sometimes becoming unstable. The low glass of moisture-proof under long-term use because the moisture in air makes the composition dissolution comprised in glass or precipitates out salt and makes light transmittance reduce, its result, have the luminous efficiency such problem of reduction.
Such as, patent document 6 discloses that and employ SiO2-TiO2-Nb2O5-R2The illuminant color coversion material possessing weatherability of O system glass. This illuminant color coversion material is because of by TiO2And Nb2O5As must composition and contain, thus to oxide glass powder give weatherability, especially moisture-proof. But, describe SiO2Content there is the tendency that chemical durability worsens when becoming less than 20 mass %. It addition, heating when using because of sintering and and glass reaction, it is easy to foam, the fluorophor of the abnormal response such as variable color when, by minimizing SiO2Content or increase R2O��ZnO��B2O3Content, thus reduce softening point, reduce fluorophor firing temperature.
As described above, it is possible to be obtained through using TiO2And Nb2O5As must the glass of composition improve the moisture-proof of glass, by reducing the fluorophor dispersing glass that the softening point of glass inhibits the inactivation of fluorophor. But, on the other hand, the requirement of the glass that further suppress fluorophor inactivation is still high. Inventors etc. further investigate, though result known be the glass of softening point equal extent, by composition containing special component, it is also possible to Fluorophotometry body inactivation further.
Therefore, present invention aim at obtaining excellent moisture resistance, improve the fluorophor dispersing glass of the effect of Fluorophotometry body inactivation.
For solving the scheme of problem
The present invention relates to a kind of fluorophor dispersing glass, it is the fluorophor dispersing glass being dispersed with fluorophor in glass, it is characterised in that this glass comprises the SiO of 1��20% in quality %2, 10��40% B2O3, 1��45% ZnO, amount to the RO (select at least one in the group that free MgO, CaO, SrO and BaO form) of 1��50%, the R of total 0��20%2O (selects free Li2O��Na2O and K2O composition group at least one), amount to 0.1��30% the free Nb of choosing2O5��TiO2And La2O3At least one in the group of composition, at least one in the group selecting free stibium oxide and stannum oxide composition of total 0.1��15%.
Oxide glass powder mixes when being sintered with oxide phosphor, if reporting the softening point that reduces glass etc. as aforementioned conventional technology, suppressing heat that fluorophor is applied, and can Fluorophotometry body inactivation. On the other hand, present invention discover that: even if softening point is equal extent, by containing stibium oxide in glass, the effect of oxide phosphor inactivation when also making suppression sinter improves.
It addition, when nitride phosphor, sulphide phosphor and oxide glass powder technique, the oxygen comprised in this oxide glass reacts with the composition in fluorophor, cause the inactivation being susceptible to fluorophor. Present invention discover that: even if softening point is equal extent, by containing stannum oxide in glass, the effect of fluorophor inactivation when also making suppression sinter improves.
It addition, stibium oxide has the tendency of the fluorophor inactivation making nitride phosphor etc. easily inactivate. On the other hand, though stannum oxide is helpless to the inactivation of inhibited oxidation thing fluorophor, but the Inactivation Effect height of nitride phosphor etc. is suppressed. Therefore, although generally avoid nitride phosphor, sulphide phosphor and stibium oxide to coexist, but the research according to the present inventor etc., it has been found that if in the scope of 0.1��15%, even if the then glass for making stibium oxide and stannum oxide coexist, it is also possible to suppress the inactivation of nitride phosphor.
The fluorophor dispersing glass that " inactivation " in this specification refers to the sintering by glass powder and fluorophor powder and obtain is visual lower in black or the situation of Lycoperdon polymorphum Vitt.
Even if it addition, visually not can confirm that inactivation, the fluorophor dispersing glass low for luminous efficiency also serves as " suppression inactivation is insufficient ", and above-mentioned " inactivation " is similarly not suitable for fluorophor dispersing glass. Typically, the luminous efficiency of fluorophor represents using following three kinds: the efficiency (absorbance) that absorbs exciting light, the exciting light absorbed are transformed to the efficiency (internal quantum) of fluorescence and are transformed to the efficiency (external quantum efficiency) of fluorescence as their long-pending exciting light. The present invention using improve Fluorophotometry body inactivation effect as problem, therefore pay close attention to internal quantum.
When using glass as described herein, the kind according to the fluorophor disperseed in glass, the complexity of the inactivation when sintering is different, especially in the presence of the tendency that nitride phosphor, sulphide phosphor easily inactivate. In the embodiment of this specification, when for nitride phosphor, as suppressing inactivation insufficient during using internal quantum less than 40%; It addition, when for oxide phosphor, as suppressing inactivation insufficient during using internal quantum less than 50%.
It addition, the fluorophor dispersing glass of the present invention such as can pass through to prepare the glass powder of aforesaid glass, make it sinter after mixing this glass powder and fluorophor powder and obtain.
The effect of invention
In accordance with the invention it is possible to obtain excellent moisture resistance, improve the fluorophor dispersing glass of the effect of Fluorophotometry body inactivation.
Detailed description of the invention
The present invention relates to a kind of fluorophor dispersing glass, it is the fluorophor dispersing glass being dispersed with fluorophor in glass, it is characterised in that this glass comprises in quality %: the SiO of 1��20%2, 10��40% B2O3, 1��45% ZnO, amount to the RO (select at least one in the group that free MgO, CaO, SrO and BaO form) of 1��50%, the R of total 0��20%2O (selects free Li2O��Na2O and K2O composition group at least one), amount to 0.1��30% the free Nb of choosing2O5��TiO2And La2O3At least one in the group of composition, at least one in the group selecting free stibium oxide and stannum oxide composition of total 0.1��15%.
By making the glass of above-mentioned shown specific composition, it is possible to suppress the inactivation of glass when sintering and the reaction of fluorophor, Fluorophotometry body. It addition, above-mentioned glass is being chemically stable, especially humidity had high-durability.
Hereinafter, the composition for the glass of the present invention describes. It should be noted that " % " of the content of ingredient represents quality % in expression glass, sometimes also it is denoted as " % " below.
For the glass used in the present invention, the composition contained in glass is SiO2��B2O3��ZnO��Al2O3��RO��R2O��Nb2O5��TiO2��La2O3, stannum oxide and stibium oxide, mentioned component substantially adds up to 100%. Alternatively, it is also possible to be allowed for arbitrary composition containing the usual glass ingredient of conduct of at most about 15%.
As above-mentioned any composition, for instance the ZrO represented with general oxide can be listed2��WO3��CeO2Deng.
It addition, containing Fe in above-mentioned glass2O3Time, the absorbance of glass reduces sometimes, is not inconsistent with the purpose of the present invention. Therefore, mentioned component has preferably been substantially free of. Specifically, the content of mentioned component is preferably less than 0.3%, is more preferably less than 0.03%.
It addition, when above-mentioned glass contains PbO, glass coloration yellowly, absorption exciting light, it is thus preferred to be substantially free of PbO. Specifically, the content of mentioned component is preferably less than 0.3%, is more preferably less than 0.03%.
Additionally, it is known that Bi2O3It is the composition as the softening point reducing glass, but containing sometimes in above-mentioned glass, sometimes reacts with fluorophor, make fluorophor inactivate, it is thus preferred to be substantially free of Bi2O3. Specifically, the content of mentioned component is preferably less than 0.3%, is more preferably less than 0.03%.
That is, currently preferred is be substantially free of Fe in glass ingredient2O3, PbO and Bi2O3��
SiO2For glass forming constituents, by with the B as other glass forming constituents2O3Coexist and can form stable glass, and contain with the scope of 1��20%. During less than 1%, glass easily becomes unstable, and during more than 20%, the softening point of glass becomes easy rising. Lower limit can also be preferably set to more than 2%, more preferably be set to more than 7%. It addition, higher limit can also be preferably less than 20%, be more preferably less than 19%.
B2O3For glass forming constituents, it is easy to make glass melting, suppress the excessive of linear expansion coefficient of glass to rise, and when baking, glass is given the mobility of appropriateness, contain with the scope of 10��40% in glass. During less than 10%, due to the relation with other composition, the mobility of glass becomes insufficient sometimes, it is possible to damage agglutinating property. On the other hand, during more than 40%, there is the tendency that chemical durability reduces. Preferably lower limit is set to more than 11%, can also more preferably be set to more than 14%. It addition, higher limit can also be preferably set to less than 30%, more preferably be set to less than 25% it is preferred that be set to less than 22%.
ZnO is the softening point of reduction glass, linear expansion coefficient is regulated the material to optimum range, contains with the scope of 1��45% in glass. Can not expecting above-mentioned effect during less than 1%, during more than 45%, glass becomes unstable, it is easy to devitrification occurs. Lower limit can also be preferably set to more than 3%, more preferably be set to more than 8%. Alternatively, it is also possible to higher limit is preferably set to less than 43%.
RO (selects the total of at least one in the group that free MgO, CaO, SrO and BaO form) and is the material of the softening point reducing glass, contains 1��50% in glass. Can not playing above-mentioned effect during less than 1%, time on the other hand more than 50%, the linear expansion coefficient of glass becomes too high sometimes. It is preferably less than 45%, is more preferably the scope of less than 42%. It addition, lower limit can also be preferably set to more than 5%, more preferably be set to more than 8%.
R2O (selects free Li2O��Na2O and K2The total of at least one in the group of O composition) it is the softening point of reduction glass, linear expansion coefficient is regulated the material to optimum range, contain with the scope of 0��30%. When content is more than 30%, alkali-soluble output increases, and chemical durability reduces. Less than 26% can also be preferably set to. It addition, lower limit can also be preferably set to more than 0.2%, more preferably be set to more than 2%.
Above-mentioned R2Among O composition, Li2O has the effect of the softening point reducing glass, on the other hand, there is, along with content increases glass, the tendency becoming easy crystallization, therefore such as can also be preferably set to less than 5%.
Speculate stibium oxide in glass with Sb2O3��Sb2O5Form contained. It addition, speculate that stannum oxide is with SnO(2-x)The form of (wherein, 0��x < 2) is contained, for instance it is believed that with SnO2, SnO form exist. The reactivity of stibium oxide and stannum oxide Fluorophotometry body and glass, is therefore contained within it is thus possible to the inactivation of significantly Fluorophotometry body by the scope to amount to 0.1��15%. Alternatively, it is also possible to be preferably set to 0.1��12%, be more preferably set to 1��10%.
If it addition, as previously mentioned in particular range, coexisting such that it is able to contain multiple fluorophor owing to making stibium oxide and stannum oxide. Research according to the present inventor etc., it has been found that if in the scope of 0.1��15%, even if being the glass making stibium oxide and stannum oxide coexist, it is also possible to suppress the inactivation of nitride phosphor. When can use multiple fluorophor, for instance two kinds of mixed oxide fluorophor and nitride phosphor like that, can utilize when compound use fluorophor to obtain desired wavelength conversion characteristic aptly.
Namely, it is preferable that make stibium oxide and stannum oxide at least contain 0.1 mass % respectively. When containing stibium oxide and stannum oxide, it is also possible to contain in the way of preferably in the scope of 0.2��15% of adding up to of stibium oxide and stannum oxide, be more preferably set to 1��15% it is preferred that be set to 1��10%.
It addition, for the kind of the fluorophor used, it is also possible in the way of monomer, use stibium oxide and stannum oxide. Preferably the content in this situation can also be set to 0.1��10%, more preferably be set to 1��8%. When using individually as described above, it is desirable to the glass used in nitride phosphor, sulphide phosphor etc. is contained within stannum oxide. Additionally, it is desirable to the glass used in oxide phosphor is contained within stibium oxide.
Nb2O5��TiO2And La2O3For the composition making the moisture-proof of glass improve, it is possible to use in the way of monomer, it is also possible to compound use, with Nb2O5+TiO2+La2O3Meter is containing 0.1��30%. When content is more than 30%, glass becomes easy devitrification, alternatively, it is also possible to be preferably set to 0.1��25%, be more preferably set to 1��21%.
It addition, Nb among above-mentioned2O5Can more effectively improve moisture-proof, it is thus preferred to containing the Nb of 0.1��20%2O5. Can also more preferably be set to 1��15 mass %.
Al2O3Suppress glass when melted, sintering time devitrification, it is preferable that contain with the scope of 0��18%. During more than 18%, the stability of glass reduces. It is more preferably the scope of less than 15%.
Devitrification during in order to suppress glass when melted or sinter, improves the chemical durability of glass, can also add ZrO outside aforesaid composition2, it is preferable that contain with the scope of 0��5%. During more than 5%, the stability of glass reduces. It is preferably the scope of below 3 mass %.
It addition, the linear expansion coefficient that the glass of the present invention is at 30 DEG C��300 DEG C is preferably 6��13ppm/ DEG C, softening point is preferably in the scope of less than 670 DEG C. By reducing softening point, it is possible to suppress to cause the inactivation of fluorophor due to heat when sintering. Less than 650 DEG C can also be preferably set to, be more preferably set to less than 630 DEG C. It addition, when softening point drops too low, moisture-proof reduces sometimes, therefore lower limit can also be preferably set to more than 400 DEG C.
Generally for fluorophor, based on the composition constituting fluorophor, the wavelength of the exciting light launched is different. If it addition, when the kind of light source is LED, LD, then the excitation wavelength of combined with fluorescent body is suitably carried out selecting. Especially, as long as the present invention has the fluorophor of excitation wavelength at wavelength 350��500nm, it becomes possible to the kind of fluorophor is used for fluorophor dispersing glass without particular limitation of ground. That is, the aforementioned phosphors granule of the present invention has excitation wavelength preferably in wavelength 350��500nm. It addition, the present invention is suitable particularly in 370nm��480nm phosphor particle with excitation wavelength, therefore can also more preferably be set to 390��480nm.
As above-mentioned phosphor particle, for instance at least one in the group of selecting free oxide, oxynitride, nitride, oxysulfide, sulfide, aluminate compound, halogen-phosphate compound, fluoride and YAG based compound composition is preferably used. Especially, for the nitride easily inactivated, the present invention also is able to utilize particularly suitablely. Alternatively, it is also possible to use multiple fluorophor.
As above-mentioned nitride phosphor, for instance (Sr, Ca) AlSiN can be listed as red-emitting phosphors3: Eu fluorophor, CaAlSiN3: Eu fluorophor, La can be listed as yellow fluorophor3Si6N11: Ce fluorophor; As oxonitride phosphor, for instance CaAlSi (ON) can be listed as red-emitting phosphors3: Eu fluorophor, ��-SiAlON:Eu fluorophor, ��-SiAlON:Eu fluorophor, (Sr, Ba) Si can be listed as green-emitting phosphor2O2N2: Eu fluorophor, Ba3Si6O12N2: Eu fluorophor.
It addition, as oxide phosphor, for instance, (Y, Gd) can be listed as yellow fluorophor3Al5O12: Ce fluorophor, Tb3Al5O12: Ce fluorophor, Lu3Al5O12: Ce fluorophor, (Sr, Ca, Ba)2SiO4: Eu fluorophor, Y can be listed as green-emitting phosphor3(Al,Ga)5O12:Ce3+Fluorophor, (Ba, Sr)2SiO4: Eu fluorophor, CaSc2O4: Ce fluorophor, BaMgAl10O17: Eu, Mn fluorophor, SrAl2O4: Eu fluorophor, (Sr, Ba) can be listed as red-emitting phosphors3SiO5: Eu fluorophor etc.
It addition, as sulphide phosphor, for instance ZnS:Cu, Al fluorophor, (Ca, Sr) Ga can be listed as green-emitting phosphor2S4: Eu fluorophor, (Ca, Sr) S:Eu fluorophor can be listed as red-emitting phosphors, as near-infrared fluorescent body, (Zn, Cd) S:Cu fluorophor can be listed. As oxysulfide fluorophor, for instance Y can be listed as red-emitting phosphors2O2S:Eu fluorophor, La2O2S:Eu fluorophor, Gd2O2S:Eu fluorophor etc.
The strength ratio of fluorescence (exciting light with), luminous efficiency change because of the thickness of the dispersion kind of phosphor particle in glass, content and fluorophor dispersing glass it addition, the conversion efficiency of the fluorophor dispersing glass of the present invention. With luminous efficiency, color rendering, the thickness of the content of phosphor particle Yu fluorophor dispersing glass is become optimum mode adjust, but the problem that when phosphor particle becomes too much, generation sintering change difficulty or exciting light not energy efficiency are irradiated to phosphor particle well. It addition, when content is very few, it becomes difficult to luminous fully. It is therefore preferable that the content with aforementioned phosphor particle mixes relative to the mode that the gross mass of this fluorophor dispersing glass is 0.01��95 volume %. Can also more preferably be set to 0.5��95 volume %.
It addition, the fluorophor dispersing glass of the present invention can also contain inorganic filler. By containing above-mentioned inorganic filler such that it is able to regulate the thermal propertys such as linear expansion coefficient when sintering fluorophor dispersing glass, softening point. As this inorganic filler, for instance magnesium oxide, aluminium nitride, boron nitride, zircon, mullite, Silicon stone, titanium white and Alumina etc. can be used. It addition, the suitable content regulating this inorganic filler, but such as can also mix relative to the mode that the gross mass of this fluorophor dispersing glass is more than 0.1 mass % and below 40 mass %.
As it was previously stated, be sintered after hybrid glass powder and fluorophor powder, it is possible to obtain the fluorophor dispersing glass of the present invention. Now, after hybrid glass powder and fluorophor powder, it is shaped to partical by the method for the non-heated such as pressurization, it is possible to the inactivation of the fluorophor caused when suppressing to sinter this pellet by thermal conductance, it is thus preferred to. It addition, than that described above, it is also possible to after hybrid glass powder with fluorophor powder, heating to can be once-forming viscosity, use mould etc. to be shaped.
Sintering temperature when carrying out above-mentioned sintering is desired for the scope of 400��750 DEG C. When sintering temperature becomes to be above 750 DEG C, phosphor degradation or glass react with fluorophor sometimes, luminous efficiency significantly reduces, and are not inconsistent with the purpose of the present invention.
Atmosphere during heating can be in air, it is also possible in the non-active gas atmosphere such as decompression or the atmosphere of vacuum, nitrogen, Ar gas, it is considered to during manufacturing cost, it is desirable to for air atmosphere. And then, for the bubble suppressing the inside of glass powder to comprise, it is possible under reduced pressure or be sintered under the atmosphere of vacuum, it is also possible to pressurize in sintering.
For the glass powder used in fluorophor dispersing glass, the particle diameter of the fluorophor powder owing to generally using is about 1��100 ��m, as long as therefore can with the general particle diameter (about 1��50 ��m) of pulverizer making, shape, it is possible to no problem use. It addition, for pulverizing, it is possible to use mortar, ball mill are pulverized, it is possible to use pollute the pulverizer of few abrasive blasting mode in operation sequence.
Additionally, except the method that the pellet of glass powder Yu fluorophor powder is sintered obtaining fluorophor dispersing glass as previously mentioned, glass powder, fluorophor powder, bonding agent and solvent etc. can also be carried out mixing paste-like of making, this paste obtain fluorophor dispersing glass. When using paste, it is sintered with specified temp after this paste is applied to base material etc., it is possible to obtain fluorophor dispersing glass. It should be noted that the volatilization when sintering of above-mentioned bonding agent, solvent, therefore fluorophor dispersing glass after sintering does not remain.
It addition, except aforesaid method, it is also possible to obtained fluorophor dispersing glass by green compact. For these green compact, glass powder, fluorophor powder, plasticizer, bonding agent and solvent etc. can be carried out mixing pulp-like of making, this slurry is utilized doctor blade method on the thin film of polyethylene terephthalate (PET) etc. molding and make its dry, thus obtain green compact. By sintering this green compact, it is possible to obtain fluorophor dispersing glass.
The fluorophor dispersing glass of the present invention can be used as the light-emitting device with fluorophor dispersing glass, LED or LD aptly. As this light-emitting device, the light source etc. of foregoing white light source, projector, sensor, laser can be listed. It addition, when being used for light-emitting device, select the fluorophor with suitable wavelength conversion performance according to purpose purposes.
The fluorophor dispersing glass of the present invention can be used as white light source aptly. When for white light source, by encapsulating as, around the LED of light source, converting the wavelength of this LED light sent with this phosphor glass, it is possible to produce white light. As the method with above-mentioned phosphor glass encapsulation LED, for instance the mixture that can enumerate send as an envoy to glass powder and fluorophor powder is coated with, be packaged in around LED after, the method being heated making it sinter; The mixture of this glass powder Yu fluorophor powder is molded in advance given shape after forming sintered body, to use adhesives etc. to be arranged on the method etc. of LED surface. It addition, the nitride phosphor useful as red-emitting phosphors especially can be encapsulated, therefore, it is possible to obtain height to drill the white light source of color.
The fluorophor dispersing glass of the present invention can be used as the light transform component of projector aptly. When for the light transform component of projector, make the wavelength conversion of the LED light sent become the light of each wavelength, produce green, yellow, redness. As the manufacture method of this light transform component, the mixture that can enumerate send as an envoy to glass powder and fluorophor powder is coated with around LED, encapsulate after, the method being heated making it sinter; The mixture of this glass powder Yu fluorophor powder is molded in advance given shape after forming sintered body, to use the method that adhesives etc. is arranged on LED surface; The method etc. of this sintered body is set in the position leaving LED specific range.
Embodiment
Examples and comparative examples of the present invention are recorded in following.
1: the making of glass powder
First, weighing various inorganic raw material according to the mode of the A��J recorded in table 1, table 2, the composition of a��h, mixing manufacture becomes raw material masterbatch. This raw material masterbatch is put in platinum crucible, in electric furnace, adds heat fusing with 1100��1400 DEG C within 1��2 hour, obtain the glass specimen of table 1, table 2. A part for gained glass flows into mould, makes bulk and is supplied in hot physical property (linear expansion coefficient, softening point) mensuration use. Remaining glass makes lamellar in being quenched double; two roller forming machine, becomes mean diameter 1��30 ��m, the maximum particle diameter glass powder less than 200 ��m with reducing mechanism granulate.
It should be noted that for stannum oxide by SnO in the present embodiment2As raw material, for stibium oxide by Sb2O3As raw material. Stannum oxide in glass becomes SnO, SnO2Etc. the state of oxidation, it is difficult to measure the clear and definite state of oxidation, therefore in table 1, table 2, it is denoted as SnO2. It addition, for the stibium oxide in glass, become Sb2O3��Sb2O5Etc. the state of oxidation, it is difficult to measure the clear and definite state of oxidation, in table, therefore it is denoted as Sb2O3. It should be noted that the content of each composition is described the value after rounding up the after arithmetic point the 1st by table 1, table 2, therefore in view of apparent sometimes aggregate values not up to 100.
Above-mentioned mean diameter and maximum particle diameter use laser diffraction type particle size determination device (Nikkiso Company Limited's system, Microtrac) to measure. Mensuration be in water after dispersing glass powder, irradiating laser thus obtaining scattering light/diffraction light, this light intensity distributions the size of the granule calculating glass powder according to program set in device is obtained.
Above-mentioned softening point uses apparatus for thermal analysis TG-DTA (RigakuCorporation system) to measure. It addition, above-mentioned linear expansion coefficient is the linear expansion coefficient obtained by the amount of tension at 30��300 DEG C when using dilatometer, heat up with 5 DEG C/min. It should be noted that the non-vitrification of g, h of table 2, therefore undetermined softening point and linear expansion coefficient, the research after being also not used for.
[table 1]
[table 2]
2: the evaluation of the inactivation of Fluorophotometry body
Embodiment 1
The red fluorophor powder of nitride ((SrCa) AlSiN is added in gained glass powder3:Eu2+, centre of luminescence wavelength 610nm), be mixed into mixed-powder (fluorophor content: 4 volume %). It should be noted that glass powder uses the composition of the A��J of table 1. Then, use mould to carry out extrusion forming and make the button shape preform of diameter 10mm, thickness 2mm. Then, by an atmosphere respectively heating within 30 minutes, be sintered obtaining sintered body. Gained sintered body is ground to thickness 1mm. Use glass powder, fluorophor powder, sintering temperature, gained sintered body tone be shown in table 3.
Embodiment 2
Glass powder uses the composition of F and the I of table 1, and fluorophor powder uses the red fluorophor (CaAlSiN of nitride3:Eu2+, centre of luminescence wavelength 630nm) powder, in addition, obtain sintered body with method similarly to Example 1. It should be noted that sintering temperature such as table 3 is remembered.
Embodiment 3
Glass powder uses the composition of the B of table 1, and fluorophor powder uses red oxide fluorophor (Y3Al5O12:Ce3+, centre of luminescence wavelength 555nm) powder, in addition, obtain sintered body with method similarly to Example 1. It should be noted that sintering temperature such as table 3 is remembered.
Embodiment 4
Glass powder uses the composition of B, E, H and I of table 1, and fluorophor powder uses red oxide fluorophor (Lu3Al5O12:Ce3+, centre of luminescence wavelength 540nm) powder, in addition, obtain sintered body with method similarly to Example 1. It should be noted that sintering temperature such as table 3 is remembered.
Embodiment 5
Glass powder uses the composition of the E of table 1, fluorophor powder uses oxonitride phosphor (��-SiAlON:Eu fluorophor, centre of luminescence wavelength 600nm) powder, fluorophor content is set to 20 volume %, in addition, obtains sintered body with method similarly to Example 1. It should be noted that sintering temperature such as table 3 now is remembered.
Comparative example 1
Glass powder uses the composition of a��f of table 2, in addition, obtains sintered body with method similarly to Example 1. It should be noted that sintering temperature such as table 3 is remembered.
Comparative example 2
Glass powder uses the composition of d, f of table 2, in addition, obtains sintered body with method similarly to Example 4. It should be noted that sintering temperature such as table 3 is remembered.
[table 3]
<mensuration of quantum efficiency>
For each sintered body obtained in embodiment 1��5 and comparative example 1,2, measure internal quantum (��int) and external quantum efficiency (��ext), it is shown in table 3. For measuring, use is connected to integrating sphere (Japan Spectroscopy Corporation's system, ILF-533) spectrofluorophotometer (Japan Spectroscopy Corporation's system, FP-6500), the integrated intensity of the exciting light spectrum that the integrated intensity of the exciting light spectrum entered in integrating sphere is denoted as A, absorb for sample is denoted as B, the integrated intensity of the fluorescence spectrum sent from sample is denoted as C, to internal quantum with C/B, external quantum efficiency is obtained with C/A. Internal quantum and external quantum efficiency are more high it may be said that luminous efficiency is more high.
It should be noted that the internal quantum of each fluorophor used during for research is measured before glass-encapsulated, result (SrCa) AlSiN3:Eu2+Be 84%, CaAlSiN3:Eu2+Be 83%, Y3Al5O12:Ce3+Be 83%, Lu3Al5O12:Ce3+Be 81%, ��-SiAlON:Eu be 77%.
Employ the internal quantum of the embodiment 1,2 of nitride phosphor to be the scope inside and outside portion quantum efficiency of 42��62% and be in the scope of 32��49%, it is possible to suppress the inactivation of nitride phosphor.
The suppression inactivation of a��e of comparative example 1 is all insufficient. Although it addition, the glass d of comparative example 1 is except each falling within forming in the scope that technical scheme 1 is recorded except by stibium oxide and two kinds of compositions of stannum oxide, but actually internal quantum and external quantum efficiency are low, it is suppressed that inactivation is insufficient. It addition, glass f is the composition suppressing Inactivation Effect high, containing stibium oxide and stannum oxide, do not contain Nb2O5��TiO2And La2O3Any one. From the foregoing, by containing stibium oxide and stannum oxide in the composition, it is possible to suppress inactivation.
It addition, the internal quantum employing the embodiment 3,4 of oxide phosphor is 81��83%, external quantum efficiency is in the scope of 70��72%, it is possible to the inactivation of inhibited oxidation thing fluorophor. On the other hand, for forming without the d by the comparative example 2 of stibium oxide and stannum oxide, internal quantum is 53%, external quantum efficiency is 42%, though inactivation can be suppressed, but time compared with embodiment, internal quantum and external quantum efficiency are relatively low value. In addition we know the composition of f contains stibium oxide and stannum oxide and does not contain Nb2O5��TiO2And La2O3Any one, internal quantum is 78%, external quantum efficiency is 68%, it is suppressed that the effect of inactivation is high.
It addition, for the embodiment 5 employing oxonitride phosphor, itself and the internal quantum before glass-encapsulated do not change, it is possible to suppress inactivation.
As can be observed from the foregoing, when the glass used in fluorophor dispersing glass is contained within stibium oxide, stannum oxide, the effect suppressing inactivation is improved. It addition, when containing stibium oxide and stannum oxide, even for nitride phosphor, for oxide phosphor, for oxonitride phosphor, display that the effect suppressing inactivation.
3: the evaluation of sulphide phosphor
Embodiment 6
Glass powder uses the composition of the B of table 1, fluorophor powder uses sulphide phosphor ((Zn, Cd) S:Cu fluorophor, centre of luminescence wavelength 850nm) powder, fluorophor content is set to 16 volume %, the thickness of sintered body is ground to 0.5mm, in addition, sintered body is obtained with method similarly to Example 1. It should be noted that sintering temperature now is set to 625 DEG C.
<the luminous evaluation of sulphide phosphor>
The sulphide phosphor used in embodiment 6 can not obtain external quantum efficiency with aforesaid device, hence for embodiment 6, studies the luminescence of fluorophor simply by following method.
First, the light (glow peak wavelength 445nm) of the blue led lighted with the electric current of 300mA is injected into the one side of the fluorophor dispersing glass that method described above obtains. Then, in the integrating sphere after making the light penetrated by the face of opposite side be injected into correction, input small-sized beam splitter (OceanOpticsInc. system, HR-4000) by optical fiber, obtain luminescent spectrum (energy distribution curve). Calculate the integrated intensity of the fluorescence spectrum released from sample, obtain the radiant flux of the fluorescence spectrum of embodiment 6.
Then, in order to compare, it is produced in organosilicon to be dispersed with the button shape molded body of the same diameter 10mm of sulphide phosphor 16 volume %, thickness 0.5mm. For gained molded body, implement the mensuration of above-mentioned luminescent spectrum in the same manner as fluorophor dispersing glass. Its result, the radiant flux employing the sintered body of glass powder B is 9.14uW, the radiant flux that employs the molded body of organosilicon is 7.31uW, and above-mentioned sintered body is 125% relative to the radiant flux of above-mentioned molded body.
As can be observed from the foregoing, time compared with the scattered sulphide phosphor of institute in organosilicon, the radiant flux of the fluorophor dispersing glass of the present invention increases. Radiant flux represents the value in the unit interval through the emittance in certain face, and when fluorophor inactivation, value reduces. It follows that the composition of the present invention is compared with resins such as the organosilicons used in the past, sulphide phosphor is not made to inactivate.
4: the evaluation of moisture-proof
Embodiment 7
The red fluorophor powder of nitride ((SrCa) AlSiN is added in the glass powder of the A��J of table 13:Eu2+, centre of luminescence wavelength 610nm), be mixed and made into mixed-powder (fluorophor content: 4 volume %). Then, use mould to carry out extrusion forming and make the button shape preform of diameter 10mm, thickness 2mm. Then, heating obtains sintered body thus being sintered in 30 minutes respectively in an atmosphere. The sintered body obtained is ground to thickness 1mm. The glass powder of use, fluorophor powder, sintering temperature are shown in table 4.
Embodiment 8
Red oxide fluorophor (Y is added in the glass powder of B, F, H, I of table 13Al5O12:Ce3+, centre of luminescence wavelength 555nm) powder, be mixed and made into mixed-powder. Fluorophor content now is set to 10,12,19 volume % as shown in table 4. Then, use mould to carry out extrusion forming and make the button shape preform of diameter 10mm, thickness 2mm. Then, heating obtains sintered body thus being sintered in 30 minutes respectively in an atmosphere. The sintered body obtained is ground to thickness 1mm. The glass powder of use, fluorophor powder, sintering temperature are shown in table 4.
Embodiment 9
Use the glass powder of A, D, H of table 1 as glass powder, use red oxide fluorophor (Lu as fluorophor3Al5O12:Ce3+, centre of luminescence wavelength 540nm) powder, fluorophor content is set to 8 volume %, in addition, obtains sintered body with method similarly to Example 8. It should be noted that sintering temperature such as table 4 now is remembered.
Comparative example 3
Use the glass powder of the f of table 2 as glass powder, obtain sintered body with method similarly to Example 7 in addition. It should be noted that sintering temperature now is shown in table 4.
Comparative example 4
The f of table 2 is used, additionally, obtain sintered body with method similarly to Example 9 as glass powder. It should be noted that sintering temperature such as table 4 now is remembered.
[table 4]
<anti-moisture test>
For embodiment 7��9, comparative example 3,4, measure external quantum efficiency in the same manner as preceding method, carry out anti-moisture test afterwards. In anti-moisture test, by gained sintered body in HAST (unsaturated steam under pressure test), after placing 96 hours when with temperature 130 DEG C, humidity 85%, measure the external quantum efficiency after anti-moisture test as described above, obtain the reduction rate of the external quantum efficiency that anti-moisture test causes. It should be noted that the reduction rate of external quantum efficiency is calculated by the formula of { 1-(external quantum efficiency before external quantum efficiency/anti-moisture test after anti-moisture test) } �� 100 (%). In this specification, when the reduction rate of the external quantum efficiency calculated is less than 10%, moisture-proof is good.
Any one the reduction rate of external quantum efficiency of embodiment 7��9 is 0��4%, has good moisture-proof. On the other hand, the reduction rate of comparative example 3,4 is more than 45%, and moisture-proof is poor.
Claims (7)
1. a fluorophor dispersing glass, it is the fluorophor dispersing glass being dispersed with fluorophor in glass, it is characterised in that this glass comprises:
The SiO of 1��20 mass %2��
The B of 10��40 mass %2O3��
The ZnO of 1��45 mass %,
Amount to 1��50 mass % RO, wherein RO select free MgO, CaO, SrO and BaO form group at least one,
Amount to the R of 0��20 mass %2O, wherein R2O selects free Li2O��Na2O and K2O composition group at least one,
Amount to the free Nb of choosing of 0.1��30 mass %2O5��TiO2And La2O3Composition group at least one,
Amount at least one in the group selecting free stibium oxide and stannum oxide composition of 0.1��15 mass %.
2. fluorophor dispersing glass according to claim 1, it is characterised in that described glass at least contains stibium oxide and the stannum oxide of 0.1 mass % respectively.
3. fluorophor dispersing glass according to claim 1, it is characterised in that described glass contains the Nb of 0.1��20 mass %2O5��
4. the fluorophor dispersing glass according to any one of claims 1 to 3, it is characterised in that described glass linear expansion coefficient at 30 DEG C��300 DEG C is 6��13ppm/ DEG C, softening point is less than 670 DEG C.
5. the fluorophor dispersing glass according to any one of claims 1 to 3, it is characterized in that, described fluorophor is the granule of at least one in the group selecting free oxide, oxynitride, nitride, sulfide, oxysulfide, halogen-phosphate compound, fluoride and YAG based compound to form.
6. a fluorophor dispersing glass, it is characterised in that the fluorophor dispersing glass according to any one of claims 1 to 3 contains inorganic filler.
7. a light-emitting device, it is characterised in that it has the fluorophor dispersing glass according to any one of claim 1��6 and LED or LD.
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| JP2014238387 | 2014-11-26 | ||
| JP2014-238387 | 2014-11-26 | ||
| JP2015206833A JP2016108216A (en) | 2014-11-26 | 2015-10-21 | Fluorophor dispersion glass |
| JP2015-206833 | 2015-10-21 |
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