CN105637659B - Wavelength convert component and luminescent device - Google Patents
Wavelength convert component and luminescent device Download PDFInfo
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- CN105637659B CN105637659B CN201480056307.1A CN201480056307A CN105637659B CN 105637659 B CN105637659 B CN 105637659B CN 201480056307 A CN201480056307 A CN 201480056307A CN 105637659 B CN105637659 B CN 105637659B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
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- 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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77347—Silicon Nitrides or Silicon Oxynitrides
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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
- 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
- C03C14/004—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 particles or flakes
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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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- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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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
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- 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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
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- 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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- 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
- C09K11/0883—Arsenides; Nitrides; Phosphides
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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 present invention provides in the case of the light of irradiation LED or LD, through when luminous intensity the few wavelength convert component of reduction, which is characterized in that：Include the sintered body of mixed-powder, which contains (a) as glass glass powder of the composition containing alkali metal element and element of multivalence and (b) inorganic phosphor powder.
Description
Technical field
The present invention relates to by light emitting diode (LED：Light Emitting Diode) or laser diode (LD：Laser
) etc. Diode the wavelength convert of the light sent out is the wavelength convert component of other wavelength.
In recent years, as the next-generation light source for replacing fluorescent lamp and incandescent lamp, from low consumption electric power, small-size light-weight, light quantity
It adjusts from the perspective of being easy, to using the light source of LED or LD to focus on raising.One as such next-generation light source
Example, such as disclose in patent document 1 on the LED for projecting blue light configured with the part for absorbing the light from LED
And it is converted into the light source of the wavelength convert component of sodium yellow.The light source sends out as the blue light projected from LED and from wave
The white light of the synthesis light for the sodium yellow that long converting member projects.
As wavelength convert component, always using making obtained from inorganic phosphor powder is scattered in resinous substrates
Part.But using the wavelength convert component, there are resins to be deteriorated due to the light from LED, the brightness of light source
The problem of being easy to be lower.Mould resin is especially in the presence of due to short wavelength (blue~ultraviolet) light of the LED heat and high energy sent out and
Deterioration, the problem of discoloration occurs and deforms.
Therefore, motion has by replacing resin and disperses in glass matrix obtained from fixed inorganic fluorophor powder completely
The wavelength convert component that inoganic solids are constituted (for example, referring to patent document 2 and 3).The wavelength convert component has as base-material
Glass be not easy due to LED chip heat and irradiation light and deteriorate, be not susceptible to change colour and deform the problem of feature.
But above-mentioned wavelength convert component there are inorganic phosphor powder due to manufacture when firing and deteriorate, be easy hair
The problem of raw brightness is deteriorated.It is especially used on the way in general lighting, special lighting etc., due to requiring high colour rendering, so needing
The relatively low inorganic phosphor powder of heat resistances such as red or green are used, there are the deteriorations of inorganic phosphor powder to become aobvious
The tendency of work.Therefore, motion makes the wavelength convert of softening point reduction by by containing alkali metal element in so that glass powder is formed
Component (for example, referring to patent document 4).The wavelength convert component by comparing the firing of low temperature due to can be manufactured
So the deterioration of inorganic phosphor powder when can inhibit to fire.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-208815 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2003-258308 bulletins
Patent document 3：No. 4895541 bulletins of Japanese Patent No.
Patent document 4：Japanese Unexamined Patent Publication 2007-302858 bulletins
Invention content
Problem to be solved by the invention
But the above-mentioned wavelength convert component containing alkali metal element in glass matrix there are luminous intensity be easy through when
(over time) the problem of reducing.Further output with LED and the light sources such as LD in recent years increases, and shines strong
Degree through when reduce the case where become increasingly significantly.
Therefore, the purpose of the present invention is to provide in the case of the light of irradiation LED or LD, through when luminous intensity drop
Low few wavelength convert component.
The solution to the problem
The wavelength convert component of the present invention is characterized in that：Include the sintered body of mixed-powder, which contains (a)
As glass glass powder of the composition containing alkali metal element and element of multivalence and (b) inorganic phosphor powder.In the present invention,
" element of multivalence " refers to the element that can use multiple valence mumbers.
As described above, as the LED for irradiating height output to the wavelength convert component containing alkali metal element in glass matrix
Or LD light when, there are luminous intensity through when reduce the case where.About detailed reason, present inventor is presumed as follows.
When irradiating exciting light to the glass matrix in the composition containing alkali metal element, due to the energy of exciting light, deposit
It is that the outermost electronics of the oxonium ion in glass matrix is excited, leaves oxonium ion, a part and the alkali in glass matrix
Ions binding forms paint centre (herein, forming vacancy after basic ion is detached from).On the other hand, due to electron detachment and
The hole of generation is moved in glass matrix, and the vacancy that a part is formed after basic ion is detached from captures and formed in coloring
The heart.It is considered that these paint centres formed in glass matrix become the absorption source of exciting light and fluorescence, to which wavelength turns
Changing the luminous intensity of component reduces.
Therefore, in order to inhibit above-mentioned phenomenon, wavelength convert component of the invention contains element of multivalence in glass composition.When
It is more when there is the ion for the element of multivalence for being easy to happen valence mumber variation near the paint centre that the above-mentioned hole of capture is formed
Valence element ion provides electronics to hole, and the hole is made to disappear.Herein, when the paint centre for capturing electronics is present in multivalence member
When near plain ion, element of multivalence ion captures electronics from paint centre, is thereby returned to initial electronic state.It is considered that
As a result, element of multivalence ion captures electronics as the carrier of electronics from the paint centre for capturing electronics, by the electronics
Be supplied to the paint centre of electron deficiency, carry out electronics and hole in conjunction with.As a result, can inhibit in glass matrix
The electronics of generation and hole in glass matrix basic ion and vacancy play a role, inhibit wavelength convert component through when hair
The reduction of luminous intensity.
In the wavelength convert component of the present invention, preferably above-mentioned element of multivalence is selected from least one of Ce, As, Mo and W
Element.
In the wavelength convert component of the present invention, preferably above-mentioned glass powder is contained in terms of mole % that following oxides convert
0.1~35% Li2O+Na2O+K2O。
In the wavelength convert component of the present invention, preferably above-mentioned glass powder is contained in terms of mole % that following oxides convert
0.001~10% CeO2+As2O3+MoO2+WO3。
In the wavelength convert component of the present invention, preferably above-mentioned glass powder is contained in terms of mole % that following oxides convert
30~80% SiO2, 1~40% B2O3, 0.1~35% Li2O+Na2O+K2O, 0.1~45% MgO+CaO+SrO+
The CeO of BaO and 0.001~10%2+As2O3+MoO2+WO3。
In the wavelength convert component of the present invention, preferably above-mentioned glass powder is contained in terms of mole % that following oxides convert
30~80% SiO2, 1~55% B2O3, 0~20% Li2O, 0~25% Na2O, 0~25% K2O, 0.1~35%
Li2O+Na2O+K2The CeO of O and 0.001~10%2+As2O3+MoO2+WO3。
In the wavelength convert component of the present invention, preferably above-mentioned inorganic phosphor powder is selected from nitride phosphor, nitrogen oxygen
Compound fluorophor, oxide phosphor, sulphide phosphor, oxysulfide fluorophor, halide fluorophor and thioaluminate phosphor
At least one of body.
The wavelength convert component of the present invention is characterized in that：It disperses inorganic phosphor powder in the matrix comprising sintered body
End forms, which is the sintered body that the glass powder containing alkali metal element and element of multivalence is formed as glass.
The luminescent device of the present invention is characterized in that：Including above-mentioned arbitrary wavelength convert component and to above-mentioned wavelength conversion section
Part irradiates the light source of exciting light.
The effect of invention
In accordance with the invention it is possible in the case of providing the light in irradiation LED or LD, through when luminous intensity reduction it is few
Wavelength convert component.
Description of the drawings
Fig. 1 is the schematic diagram for an embodiment for indicating the luminescent device of the present invention.
Specific implementation mode
The wavelength convert component of the present invention is characterized in that：Include the sintered body of mixed-powder, which contains (a)
As glass glass powder of the composition containing alkali metal element and element of multivalence and (b) inorganic phosphor powder.Hereinafter, to each structure
It is described in detail at ingredient.
Glass powder has in the wavelength convert component of the present invention as stably keeping inorganic phosphor powder
Medium effect.Herein, according to the composition of glass powder, it is poor to exist when firing and in the reactivity of inorganic phosphor powder
Not, therefore glass composition suitable for the inorganic phosphor powder that uses is preferably selected.
In order to make softening point reduce, glass powder contains alkali metal element (in Li, Na and K as glass composition
It is at least one).Specifically, it is preferable that glass powder in terms of mole % that following oxides convert containing 0.1~35% Li2O+
Na2O+K2O, further preferably 1~25%, further preferably 2~20%.If Li2O+Na2O+K2The content of O is very few, then
It is not easy to obtain said effect, on the other hand, if excessively, chemical durability is easily reduced.In addition, as described later, Li2O、
Na2O and K2The content of O preferably suitably sets appropriate range according to glass compositional system.
In addition, glass powder contains element of multivalence, thus, it is possible to inhibit wavelength convert component through when luminous intensity
It reduces.As element of multivalence, can enumerate selected from least one of Ce, As, Mo and W element.Especially Ce can significantly press down
System through when luminous intensity reduction, further glass powder itself is not easy to colour, therefore preferably.
It is preferred that glass powder in terms of mole % that following oxides convert containing 0.001~10% CeO2+As2O3+MoO2
+WO3, further preferably 0.01~5%, further preferably 0.1~3%.If CeO2+As2O3+MoO2+WO3Content mistake
It is few, then it is not easy to obtain said effect, on the other hand, if excessively, there are glass powders itself to colour and luminous intensity reduction
Tendency.In addition, the content of each element of multivalence is also respectively preferably above range.
Furthermore it is preferred that glass powder contain 10~99 moles of % be selected from SiO2、B2O3、P2O5、Bi2O3And TeO2In extremely
Few one kind.Specifically, SiO can be enumerated2-B2O3- RO (R is selected from least one of Mg, Ca, Sr and Ba element)-R '2O
(R ' is selected from least one of Li, Na and K element) class glass, SnO-P2O5-R’2O classes glass, SiO2-B2O3-R’2O class glass
Glass, SiO2-B2O3-ZnO-R’2O class glass etc..
As SiO2-B2O3-RO-R’2O class glass, for example, preferably in terms of mole % of following oxides conversion containing 30~
80% SiO2, 1~40% B2O3, 0.1~35% Li2O+Na2O+K2O, 0.1~45% MgO+CaO+SrO+BaO and
0.001~10% CeO2+As2O3+MoO2+WO3.Below to limiting glass composition in this way the reasons why, illustrates.
SiO2It is the ingredient to form glass mesh.SiO2Content be preferably 30~80%, more preferably 40~60%.
If SiO2Content it is very few, then exist chemical durability reduction tendency.On the other hand, if SiO2Content it is excessive, then it is soft
Change point to get higher, therefore in order to keep sintering abundant, needs to carry out high-temperature firing.As a result, the inorganic phosphor powder when firing
It is easy deterioration.
B2O3It is the big ingredient of effect for making fusion temperature reduce and improving meltbility.B2O3Content be preferably 1~
40%, more preferably 5~30%.If B2O3Content it is very few, then be not easy to obtain said effect.On the other hand, if B2O3's
Content is excessive, then there is the tendency of chemical durability reduction.
Li2O、Na2O and K2O is the ingredient for making softening point reduce.Li2O、Na2O and K2The content (total amount) of O is preferably
0.1~35%, more preferably 1~25%, further preferably 2~20%.If the content of these ingredients is very few, softening point
It is not easy to reduce, on the other hand, if these ingredients are excessive, chemical durability and weatherability are easily reduced.
In addition, Li2O、Na2O and K2The preferred scope of the content of each ingredient of O is as follows.Li2The content of O is preferably 0~
10%, more preferably 0.1~5%.Na2The content of O is preferably 0~15%, and more preferably 0.1~10%.K2The content of O is preferred
It is 0~15%, more preferably 0.1~10%.
MgO, CaO, SrO and BaO are the ingredients for making fusion temperature reduce and improving meltbility.In addition, there is also inhibition by BaO
With the effect of inorganic phosphor powder reacted.The content (total amount) of MgO, CaO, SrO and BaO are preferably 0.1~45%, more
Preferably 1~40%, further preferably 2~35%.If the content of these ingredients is very few, it is not easy to obtain said effect,
On the other hand, if excessively, there are the tendencies that chemical durability reduces.
In addition, the preferred scope of the content of each ingredient of MgO, CaO, SrO and BaO is as follows.The content of MgO is preferably 0~
10%, more preferably 0~5%.The content of CaO is preferably 0~30%, and more preferably 0~20%.The content of SrO is preferably 0~
20%, more preferably 0~10%.The content of BaO is preferably 0~40%, and more preferably 0.1~30%.
CeO2、As2O3、MoO2、WO3Total amount and other content it is as described above.
In glass powder, following ingredients can also be contained in addition to mentioned component.
Al2O3It is the ingredient for improving chemical durability.Al2O3Content be preferably 0~20%, more preferably 1~18%.
If Al2O3Content it is excessive, then exist meltbility reduction tendency.
ZnO is the ingredient for making fusion temperature reduce and improving meltbility.The content of ZnO is preferably 0~20%, more preferably
0.1~10%.If the content of ZnO is excessive, chemical durability is easily reduced.
In addition, in order to realize the raising etc. of chemical durability, Ta can also be made2O5、TiO2、Nb2O5、Gd2O3、La2O3、
Y2O3、Bi2O3Or ZrO2Contain respectively to 15%.
As SnO-P2O5-R’2O class glass, such as contain 35~80%SnO, 5~40% preferably in terms of mole %
P2O5, 0~30% B2O3, 0.1~5% Li2O+Na2O+K2The CeO of O and 0.001~10%2+As2O3+MoO2+WO3.Below
The reasons why limiting glass composition in this way is illustrated.
SnO is the ingredient to form glass mesh and softening point is made to reduce.The content of SnO is preferably 35~80%, more
Preferably 45~75%.If the content of SnO is very few, got higher there are softening point or weatherability reduce tendency.On the other hand,
If the content of SnO is excessive, there is the tendency that devitrification object and decrease in transmission as caused by Sn is precipitated, as a result, wavelength
The luminous intensity of converting member is easily reduced.In addition, it becomes difficult to vitrifying.
P2O5It is the ingredient to form glass mesh.P2O5Content be preferably 5~40%, more preferably 10~30%.Such as
Fruit P2O5Content it is very few, then become difficult to vitrifying.On the other hand, if P2O5Content it is excessive, then there is softening point and get higher
Or the significantly reduced tendency of weatherability.
B2O3It is the ingredient for improving weatherability and promoting split-phase.In addition, also having the effect of making stabilization.B2O3
Content be preferably 0~30%, more preferably 1~25%.If B2O3Content it is excessive, then weatherability is easily reduced.In addition,
There are softening points to become excessively high tendency.
Li2O、Na2O and K2O is the ingredient for making softening point reduce.Li2O、Na2O and K2The content (total amount) of O is preferably
0.1~5%, more preferably 1~4%.If the content of these ingredients is very few, softening point is difficult to decrease.On the other hand, if
These ingredients are excessive, then chemical durability is easily reduced.Additionally, there are what split-phase became that too much, light scattering loss becomes larger to incline
To.Li2O、Na2O and K2The content of each ingredients of O is respectively preferably 0~5%, more preferably 0.1~4%, further preferably 1~
4%.
CeO2、As2O3、MoO2、WO3Total amount and other content it is as described above.
In addition, other than mentioned component, low-firing is set to be easy to carry out in order to improve meltbility or softening point be made to reduce,
MgO, CaO, SrO or BaO can also be contained to 5% with total gauge.In addition, in order to realize the raising etc. of chemical durability,
Al can be contained respectively2O3、ZrO2、ZnO、Ta2O5、TiO2、Nb2O5、Gd2O3、Bi2O3、TeO2Or La2O3To 15%.
As SiO2-B2O3-R’2O class glass, such as preferably contain 30~80% SiO in terms of mole %2, 1~55%
B2O3, 0~20% Li2O, 0~25% Na2O, 0~25% K2O, 0.1~35% Li2O+Na2O+K2O and 0.001~
10% CeO2+As2O3+MoO2+WO3。
In addition, in addition to mentioned component, in order to improve meltbility, additionally it is possible to total gauge contain MgO, CaO, SrO and
BaO to 30%.In addition to this, ZnO to 10% can also be contained in order to improve meltbility, contains P2O5To 5%, in order to improve
Chemical durability contains Al2O3To 10%, contain Ta respectively2O5、TiO2、Nb2O5、Gd2O3Or La2O3To 15%.
As SiO2-B2O3-ZnO-R’2O class glass, such as preferably contain 5~50% SiO in terms of mole %2, 10~
55% B2O3, 30~80% ZnO, 0~20% Li2O, 0~20% Na2O, 0~20% K2O, 0.1~25%
Li2O+Na2O+K2O, 0~10% MgO, 0~10% CaO, 0~10% SrO, 0~10% BaO and 0.001~10%
CeO2+As2O3+MoO2+WO3。
In addition, in addition to mentioned component, Al can also be contained in order to improve chemical durability2O3To 5%, contain respectively
Ta2O5、TiO2、Nb2O5、Gd2O3Or La2O3To 15%.
The grain size of glass powder is not particularly limited, such as preferably at most grain size D99It is 200 μm or less (especially 150 μm
Hereinafter, being further 105 μm or less), and average grain diameter D50For 0.1 μm or more (especially 1 μm or more, further for 2 μm with
On).If the maximum particle diameter D of glass powder99Excessive, then in obtained wavelength convert component, exciting light is difficult to scatter, and shines
Efficiency is easily reduced.In addition, if average grain diameter D50Too small, then in obtained wavelength convert component, excitation light scattering is excessive,
Luminous efficiency is easily reduced.
In addition, in the present invention, average grain diameter D50With maximum particle diameter D99It refer to the value measured using laser diffractometry.
As inorganic phosphor powder, without spy as long as the inorganic phosphor powder for being generally possible to buy on the market
It does not limit.For example, can enumerate nitride phosphor powder, nitrogen oxides fluorophor powder, oxide phosphor powder (including
The Garnets such as YAG fluorophor powders fluorophor powder), sulphide phosphor powder, oxysulfide fluorophor powder, halide
Fluorophor powder (halogen-phosphate compound etc.) and chlorate MClO 3 fluorescent substance powder etc..In these inorganic phosphor powder, nitride is glimmering
Less susceptible deterioration when body of light powder, nitrogen oxides fluorophor powder and oxide phosphor powder are due to heat resistance height, firing
And it is preferred that.Near ultraviolet~blue excitation light is converted in addition, nitride phosphor powder and nitrogen oxides fluorophor powder have
To green~red wide wavelength region and luminous intensity also relatively high feature.Therefore, nitride phosphor powder and nitrogen oxygen
Compound fluorophor powder is effective particularly as the inorganic phosphor powder for White LED element wavelength convert component.
As above-mentioned inorganic phosphor powder, can enumerate 300~500nm of wavelength have excitation band, wavelength 380~
780nm has an inorganic phosphor powder of glow peak, especially blue (440~480nm of wavelength), green (wavelength 500~
540nm), yellow (540~595nm of wavelength) or red (600~700nm of wavelength) luminous inorganic phosphor powder.
The exciting light of ultraviolet~near ultraviolet as 300~440nm of illumination wavelength then sends out the inorganic fluorescent of the light of blue
Body powder can enumerate (Sr, Ba) MgAl10O17：Eu2+、(Sr,Ba)3MgSi2O8：Eu2+ etc..
The exciting light of ultraviolet~near ultraviolet as 300~440nm of illumination wavelength then sends out the inorganic glimmering of the fluorescence of green
Body of light powder can enumerate SrAl2O4：Eu2+、SrBaSiO4：Eu2+、Y3(Al,Gd)5O12：Ce3+、SrSiOn：Eu2+、
BaMgAl10O17：Eu2+、Mn2+、Ba2MgSi2O7：Eu2+、Ba2SiO4：Eu2+、Ba2Li2Si2O7：Eu2+、BaAl2O4：Eu2+ etc..
The exciting light of blue as 440~480nm of illumination wavelength then sends out the inorganic phosphor powder of the fluorescence of green,
SrAl can be enumerated2O4：Eu2+、SrBaSiO4：Eu2+、Y3(Al,Gd)5O12：Ce3+、SrSiOn：Eu2+、β-SiAlON：Eu2+
Deng.
The exciting light of ultraviolet~near ultraviolet as 300~440nm of illumination wavelength then sends out the inorganic glimmering of the fluorescence of yellow
Body of light powder can enumerate La3Si6N11：Ce3+ etc..
The exciting light of blue as 440~480nm of illumination wavelength then sends out the inorganic phosphor powder of the fluorescence of yellow,
Y can be enumerated3(Al,Gd)5O12：Ce3+、Sr2SiO4：Eu2+。
The exciting light of ultraviolet~near ultraviolet as 300~440nm of illumination wavelength then sends out the inorganic glimmering of red fluorescence
Body of light powder can enumerate CaGa2S4：Mn2+、MgSr3Si2O8：Eu2+,Mn2+、Ca2MgSi2O7：Eu2+,Mn2+ etc..
The exciting light irradiation of blue as 440~480nm of illumination wavelength then sends out the inorganic phosphor of red fluorescence
Powder can enumerate CaAlSiN3：Eu2+、CaSiN3：Eu2+、(Ca,Sr)2Si5N8：Eu2+、α-SiAlON：Eu2+ etc..
Alternatively, it is also possible to coordinate exciting light, luminous wavelength region, a variety of inorganic phosphor powder are used in mixed way.Example
Such as, in the case where irradiating the exciting light of ultraviolet range and obtain white light, the fluorescence of blue, green, yellow, red will be sent out
Inorganic phosphor powder is used in mixed way.
If the content of the inorganic phosphor powder of wavelength convert component is excessive, existing becomes not easy-sintering or porosity
Bigger tendency.As a result, in obtained wavelength convert component, generation exciting light is not easy efficiency and is irradiated to nothing well
The problems such as machine fluorophor powder or mechanical strength are easily reduced.On the other hand, if the content of inorganic phosphor powder is very few,
It is difficult to obtain desired luminous intensity.From such a viewpoint, inorganic phosphor powder in wavelength convert component contains
Amount in terms of quality % preferably 0.01~50%, more preferably 0.05~40%, further preferably 0.1~30% in the range of
Adjustment.
In addition, so that wavelength convert component generate fluorescence to excitation light incident side reflection, only mainly fluorescence is taken
Go out in the wavelength convert component to outside, is not limited to above-mentioned explanation, it can be so that luminous intensity becomes maximum
Mode increases the content (for example, in terms of quality %, 50%~80%, and then 55~75%) of inorganic phosphor powder.
The wavelength convert component of the present invention to being used as glass by forming the glass containing alkali metal element and element of multivalence
The mixed-powder of powder is fired and manufactures.Thus it obtains by being formed containing alkali metal element and element of multivalence as glass
Glass powder sintered body constitute matrix in dispersion inorganic phosphor powder made of wavelength convert component.
Firing temperature is within softening point ± 150 DEG C of glass powder, the range preferably within ± 100 DEG C is suitably adjusted
It is whole.If firing temperature is too low, glass powder will not fully flow, it is difficult to obtain fine and close sintered body.On the other hand, such as
Fruit firing temperature is excessively high, it is likely that inorganic phosphor powder dissolves out in glass powder and luminous intensity is reduced.Or
It is possible that being coloured in component diffusion to glass powder contained in inorganic phosphor powder so that luminous intensity reduces.
It is carried out preferably in reduced atmosphere in addition, firing.Specifically, firing atmosphere be preferably less than 1.013 ×
105Pa, more preferably 1000Pa are hereinafter, further preferably 400Pa or less.It is residual in wavelength convert component thereby, it is possible to reduce
The amount for the bubble deposited.As a result, the light scattering factor in wavelength convert component can be reduced, luminous efficiency can be improved.Separately
Outside, entire ablating work procedure can be carried out in reduced atmosphere, such as can also only be fired process in reduced atmosphere, not
Be reduced atmosphere atmosphere (such as under atmospheric pressure) in carry out its before and after heating process, cooling process.
The shape of wavelength convert component of the present invention is not particularly limited, for example, can be not only plate, column, it is spherical,
Its own component with specific shape such as hemispherical, hemispherical dome shape, or in the bases such as glass substrate and ceramic substrate
The component for the overlay film shape that material surface is formed.
Fig. 1 shows an embodiments of the luminescent device of the present invention.As shown in Figure 1, luminescent device 1 includes wavelength convert
Component 2 and light source 3.Light source 3 irradiates exciting light L to wavelength convert component 2in.It is incident on the exciting light L of wavelength convert component 2in
It is converted into the light of other wavelength, from 3 opposite side of light source as LoutIt projects.At this point, can also make the light after wavelength convert with not
The synthesis light of exciting light for being wavelength-converted and transmiting projects.
Embodiment
Below based on embodiment, the present invention is described in detail, and the present invention is not limited to these embodiments.
(1) making of glass powder
Table 1 indicates the composition of the glass powder used in the present embodiment.
[table 1]
First, the preparation raw material in the way of as being formed shown in table 1.By raw material at 800~1500 DEG C in platinum crucible
Temperature melting 1~2 hour and vitrifying, melten glass is flowed out between a pair of of chill roll and is shaped to membranaceous.Utilize ball milling
Machine is classified after crushing membranaceous glass, obtains average grain diameter D50For 2.5 μm of glass powder.
The density of each glass powder and softening point using according to it is each measure by melten glass be shaped to it is blocky or it is cylindric simultaneously
The sample annealed and obtained is measured.Softening point uses elongate fiber method, becomes 10 using viscosity7.6The temperature of dPas
Degree.Density is acquired using Archimedes method.
(2) making of wavelength convert component
Table 2~4 indicate the embodiment of the present invention (sample No.2~3,5~6,8~9,11~12,14~15,17~18,
20~21,23~24,26~27) and comparative example (sample No.1,4,7,10,13,16,19,22,25).
[table 2]
[table 3]
[table 4]
For glass powder recorded in table 1, specified amount mixing Y is pressed in table 23(Al、Gd)5O12：Ce3+ (YAG) fluorescence
Body powder presses specified amount mixing (Ca, Sr) in table 32Si5N8：Eu2+ (SCASN) fluorophor powders press specified amount in table 4
Blend alpha-SiAlON：Eu2+ (α-SiAlON) fluorophor powder and obtain mixed-powder.Mixed-powder is pressurizeed using metal mold
It is molded and makes the cylindric preform of diameter 1cm.It is obtained by firing preform with the temperature described in table
Sintered body implement processing, obtain 1.2mm square, thickness 0.2mm wavelength convert component.Obtained wavelength convert component is carried
It sets in the LED chip of emission wavelength 445nm, is powered with 700mA, 100 hours Continuous irradiations are carried out in integrating sphere.About hair
Light spectrum, the Energy distribution of the light using general luminescent spectrum measurement device to being sent out from wavelength convert component upper surface compose into
Row measures.By the way that the luminescent spectrum obtained is multiplied with standard relatlve visibility, full light beam value is calculated.In pre-irradiation and photograph
Full light beam value is calculated after penetrating 100 hours.The change rate of full light beam value is with the full light beam value divided by pre-irradiation after irradiating 100 hours
Full light beam value indicates that expression is in table 2~4 multiplied by with value (%) obtained from 100.
By table 2~4 it is found that the wavelength convert component of embodiment full light beam value is also almost after irradiating 100 hours exciting lights
It does not reduce.On the other hand, the wavelength convert component of comparative example full light beam value after irradiating 100 hours exciting lights is greatly reduced.
Industrial utilizability
The wavelength convert component of the present invention is suitable as the general illuminations such as White LED and special lighting (for example, projector light
Source, automobile headlamp light source) etc. component parts.
Symbol description
1 luminescent device
2 wavelength convert components
3 light sources
Claims (4)
1. a kind of wavelength convert component, it is characterised in that：
Include the sintered body of mixed-powder, the mixed-powder contain (a) as glass composition containing alkali metal element and selected from Ce,
The glass powder of the element of multivalence of at least one of As and Mo and (b) inorganic phosphor powder,
The glass powder is in terms of mole % that following oxides convert containing 30~80% SiO2, 1~40% B2O3、0.1
~35% Li2O+Na2O+K2O, the CeO of 0.1~45% MgO+CaO+SrO+BaO and 0.001~10%2+As2O3+MoO2,
Or
The glass powder is in terms of mole % that following oxides convert containing 30~80% SiO2, 1~55% B2O3, 0~
20% Li2O, 0~25% Na2O, 0~25% K2O, 0.1~35% Li2O+Na2O+K2O's and 0.001~10%
CeO2+As2O3+MoO2。
2. wavelength convert component as described in claim 1, it is characterised in that：
The inorganic phosphor powder is glimmering selected from nitride phosphor, nitrogen oxides fluorophor, oxide phosphor, sulfide
At least one of body of light, oxysulfide fluorophor, halide fluorophor and chlorate MClO 3 fluorescent substance.
3. a kind of wavelength convert component, it is characterised in that：
It disperses inorganic phosphor powder in the matrix comprising sintered body and forms, which is to contain alkali as glass composition
The sintered body of metallic element and glass powder selected from least one of Ce, As and Mo element of multivalence,
The glass powder is in terms of mole % that following oxides convert containing 30~80% SiO2, 1~40% B2O3、0.1
~35% Li2O+Na2O+K2O, the CeO of 0.1~45% MgO+CaO+SrO+BaO and 0.001~10%2+As2O3+MoO2,
Or
The glass powder is in terms of mole % that following oxides convert containing 30~80% SiO2, 1~55% B2O3, 0~
20% Li2O, 0~25% Na2O, 0~25% K2O, 0.1~35% Li2O+Na2O+K2O's and 0.001~10%
CeO2+As2O3+MoO2。
4. a kind of luminescent device, it is characterised in that：
The light source of exciting light is irradiated including wavelength convert component according to claim 2 or 3 and to the wavelength convert component.
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| JP2013-259849 | 2013-12-17 | ||
| JP2013259849A JP6222452B2 (en) | 2013-12-17 | 2013-12-17 | Wavelength conversion member and light emitting device |
| PCT/JP2014/081720 WO2015093267A1 (en) | 2013-12-17 | 2014-12-01 | Wavelength-conversion member and light-emitting device |
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| CN105637659B true CN105637659B (en) | 2018-10-19 |
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| TWI598540B (en) | 2015-09-07 | 2017-09-11 | 台達電子工業股份有限公司 | Wavelength converting module and light source module using the same |
| JP6906277B2 (en) * | 2016-06-27 | 2021-07-21 | 日本電気硝子株式会社 | Wavelength conversion member and light emitting device using it |
| JP7022367B2 (en) | 2017-09-27 | 2022-02-18 | 日本電気硝子株式会社 | Glass used as wavelength conversion material, wavelength conversion material, wavelength conversion member and light emitting device |
| CN109516694B (en) * | 2018-11-07 | 2021-11-30 | 深圳市齐尚光科技有限公司 | Fluorescent glass, preparation method thereof and light-emitting device |
| CN113272260A (en) * | 2019-03-08 | 2021-08-17 | 日本电气硝子株式会社 | Wavelength conversion member and light emitting apparatus |
| CN113054082B (en) * | 2019-12-27 | 2022-10-18 | 鑫虹光电有限公司 | Fluorescent glass composite material, fluorescent glass substrate comprising same, and light conversion device |
| CN111574062B (en) * | 2020-03-31 | 2022-10-18 | 温州大学 | Nitride red-light glass and application thereof |
Citations (1)
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|---|---|---|---|---|
| WO2011013505A1 (en) * | 2009-07-27 | 2011-02-03 | コニカミノルタオプト株式会社 | Phosphor-dispersed glass, and process for production thereof |
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| TW383508B (en) | 1996-07-29 | 2000-03-01 | Nichia Kagaku Kogyo Kk | Light emitting device and display |
| JP4158012B2 (en) | 2002-03-06 | 2008-10-01 | 日本電気硝子株式会社 | Luminescent color conversion member |
| JP4895541B2 (en) | 2005-07-08 | 2012-03-14 | シャープ株式会社 | Wavelength conversion member, light emitting device, and method of manufacturing wavelength conversion member |
| JP5483795B2 (en) | 2006-04-11 | 2014-05-07 | 日本電気硝子株式会社 | Luminescent color conversion material and luminescent color conversion member |
| JP2013055269A (en) * | 2011-09-06 | 2013-03-21 | Nippon Electric Glass Co Ltd | Wavelength conversion member and light-emitting device |
| JP2014157856A (en) * | 2013-02-14 | 2014-08-28 | Asahi Glass Co Ltd | Optical conversion member, and illumination light source having the same |
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| TW201527487A (en) | 2015-07-16 |
| TWI628261B (en) | 2018-07-01 |
| CN105637659A (en) | 2016-06-01 |
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| KR102258536B1 (en) | 2021-05-28 |
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| JP6222452B2 (en) | 2017-11-01 |
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