CN101128564B - Fluorophor and method for producing the same, and light-emitting device using the same - Google Patents
Fluorophor and method for producing the same, and light-emitting device using the same Download PDFInfo
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- CN101128564B CN101128564B CN2006800062270A CN200680006227A CN101128564B CN 101128564 B CN101128564 B CN 101128564B CN 2006800062270 A CN2006800062270 A CN 2006800062270A CN 200680006227 A CN200680006227 A CN 200680006227A CN 101128564 B CN101128564 B CN 101128564B
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- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical class [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- Luminescent Compositions (AREA)
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- Led Device Packages (AREA)
Abstract
This invention provides a fluorescent substance as a fluorescent material for white LED using blue LED or ultraviolet LED as a light source. The fluorescent substance comprises a-type sialon represented by general formula: (M1)X(M2)Y(Si)12-(m+n)Al)m+n(O)n(N)16-n wherein M1 represents one or more elements selected from the group consisting of Li, Mg, Ca, Y, and lanthanide metals (excluding La and Ce); M2 represents one or more elements selected from Ce, Pr, Eu, Tb, Yb, and Er; and 0.3 = X + Y = 1.5, 0 < Y = 0.7, 0.6 = m = 3.0, 0 = n = 1.5, and X + Y = m/2. The fluorescent substance is characterized in that the content of oxygen in the a-type sialon in a powder form is larger by not more than 0.4% by mass than a value obtained by calculation based on the above general formula.
Description
Technical field
The present invention relates to excited and send alpha-siaion (sialon) fluor, its method of manufacture of visible rays and used the luminous element of this fluor, particularly White LED by ultraviolet ray and even blue light.
Background technology
As fluor, well-known have fertile material to use silicate, phosphoric acid salt, aluminate or sulfide, and luminescence center has used the fluor of transition metal or rare earth metal.On the other hand, for White LED, had that high-octane excitaton source excites and the element that sends visible rays is gazed at by ultraviolet ray or blue light etc., and develop.But there is the problem that is exposed to excitaton source and causes the brightness decline of fluor in aforementioned existing fluor.As the less fluor of brightness decline degree, what gazed at recently is nitride and oxonitride phosphor, and this is because their crystalline texture is stable, be exciting light or luminous can be to the material of long wavelength side displacement.
The known alpha-siaion that is activated as the specific rare earth element of nitride and oxonitride phosphor has useful fluorescent characteristic, and (with reference to patent documentations 1～5, non-patent literature 1) such as White LEDs used it in research.In addition, find Ca that rare earth element has been activated
2(Si, Al)
5N
8, CaSiAlN
3And β type Sialon has same fluorescent characteristic (with reference to patent documentation 6, non-patent literature 2,3).The fluor (below, also be called nitride phosphor, oxonitride phosphor successively) of nitride such as aluminium nitride AlN, silicon nitride magnesium, nitrogenize silico-calcium, silicon nitride barium, gan, silicon nitride zinc and oxynitride has been proposed in addition.
Alpha-siaion through under the high temperature in nitrogen to by silicon nitride, aluminium nitride AlN, aluminum oxide and invade mixed powder that the oxide compound etc. of the element of solid solution between lattice forms and calcine and obtain.Can obtain various fluorescent characteristic according to the ratio of silicon nitride and aluminum compound, kind and the ratio etc. that becomes the element of luminescence center of invading the element of solid solution.The element of invading solid solution is Ca, Li, Mg, Y or lanthanum family metal (except La and the Ce), in order to ensure electroneutral, has the Si-N key partly by Al-N key and the substituted structure of Al-O key.Because invading the part of the element of solid solution is the rare earth element that becomes luminescence center, so manifest fluorescent characteristic.
But there be the problem of luminous efficiency not as good as luminescent lamp in the White LED that obtains now, from considering that in the energy-conservation angle of industrial field the LED that luminous efficiency is superior to luminescent lamp, particularly White LED are developed in strong request.
Different with monochromatic ray, white must be the combination of multicolour, and general White LED is constituting of the excitaton source fluor that sends visible rays by ultraviolet LED or blue led with aforementioned LED.Therefore, in order to improve the efficient of White LED, when must improve in the luminous efficiency of the LED of ultraviolet LED or blue led itself, the luminous efficiency that is used in fluor wherein improves, and light outgoing to the outside efficient of sending is improved.For the general illumination that comprises that enlarges White LED is used in interior purposes, above-mentioned all efficient is improved.
As the compound method of this fluor, known when for example being alpha-siaion powder, in the presence of carbon, in nitrogen atmosphere to aluminum oxide (Al
2O
3), silicon oxide (SiO
2), the mixed powder of metal that can solid solution in lattice or oxide compound of element etc. carries out the reduction nitridation method (with reference to non-patent literature 4～6) of heat treated.
The characteristic of this method is that raw material powder is inexpensive, can under the lesser temps about 1500 ℃, synthesize.But, can produce multiple intermediate product in the building-up process, can produce gaseous constituents such as SiO or CO simultaneously, therefore be difficult to obtain single-phase body, the strictness control that is difficult to form and the control of granularity.
In addition,, pulverize the gained sintered compact again, also can obtain α type or β type siaion powder through at high temperature the mixture of the metal of silicon nitride, aluminium nitride AlN and solid solution in their lattice or the oxide compound of element etc. being calcined.But, of the back, the problem that exists the crushing operation of sintered compact that the luminous intensity of fluor is descended.
In addition, White LED generally is scattered in the sealing materials such as epoxy resin with the particle of micron-scale with fluor and is used.But, its dispersion state and make a big impact with the consistency of sealing material outgoing efficient to the light of LED.And, with the luminous efficiency that improves fluor with prevent that deterioration from being purpose, the surface applied of fluor is also inquired into, its effect is different because of fluor, therefore also can have uncertain (with reference to patent documentation 7～9) completely without effect sometimes.
In addition, the specific refractory power of nitride or oxynitride is greater than the such oxynitride based phosphor of the YAG:Ce that was used to White LED in the past, and proportion is less, so if resemble the oxide phosphor and use, then can't obtain the enough characteristics of luminescences as LED.
Patent documentation 1: Japanese Patent Laid is opened the 2002-363554 communique
Patent documentation 2: Japanese Patent Laid is opened the 2003-336059 communique
Patent documentation 3: Japanese Patent Laid is opened the 2003-124527 communique
Patent documentation 4: Japanese Patent Laid is opened the 2003-206481 communique
Patent documentation 5: Japanese Patent Laid is opened the 2004-186278 communique
Patent documentation 6: Japanese Patent Laid is opened the 2004-244560 communique
Patent documentation 7: Japanese Patent Laid is opened the 2001-303037 communique
Patent documentation 8: Japanese Patent Laid is opened the 2000-204368 communique
Patent documentation 9: International Publication WO96/09353 text
Non-patent literature 1:J.W.H.van Krebel, " On new rare-earth doped M-Si-Al-O-N materials ", TU Eindhoven, The Netherlands, p.145-161 (1998)
Non-patent literature 65 Applied Physics association lecture meetings in 2: the preparatory original text collection (in September, 2004, northeast university of institute) No.3p.1282-1284 that gives a lecture
3: the 52 applied physics of non-patent literature are associated and costar preparatory original text collection (in March, 2005, the outstanding beautiful university) No.3p.1615 that gives a lecture of lecture
Non-patent literature 4:M.Mitomo etc., " Preparation of α-SiAlON Powders byCarbothermal Reduction and Nitridation ", Ceram.Int., 14,43-48 (1988)
Non-patent literature 5:J.W.T.van Rutten etc., " Carbothermal Preparation andCharacterization of Ca-α-SiAlON ", J.Eur.Ceram.Soc., 15,599-604 (1995)
Non-patent literature 6:K.Komeya etc., " Hollow beads Composed of Nanosize Ca α-S iAlON Grains ", J.Am.Ceram.Soc., 83,995-997 (2000)
The announcement of invention
As stated, in the prior art, there is following problem in the powder of nitride phosphor or oxonitride phosphor.That is, only contain nitride that constitutes element and the compound that contains active element perhaps constitute element with reduction nitridations such as carbon hopcalite, can't obtain to possess the fluor powder of enough characteristics through Hybrid Heating.
Particularly Hybrid Heating contains in the method for manufacture of known in the past nitride or oxynitride of the nitride that constitutes element and the compound that contains active element; Because the liquid phase sintering in the calcination process; It is very firm that interparticle combination becomes; Therefore in order to obtain the powder of desired particle size, must under harsh condition, carry out pulverization process.In addition, pulverization conditions is harsh more, and to sneak into the chance of impurity many more, can import defective at each particle surface simultaneously.Fluorescence is sent in the optical excitation that is excited near the surface owing to fluor, so the surface imperfection that is caused by pulverization process can affect greatly fluorescent characteristic, has the problem of characteristics of luminescence deterioration.
In addition, nitride powder contains the oxygen as unavoidable impurities, and this oxygen is included in the oxygen of intragranular solid solution and is present in these 2 kinds of the oxygen of particle surface with the form of oxide compound epithelium.It is different because of the kind of the manufacturing processed of nitride powder, preservation state, nitride etc. to be present in oxygen in the particle (below be called solid solution oxygen) and the amount that is present in surperficial oxygen (below be called surface oxygen); Therefore, cause adopting the characteristics of luminescence of nitride raw material synthetic fluor different.
In addition, because the specific refractory power of nitride and oxynitride is greater than the such oxynitride based phosphor of the YAG:Ce that was used to White LED in the past, and proportion is little, so if resemble use the oxide phosphor, then can't obtain the enough characteristics of luminescences as LED.
In the prior art; The such solid solution of kind, amount, ratio that the improvement of the luminous efficiency of alpha-siaion fluor mainly is conceived to become the replacement amount of Al-N in the alpha-form si nitride of crystallization skeleton, Al-O key or invades intracell solid solution element is formed and is carried out, and also the factor beyond forming is not inquired into.
In addition, the alpha-siaion sintered compact that obtains through high-temperature calcination is pulverized, obtained alpha-siaion powder, but the problem that exists the influence that is attached to the impurity of alpha-siaion powder because of crushing operation to cause the luminous intensity of fluor to descend.
In addition, White LED generally is dispersed in the sealing materials such as epoxy resin with the particle of micron-scale with fluor and is used.Consider from dispersiveness resin or the uneven angle of color development, must the regulation size of particles.The alpha-siaion fluor is made up of the offspring that a plurality of tiny primary particle sintering form.Usually, the granular information that is obtained by particle size distribution is exactly the information of this offspring, when being used for fluor aforementioned offspring is inquired into, but also is not conceived to primary particle research.
The present invention is the invention that is used to solve above-mentioned problem, its objective is the luminous element that the good Sialon fluor of luminous efficiency is provided and has used this fluor, particularly is the good White LED of luminous efficiency of light source with blue led or ultraviolet LED.
The present inventor has carried out various experimental discussions back discoveries to nitride phosphor and oxonitride phosphor; Various factorss such as the state through suitably making up oxygen amount in the fluor, fluorophor particle surface, surface applied, sealing resin; The fluorescent characteristic of this fluor about can be largely, thus the present invention accomplished.
Particularly carrying out various discussions back for alpha-siaion finds; The alpha-siaion of ad hoc structure has the peak in the wavelength region may of the scope of 550～600nm; And luminous efficiency is good, is applicable to LED, particularly is the good White LED of luminous efficiency of light source with blue led or ultraviolet LED.
That is, the present invention provides fluor, it is characterized in that, said fluor is by general formula: (M1)
X(M2)
Y(Si)
12-(m+n)(Al)
M+n(O)
n(N)
16-nThe powdery fluorescent body that the alpha-siaion of expression forms, in the formula, M1 is for being selected from the element more than a kind of Li, Mg, Ca, Y and lanthanum family metal (except La and the Ce); M2 is the element more than a kind that is selected from Ce, Pr, Eu, Tb, Yb and Er; 0.3≤X+Y≤1.5,0＜Y≤0.7,0.6≤m≤3.0; 0≤n≤1.5, X+Y=m/2; Oxygen level in the powder of aforementioned alpha-siaion be no more than based on aforementioned formula calculate this value of scope internal ratio of 0.4 quality % of value big.
In addition; The present invention relates to the powdery fluorescent body that the particle by the nitride of metal or oxynitride constitutes; It is characterized in that having thick (10～180)/n (unit: transparent film nanometer) at least a portion surface of the particle of the nitride of aforementioned metal or oxynitride.Here, n is the specific refractory power 1.2～2.5 of transparent film.In the preferred implementation of the present invention, n is 1.5～2.0.Be preferably at least a portion surface that this transparent film likewise is formed at the particle of Sialon.
The present invention provides fluor, and the aforementioned formula of this fluor is (M1)
X(M2)
Y(Si, Al)
12(O, N)
16, in the formula, 0.3≤X+Y≤1.5,0＜Y≤0.7, the mean aspect ratio of primary particle of powder that constitutes aforementioned alpha-siaion is below 3, and the diameter of the above particle of 80% (number percentage) of aforementioned primary particle is 3～10 μ m.
The present invention provides fluor, the aforementioned formula of this fluor be (Ca, Eu)
M/2(Si)
12-(m+n)(Al)
M+n(O)
n(N)
16-n, Eu content is 0.1～0.35at%, and lattice parameter a is 0.780～0.790nm, and lattice parameter c is 0.560～0.580nm.
Be preferably in above-mentioned each fluor, M1 contains Ca at least, and M2 contains Eu at least, and being more preferably aforementioned M1 is Ca, and M2 is Eu.
Be preferably in the above-mentioned fluor; M1 contains Ca at least; M2 contains Eu at least, and 0.01＜Y/ (X+Y)＜0.3, possesses maximum strength through irradiation luminous wavelength and is positioned at ultraviolet ray or the visible light of 100～500nm and has the characteristics of luminescence at peak in the wavelength region may of the scope of 550～600nm.
Be preferably in the fluor that the powder of aforementioned alpha-siaion forms, the median size that constitutes the particle of alpha-siaion is 1～20 μ m, is more preferably impurity beyond the element that constitutes alpha-siaion below 1 quality %.
The present invention also provides luminous element, it is characterized in that, contains LED that the maximum strength of aforementioned phosphors and emission wavelength is positioned at 240～480nm as integrant.Be preferably in this luminous element, LED is imbedded in the identical resin layer of specific refractory power 1.58～1.85 with nitride or oxonitride phosphor, this resin layer surface is covered by the resin of specific refractory power 1.3～1.58.
The present invention also provides lighting fixtures, it is characterized in that, is made up of illuminating source and fluor, has used aforementioned phosphors at least.As aforementioned phosphors; The preferred M1 that uses contains Ca at least; M2 contains Eu at least; And 0.01＜Y/ (X+Y)＜0.3; Possess through the wavelength region may in the scope of 550～600nm has the fluor of the characteristics of luminescence at peak for excitaton source shines with the ultraviolet ray of wavelength with 100～500nm or visible light, and possess the fluor that has the characteristics of luminescence at peak for excitaton source shines in the wavelength region may of the scope of 500～550nm through with the ultraviolet ray of wavelength or visible light with 100～500nm.
In addition, the present invention also provides the lighting fixtures that has used fluor, and this lighting fixtures is made up of illuminating source and fluor, and aforementioned phosphors is by general formula: (Ca, Eu)
M/2(Si)
12-(m+n)(Al)
M+n(O)
n(N)
16-nThe alpha-siaion of expression constitutes, and the Eu content of this alpha-siaion is 0.1～0.35at%, and lattice parameter a is 0.780～0.790nm, and lattice parameter c is 0.560～0.580nm.Being preferably this lighting fixtures is that excitaton source shines with ultraviolet ray or visible light.
In addition, the present invention also provides the method for manufacture of fluor, and it is a general formula: (M1)
X(M2)
Y(Si)
12-(m+n)(Al)
M+n(O)
n(N)
16-nThe method of manufacture of the fluor that the alpha-siaion of expression forms, in the formula, M1 is for being selected from the element more than a kind of Li, Mg, Ca, Y and lanthanum family metal (except La and the Ce); M2 is the element more than a kind that is selected from Ce, Pr, Eu, Tb, Yb and Er; 0.3≤X+Y≤1.5,0＜Y≤0.7,0.6≤m≤3.0; 0≤n≤1.5, X+Y=m/2; The method is characterized in that,, use oxygen-free calcium cpd as the Ca raw material.
In addition, the present invention also provides the method for manufacture of fluor, and it is a general formula: (M1)
X(M2)
Y(Si)
12-(m+n)Al)
M+n(O)
n(N)
16-nThe method of manufacture of the fluor that the alpha-siaion of expression forms, in the formula, M1 is for being selected from the element more than a kind of Li, Mg, Ca, Y and lanthanum family metal (except La and the Ce); M2 is the element more than a kind that is selected from Ce, Pr, Eu, Tb, Yb and Er; 0.3≤X+Y≤1.5,0＜Y≤0.7,0.6≤m≤3.0; 0≤n≤1.5, X+Y=m/2; The method is characterized in that, as the Ca raw material, and with oxygen-free calcium cpd and oxygen containing calcium cpd.Be preferably in the method for manufacture of this fluor, use with respect to oxygen containing calcium cpd with molar ratio computing at the oxygen-free calcium cpd more than 0.5 times.Be more preferably in the method for manufacture of this fluor, the oxygen amount in all raw materials is below 4 quality %.
In addition, the present invention also provides the method for manufacture of fluor, the method is characterized in that, after the method for manufacture of utilizing aforementioned fluor of the present invention is made fluor, again aforementioned phosphors is carried out s.t..Method of manufacture is to make general formula preferably: Ca
XM2
Y(Si)
12-(m+n)(Al)
M+n(O)
n(N)
16-n(M2 is the element more than a kind that is selected from Ce, Pr, Eu, Tb, Yb and Er; 0.3≤X+Y≤1.5,0＜Y≤0.7,0.6≤m≤3.0; 0≤n≤1.5; X+Y=m/2) pulverous fluor of the alpha-siaion of expression formation is suspended in organic solvent, in this suspension-s, drips organometallic complex or metal alkoxide, forms thick (10～180)/n (unit: transparent film nanometer) at least a portion surface of the alpha-siaion particle that constitutes fluor.Perhaps, method of manufacture is to make aforementioned phosphors be suspended in water preferably, when keeping pH certain, drips aqueous metal salt, forms thick (10～180)/n (unit: transparent film nanometer) at least a portion surface of the alpha-siaion particle that constitutes fluor.Here, n is the specific refractory power 1.2～2.5 of transparent film.
Fluor preferably of the present invention is the alpha-siaion of nitride or oxynitride or specific composition; And oxygen level is by specific; Perhaps has the structure that is provided with the transparent material of regulation specific refractory power at least a portion surface of the particle that constitutes this fluor with specific thickness; So compare with fluor in the past, can obtain fluorescent characteristic, the particularly effect of the excellent in luminous characteristics of 400～700nm scope.By this, applicable to various LED, particularly can obtain good White LED through combination with the LED that has maximum strength at emission wavelength 240～480nm.
The visible light that alpha-siaion with ad hoc structure of the present invention can be had ultraviolet ray or visible light, particularly a 440～480nm of 100～500nm wavelength excites effectively and the scope that is created in 550～600nm has the light at peak; So be applicable to various lighting fixturess, particularly be the White LED of light source, can obtain high-duty by good luminescent characteristic with blue led or ultraviolet LED.
Because lighting fixtures of the present invention has used the aforementioned fluor that is formed by alpha-siaion; Even so at high temperature use brightness flop also less; And can increase the service life, the blue led of visible light that particularly can send 440～480nm when the illuminating source, the combination of light through this illuminating source and the light that sends from alpha-siaion; Can easily obtain white light, be applicable to various uses.
Utilize the method for manufacture of fluor of the present invention, can stablize and make fluor in a large number with aforementioned characteristic.
The simple declaration of accompanying drawing
Fig. 1 is the schematic cross-section of an example of expression fluor of the present invention.
Fig. 2 is the schematic cross-section as the bullet cut LED of an example of luminous element of the present invention.
Fig. 3 is another routine schematic cross-section of expression luminous element of the present invention.
Fig. 4 is the simple declaration figure of the described lighting fixtures of embodiments of the invention 2-4 (surface mounting LED).
The explanation of symbol: 1 sealing material for the fluor of packing into, 2 is semiconductor element portion, and 3 is lead frame, and 4 is lead; 5 is the bullet cut transparent resin, and 6 is fluor, and 7 is resin layer, and 8 is sealing resin; 9 is nitride or oxonitride phosphor, and 10 is transparent film, and 11 is the blue led sheet, and 12 is the alpha-siaion fluor; 13 is lead frame, and 14 is sealing resin, and 15 is container, and 16,17 is the electroconductibility terminal.
The best mode that carries out an invention
The present invention is that the condition of (1)～(4) below satisfying can be guaranteed good fluorescent characteristic to the result that nitride phosphor or oxonitride phosphor have carried out various experimental discussions.Promptly; (1) is the alpha-siaion of specific composition; And oxygen level is limited to particular value; (2) form at least a portion surface of nitride phosphor or oxonitride phosphor the structure that is provided with the transparent material of regulation specific refractory power with specific thickness, (3) with the size and dimension of the composition of alpha-siaion and primary particle thereof specific or (4) composition and the crystalline texture of alpha-siaion is specific.
At first, above-mentioned (1) is elaborated.Below as do not have special the qualification, percentage is represented quality %.
Fluor preferably of the present invention is formed by the alpha-siaion of specific composition.That is, alpha-siaion is with general formula: (M1)
X(M2)
Y(Si)
12-(m+n)(Al)
M+n(O)
n(N)
16-n(in the formula; M1 is for being selected from the element more than a kind of Li, Mg, Ca, Y and lanthanum family metal (except La and the Ce); M2 is the element more than a kind that is selected from Ce, Pr, Eu, Tb, Yb and Er) expression is known, and the alpha-siaion that the present invention's selection has the relation of 0.3≤X+Y≤1.5,0＜Y≤0.7,0.6≤m≤3.0,0≤n≤1.5, X+Y=m/2.The alpha-siaion of this composition is extremely important for obtaining the good fluor of fluorescent characteristic.
In the aforementioned component, consider the preferred Ca of M1 from obtaining the stable fluorescence characteristic with low cost.In this case, consider that from obtaining good fluorescent characteristic M2 selects Eu.In addition, Y is with respect to X+Y, and lower limit is preferably more than 0.01, better is more than 0.02, and the upper limit is preferably below 0.5, better is below 0.3.If Y surpasses the upper limit (0.5) with respect to X+Y, then can cause so-called concentration quenching, the luminous intensity of fluor descends, and because the Eu valency is high, so can cause cost to rise.If less than 0.01, then luminescence center reduces Y with respect to X+Y, brightness descends.
The present invention have the contained oxygen amount of the alpha-siaion powder of aforementioned specific composition be no more than based on aforementioned formula calculate value 0.4 quality %, be preferably 0.25 quality %, better be the big formation of this value of scope internal ratio of 0.15 quality %, can obtain fluorescent characteristic based on this formation and be superior to effect in the past.Consequently, the lower limit of the oxygen amount that aforementioned alpha-siaion powder is contained is preferably more than the 0.8 quality %, better is more than the 1.0 quality %, and the upper limit is preferably below the 2.5 quality %, better is below the 2.0 quality %.
When adopting aforementioned formation,, nitride or oxonitride phosphor that interparticle sintering has been done one's utmost to suppress can be obtained, the just effect of corpusculed easily of pulverizing through degree of crushing can be obtained though reason is indeterminate.Based on this effect, can obtain to form the characteristic of the granularity that is suitable as fluor.In addition, this fluor makes pulverization process produce because of aforementioned characteristic surface imperfection reduces, so infer the characteristic that helps aforementioned excellent in luminous characteristics.
Below, (2) are detailed.
The present invention is based on following conclusion.That is, at least a portion surface configuration through being formed on the particle that constitutes nitride or oxonitride phosphor the structure of specific transparent film of specific thickness, the fluorescent characteristic of this fluor improves.That is to say, when particle surface is provided with the transparent film of regulation material with specific thickness, can improve the fluorescent characteristic of fluor.
The transparent film that is arranged at particle surface is inquired into the back find that there is suitable thickness range in transparent film, if littler than specific thickness; Then be difficult to be provided with the high transparent film of homogeneity; In addition, make the defective on fluorophor particle surface reduce or prevent that the effects such as reflection of the light (abbreviating exciting light as) of the excited fluophor of particle surface from weakening, if blocked up; Then cause the absorption of the light that film itself causes, the tendency that therefore exists the luminous efficiency of fluor to descend.In addition, in order to obtain good fluorescent characteristic with high reproducibility, only specific thickness is also not enough, preferably also considers to set the specific refractory power of transparent film.
Promptly; The invention is characterized in; Fluor is pulverous fluor that the particle by the nitride of metal or oxynitride constitutes; Have that (unit: nanometer, n: the thickness specific refractory power of transparent film) is provided with the structure of the transparent film of refractive index n (1.2～2.5) with (10～180)/n at least a portion surface of its constituent particle.Should constitute through adopting, in the luminous reflectance and absorption of the defective of the particle surface that prevents fluor, the excitation light absorbing rate raising of fluor can stably provide high efficiency fluor.If beyond aforementioned numerical range, then the variable thickness of transparent film is enough surely in suitable thickness range, so not ideal.What the particle with transparent film of the present invention was more satisfactory is to be provided with transparent film at whole particle surface, should structure if observe with scanning electron microscope, then can be observed the for example illustrative form of Fig. 1.In this example, the whole surface of nitride or oxonitride phosphor 9 is covered by transparent film 10.But if the part of particle surface among the present invention, that is, roughly over half being capped just can reach effect of the present invention.
Constitute aforementioned transparent film material so long as aforementioned refractive index n be 1.2～2.5 transparent (special good be according to purposes from ultraviolet ray to blue region; Particularly in 240～480nm zone; Having the material of transmissivity in the transparency more than 80%) material gets final product, and can use any material.As this material, but inorganicss such as illustration silicon-dioxide, titanium oxide, aluminum oxide, Natural manganese dioxide, Sellaite, resins such as PS, polycarbonate, polyvinyltoluene.Wherein, for the effect that weakens of the surface imperfection that possesses fluor, preferably select inorganics.
In addition, when fluor was used for purposes such as LED, most examples were fluor to be imbedded resin use, and in this case, between aforementioned resin and fluor surface, have aforementioned transparent film layer.At this moment, consider that the specific refractory power of hoping transparent film is between the specific refractory power of the specific refractory power of aforementioned resin and fluor constituent particle from the optics aspect.For example, the specific refractory power of silicon nitride is 2.0, and the specific refractory power of the silicone resin that epoxy resin that is widely used as the sealing material that constitutes LED or consideration are used to ultraviolet LED is all near 1.5.The specific refractory power of nitride or oxonitride phosphor does not have the data of announcement, but can confirm experimentally that its specific refractory power is bigger.If the refringence of fluor and sealing resin is bigger, the exciting light that then causes arriving the fluor surface through sealing resin is reflected on this surface.Therefore, form film on the fluor surface and help reducing reflectivity, that is, help improving the fluorescence efficiency of fluor with suitable specific refractory power.So the better scope of the specific refractory power of transparent film is 1.5～2.0, better be 1.6～1.9.As this material, but illustration Natural manganese dioxide or aluminum oxide.
Preferably suitably select the material and the thickness thereof of transparent film according to transparent film material and purposes.Concrete example is described below.That is, since magnesian specific refractory power near 1.75, so its thickness is 5～100nm; When fluor is used for burst of ultraviolel type White LED; The thickness of transparent film is preferably 5～70nm, is preferably 10～60nm, when being used for blue excitation type White LED; The thickness of transparent film is preferably 10～100nm, is preferably 15～80nm.
The principal constituent of known blueness or ultra-violet light-emitting element is a gan, and its specific refractory power is about 2.4～2.5 very large value.In this case, in order to obtain light from luminous element effectively, the resin covering luminous element that the most handy specific refractory power is high.And, cover the most employing of resin (imbedding the resin of fluor) of fluor and the same resin of resin of covering luminous element.In this purposes, preferably use the resin of high refractive index such as polycarbonate resin, fluorenes based epoxy resin, fluorenes class silicone resin, phenyl silane class silicone resin, sulphur based epoxy resin.In addition, in order to improve the efficient of beam projecting to luminous element, the resin of handy low-refraction covers the outside of these resins.As this resin, can give an example epoxy resin, silicone resin, fluorine resin, fluorine-containing epoxy resin etc.
Therefore; When nitride phosphor or oxonitride phosphor are used for luminous element; The structure of luminous element is if be provided with the transparent film of specific refractory poweres 1.6～1.9 such as aluminum oxide or Natural manganese dioxide on fluor (constituent particle) surface, with the resin of itself and specific refractory power 1.58～1.85, the for example higher mixed with resin of specific refractory power such as fluorenes based epoxy resin; With this mixture sealing semiconductor element (photodiode); Use the resin of specific refractory power 1.3～1.58 again, the resin that for example specific refractory power such as fluorine-containing epoxy resin is lower surrounds the structure of the periphery of sealing material, then can constitute the high luminous element of luminous efficiency.
The present invention comprises the maximum strength of aforementioned phosphors and emission wavelength at the LED of the 240～480nm LED as integrant.As stated, this LED reflection good fluorescent characteristic that fluor possessed manifests good illumination efficiency.In addition; The fluor that is provided with transparent film in the aforementioned phosphors at least a portion surface of fluor constituent particle has the better characteristic of luminous efficiency; So it is more satisfactory; With the specific refractory power of transparent film is that 1.6～1.9 fluor is imbedded when being used for LED behind the resin, still can reflect the good fluorescent characteristic that fluor is original, so better.
Below, for the fluor of (1), be example during for Ca with M1, its method of manufacture is detailed.
Alpha-siaion adopt will (a) silicon nitride, (b) aluminium nitride AlN and aluminum oxide any more than a kind, (c) contain the compound of M1 and (d) contain the mixing raw material that the compound of M2 gets according to an amount of mixing of desirable composition, this raw material is heated and synthesizes.The present invention satisfies 0≤n≤1.5 in order to realize oxygen level as stated, and be no more than based on general formula calculate the big such condition of this value of scope internal ratio of 0.4 quality % of value, it is characterized in that adopting the least possible raw material of oxygen consuming amount.
That is, one of method of manufacture of fluor of the present invention is characterised in that, raw material adopts that (a) silicon nitride, (b) aluminium nitride AlN, (c) contain the Ca compound, (d) contains the M2 compound, and aforementioned (c) contains the Ca compound and adopt oxygen-free calcium cpd.In this case, as aforementioned oxygen-free calcium cpd, but illustration for example calcium chloride, sulfurated lime, calcium cyanamide, carbide of calcium.Should constitute through adopting, can stablize provides by comminuted good, the good fluor of fluorescent characteristic.
Preferred implementation as the method for manufacture of fluor of the present invention contains the Ca compound as (c), can and with oxygen-free calcium cpd and oxygen containing calcium cpd.In this case, as oxygen-free calcium cpd, but the aforementioned calcium chloride of illustration, sulfurated lime, CaCl2, calcium cyanamide, carbide of calcium, as oxygen containing calcium cpd, but illustration quicklime, calcium hydroxide, lime carbonate, calcium sulfate, nitrocalcite.Adopt in the time of to constitute, can use the micro mist of CaO etc. to make reactive raw material that increases and inexpensive calcium cpd, fluor can be provided at low cost, so helped the effect of industry development by expectation.
In addition, and during, with oxygen-free calcium cpd and oxygen containing calcium cpd its ratio preferably the former with respect to the mol ratio of latter Ca more than 0.5 times.This is because make the high raw material of oxygen consuming amount can increase the oxygen amount of gained fluor, prevents that fluorescent characteristic from descending.
In addition; About aforementioned mixing raw material, when representing, satisfy 0≤n≤1.5 in order to realize oxygen level with the general formula of alpha-siaion; And be no more than based on general formula calculate the big such condition of this value of scope internal ratio of 0.4 quality % of value, the oxygen amount in the mixing raw material is preferably less.The present inventor inquires into the back and finds that the oxygen amount in the mixing raw material can obtain to satisfy the fluor of aforementioned condition, so more satisfactory effectively when 4 quality % are following.
Among the present invention, preferably also fluor (alpha-siaion) is carried out s.t..The present inventor inquires into the back and finds, through fluor is carried out s.t., can reduce the oxygen level of fluor, and consequently, fluorescent characteristic improves.In addition, should operate, and can realize to stablize the effect that obtains the better fluor of fluorescent characteristic through increasing.Being used for acid-treated acid can be the acid of using always, but is preferably the acid of the oxide compound that can remove silicon, for example mixing acid such as hydrofluoric acid or hydrofluoric acid-nitric acid, hydrofluoric acid-hydrochloric acid.
But the present inventor has also experienced the oxygen amount in the fluor and has calculated and situation below the oxygen amount of trying to achieve at analytical value substitution general formula with metal ingredient.In this case, can't obtain good fluorescent characteristic.That is, when the actual oxygen amount is less than the oxygen amount of being tried to achieve by general formula,, also thinks to have the phase different, so can't obtain the ideal fluorescent characteristic with alpha-siaion even can't confirm the situation of the crystallization phases beyond the alpha-siaion by X-ray diffraction method.
Below, the method for manufacture of the fluor of (2) is detailed.
The method that forms transparent film on the fluor surface can adopt the whole bag of tricks such as known damp process, CVD method, sputtering method, vacuum vapour deposition, spray heating decomposition; Wherein, Consider from installing angle simple and that cost is low; Preferred damp process and spray heating decomposition, the following stated is the example of damp process.
Promptly; The method of manufacture of fluor of the present invention is to make nitride or oxonitride phosphor; For example to be suspended in alcohol etc. be in the organic solvent of representative by having fluor that the aforementioned desirable alpha-siaion of forming forms; In this suspension liquid, drip organometallic complex or metal alkoxide and alkaline aqueous solution; Form the epithelium of MOX or oxyhydroxide on fluorophor particle surface, in air or in the rare gas element such as nitrogen, calcine as required then, form the method for the transparent film of specific thickness by this at least a portion surface of the alpha-siaion particle that constitutes fluor.Owing to be easy to the thickness of the transparent film that is arranged at particle surface is controlled through control dropping condition, so can stably provide fluorescent characteristic good fluor with high reproducibility.
Other preferred implementation as damp process; Can give an example and make the aforementioned phosphors constituent particle be suspended in water; PH being kept drip aqueous metal salt in certain, form thick (10～180)/n (unit: the method for transparent film nanometer) at least a portion surface of the alpha-siaion particle that constitutes fluor.N is the specific refractory power 1.2～2.5 of transparent film.This method is with stirrer or ultrasonic disperser the fluor constituent particle to be suspended in alkali, acid or the damping fluid of pH through adjustment; Drip aqueous metal salt; Form the epithelium of oxide compound or oxyhydroxide of this metal on fluor surface after, filter washing; Drying is carried out methods of heating treatment more as required in air or in the rare gas element such as nitrogen.
In this embodiment, behind the formation transparent film, utilize silane coupling agent; Be preferably epoxy silane coupling agent and handle, the resin that is embedded in when making LED and the adaptation of fluor improve, and the dispersiveness of fluor in aforementioned resin improves; Consequently, the characteristic of LED rises.
Below, the fluor of (3) is detailed.
The characteristic of the fluor that this is routine is that aforementioned formula is (M1)
X(M2)
Y(Si, Al)
12(O, N)
16, in the formula, 0.3≤X+Y≤1.5,0＜Y≤0.7, the mean aspect ratio of primary particle of powder that constitutes aforementioned alpha-siaion is below 3, and the diameter of the above particle of 80% (number percentage) of aforementioned primary particle is 3～10 μ m.Below, this fluor is described.
Alpha-siaion is that the part of the Si-N key in the alpha-form si nitride is substituted by Al-N key and Al-O key, and in order to ensure electroneutral, specific positively charged ion is invaded intracell sosoloid, with formula M
Z(Si, Al)
12(O, N)
16Expression.Here, M is specially and is selected from Li, Mg, Ca, Y and more than a kind of lanthanum family metal (except La and the Ce) for can invade intracell element.The solid solution capacity Z value of M is the numerical value by the replacement rate decision of the Al-N key of Si-N key and Al-O key.
In order to manifest fluorescent characteristic, but the part of M must be the element that solid solution becomes luminescence center, in order to obtain the luminous fluor of visible light, preferably uses the element more than a kind that is selected from Ce, Pr, Eu, Tb, Yb and Er.Invade solid solution in intracell element, if being helpless to luminous element is M1, the element that becomes luminescence center is M2, then general formula is (M1)
x(M2)
Y(Si, Al)
12(O, N)
16Here, in order to obtain the monophasic fluorescent characteristic that manifests simultaneously of alpha-siaion, preferably satisfy 0.3≤X+Y≤1.5,0＜Y≤0.7.
As previously mentioned, general alpha-siaion is through obtaining its reaction to being heated by silicon nitride, aluminium nitride AlN and the mixed powder of compound formation of invading the element of solid solution in the pyritous nitrogen atmosphere.In temperature-rise period, be situated between with silicon nitride, aluminium nitride AlN, their oxide on surface or even the formed liquid phase of compound of solid solution element, the transfer of material takes place, generate alpha-siaion.Therefore, the alpha-siaion after synthesizing is because form offspring by a plurality of primary particle sintering, or even block, so through forming its pulverizing etc. Powdered.
This routine fluor is based on the result that the relation of the characteristics of luminescence and particle shape is inquired into, that is, and and the closely-related fact of the size of primary particle, distribution and shape and the characteristics of luminescence and the fluor that obtains.That is, fluor of the present invention is except aforementioned component, and the primary particle that constitutes the powder of fluor selects its mean aspect ratio below 3, and is 3～10 μ m in the diameter of the particle of number percentage more than 80%.Being preferably mean aspect ratio below 2.5, is 3～10 μ m in the diameter of the particle of number percentage more than 85%.
Long-width ratio for primary particle; For example from LED with dispersed the sealing resin or as the luminous intensity of LED, and the angle of the inequality of tone considers that anisotropy is to be advisable for a short time; But as long as the mean aspect ratio of primary particle then has no problem below 3 aspect practical.The mean aspect ratio of primary particle can be to utilize scanning electron microscope (SEM) to measure the long-width ratio (major axis footpath/short shaft diameter) of the primary particle more than at least 500, calculate again arithmetical av.
The distribution of sizes of primary particle is preferably narrower.Under the situation of the distribution of sizes broad of primary particle, the inequality of luminous intensity and tone can take place when using this fluor.On the other hand; If primary particle is too little; When then causing the specific absorption of light to descend because of scattering, interparticle sintering carries out more firmly, therefore in order to obtain the granularity as powder (offspring) defined; Just must implement the over-drastic pulverization process, thereby particle surface can produce the generation that defective causes unfavorable conditions such as characteristics of luminescence deterioration or the property handled deterioration like this.For the foregoing reasons, among the present invention, the particle of diameter that being sized to of primary particle is had 3～10 μ m in the number percentage more than 80%.Of the back, the number percentage can be to utilize scanning electron microscope (SEM) to measure the footpath value that is equivalent to circular diameter of the primary particle more than at least 500, with the definite value of its percentage.
In addition; The present invention also studies the trace additives of alpha-siaion fluor and the relation of the characteristics of luminescence; Consequently; Contain fluorine 5～300ppm, better be 20～270ppm or boron 10～3000ppm, when better being 200～1000ppm, can obtain the better characteristics of luminescence, so more satisfactory.This phenomenon is more than fluorine content 5ppm, and boron content 10ppm is tending towards when above significantly, and the former surpasses 300ppm, and when the latter surpassed 3000ppm, effect almost no longer improved.Certainly contain fluorine and boron simultaneously.The mensuration of boron adopts the ICP spectroscopic analysis to implement, and the mensuration of fluorine adopts ion chromatography to implement.
Micro-addition means to fluorine or boron does not have special qualification, and for fluorine, the part of preferred feedstock is used fluorochemical, in synthetic, makes the method for excessive fluorin volatilization.For boron, as the trace and the method for adding equably, the crucible of filling raw materials mix powder uses hexagonal boron system crucible when preferably synthetic, utilizes in the high temperature method by the boracic volatile matter of crucible trace generation.
In addition; After in the heat treated stated; Make as the volatilization of the part of the fluorine cpd in the raw material of volatile fluorine-containing thing, the fluorine content in the may command alpha-siaion by this is perhaps after heat treated; Through the processing of acid such as hydrochloric acid or sulfuric acid, also can remove residual fluorine cpd and reach the purpose of the fluorine content in the control alpha-siaion.
As the intracell element of solid solution in alpha-siaion; When M1 selects Ca, M2 selection Eu; Ultraviolet ray or visible light through with wavelength with 100～500nm are that excitaton source shines, and can obtain the fluor that in the wavelength region may of the scope of 550～600nm, has the peak, manifests Huang～orange-colored light.When for example using blue led as excitaton source, the sodium yellow and the mixing of exciting light through sending from this fluor can obtain White LED, so can to provide with White LED etc. be the lighting fixtures of emitting white light of representative, so more satisfactory.
About the element of solid solution in the lattice of alpha-siaion, as the atomic molar ratio of the Eu that becomes luminescence center, scope is 0.01＜Y/ (X+Y)＜0.3 preferably.If Y/ (X+Y) surpasses 0.01, then can not occur owing to luminescence center reduces the phenomenon that luminosity is descended, if less than 0.3, the phenomenon that causes luminous efficiency to descend because of the Eu of solid solution interionic interference initiation concentration quenching then can not take place.
Below, as the method that obtains this routine fluor, the illustration solid solution compound method of alpha-siaion of Ca and Eu.But method of manufacture is not limited in this.
This routine fluor uses the powder of silicon nitride, aluminium nitride AlN, calcium containing compound and europium sesquioxide as raw material.Because the boiling point of fluorochemical is higher, so preferably use Calcium Fluoride (Fluorspan) in these raw materials as the fluorine source.But when all the calcium source all was Calcium Fluoride (Fluorspan), it was single-phase to be difficult to obtain alpha-siaion, so became the compound of quicklime after the heating such as best and lime carbonate.
As the method for mixing aforementioned each raw material, can adopt the method for dry mixed, remove the method for desolvating etc. after in the inert solvent that does not react in fact with each composition of raw material, carrying out wet mixing.As mixing device, preferably use V-Mixer, shaker mixer, ball mill, vibrating mill etc.
Will according to desirable composition mix and powder (being designated hereinafter simply as raw material powder) be filled in the containers such as crucible that the face that contacts with this raw material powder at least forms by SP 1; Through in nitrogen atmosphere in 1600～1800 ℃ TR internal heating specified time, obtain alpha-siaion.The container material uses SP 1 not only because its reactivity with each composition of raw material is very low, also because the boracic trace volatile component that is produced by container has the effect of crystalline growth of the primary particle of promotion alpha-siaion.Pine for agglomerating angle consideration between particle from suppressing to add, preferably insert with higher loose density as much as possible during raw materials mix powder filling container.Specifically, the raw materials mix powder is preferably in below the 40 volume % the filling ratio of synthesising container.
The heat treated temperature the inadequate problem of growth of unreacted reactant or primary particle can not occur existing in a large number more than 1600 ℃ the time, if below 1800 ℃, the interparticle sintering significant phenomenon that becomes then can not occur, so more satisfactory.
Heat-up time during heat treated can be in the inadequate problem of growth that unreacted reactant or primary particle can not occur existing in a large number, perhaps can not take place to select in the time range of unfavorable conditions such as interparticle sintering.This heat-up time, preferred about 2～24 hours.
The alpha-siaion that is obtained by aforesaid operations is block, so through its fragmentation, pulverizing being reached the powder that according to circumstances can form specified dimension with the stage treatment combination, obtain to be applicable to the powdery fluorescent body of various uses.
When using with fluor as LED, a plurality of primary particle sintering and the median size of the offspring that forms is preferably 3～20 μ m.If the median size of offspring is more than 3 μ m, then luminous intensity can not descend, if median size below 20 μ m, then the homogeneous in the resin of sealing LED disperses to become easily, it is uneven to suppress luminous intensity and tone, can actually use.
The characteristic that the block that the alpha-siaion that is obtained by above method for making forms manifests that easily disperse is good, the enough mortars of ability etc. easily is ground into designated size as breaking method, can adopt ball mill or kibbler commonly used such as vibrating mill, injector-type mill etc.
Below (4) are detailed.
This routine alpha-siaion is with general formula: (Ca, Eu)
M/2(Si)
12-(m+n)(Al)
M+n(O)
n(N)
16-nExpression, in order to obtain the monophasic fluorescent characteristic that manifests simultaneously of alpha-siaion, m and n are preferably the scope of 0.6≤m≤3.0,0≤n≤1.5, if in this scope, the characteristics of luminescence of stating after then can obtaining effectively.Specifically, this routine alpha-siaion is a general formula: (Ca, Eu)
M/2(Si)
12-(m+n)(Al)
M+n(O)
n(N)
12-n, Eu content is 0.1～0.35at%, and lattice parameter a is 0.780～0.790nm, and lattice parameter c is the fluor of 0.560～0.580nm.Being preferably Eu content is 0.1～0.25at%, and lattice parameter a is 0.780～0.789nm, and lattice parameter c is 0.563～0.577nm.
Even the alpha-siaion of above-mentioned general formula also can't obtain the sufficient characteristics of luminescence sometimes.But the Eu content of this alpha-siaion is that 0.1～0.35at%, lattice parameter a are 0.780～0.790nm, when lattice parameter c is 0.560～0.580nm, can obtain the special good fluor of the characteristics of luminescence.
As after the embodiment institute illustration stated, this routine lattice parameter a is that 0.784～0.787nm, lattice parameter c are that the alpha-siaion of 0.569～0.572nm obtains through specific its composition strictly.That is, it is 0.1～0.35at% that the fusion raw material satisfies Eu content, synthetic alpha-siaion when the atmosphere gas to thereafter calcining raw materials the time is controlled.In addition, if satisfy 0.6≤m≤3.0,0≤n≤1.5, the alpha-siaion that then easier acquisition has the lattice parameter of aforementioned specified range.
As previously mentioned, generally through in the pyritous nitrogen atmosphere, making its reaction obtain alpha-siaion to heating by silicon nitride, aluminium nitride AlN and the mixed powder of compound formation of invading the element of solid solution.In temperature-rise period, be situated between with silicon nitride, aluminium nitride AlN, their oxide on surface or even the formed liquid phase of compound of solid solution element, the transfer of material takes place, generate alpha-siaion.Therefore, the alpha-siaion after synthesizing is because form offspring by a plurality of primary particle sintering, or even block, so form suitable powder shape fluor through it is pulverized to wait.
This routine alpha-siaion also is so, that is, the alpha-siaion after synthesizing is same because a plurality of primary particle sintering form offsprings, or even block, so the powdery fluorescent body through acquisitions such as its pulverizing, fragmentation are formed by alpha-siaion.
More than through pulverize, powdery fluorescent body that the broken alpha-siaion that obtains forms when the median size of the particle of the powder of formation alpha-siaion is 1～20 μ m, can obtain the higher characteristics of luminescence.The median size of particle is in aforementioned range if this is, then can suppress excessive micronization generation scattering and the luminous intensity that specific absorption descends or meal causes of the light that causes and the appearance of anisochromatic situation.
The alpha-siaion powder that is synthesized or pulverizes is sneaked into various impurity easily in its manufacturing processed.Present inventor's discussion result is that luminous intensity decline can not take place when 1 quality % is following the impurity that constitutes in the alpha-siaion powder beyond the element, can actually use.
Be used for suppressing each raw material of aforementioned impurity level blending means and mixing device, the pyritous nitrogen atmosphere method that heating makes its reaction to raw material powder and condition and synthetic after breaking method etc. the method for manufacture with the fluor of aforementioned (3) is identical in fact, omit its explanation.
Fluor of the present invention (alpha-siaion) has the scope that excites from the broad of ultraviolet ray to visible light, sends visible light, so be applicable to luminous element and lighting fixtures.The fluor of particularly selecting Ca and Eu as the intracell intrusion element of alpha-siaion and obtaining, having spike length is the high brightness luminescent characteristic of Huang～orange-colored light of 550～600nm.
Therefore; It is that the luminous element of integrant or the fluor that uses the lighting fixtures that this luminous element constituted use that alpha-siaion of the present invention is used as with illuminating source and fluor; Be that excitaton source shines the wavelength region may that possesses in the scope of 550～600nm and has the characteristics of luminescence at peak particularly, therefore have through being easy to obtain the characteristic of white light with the blue led combination through visible light with the wavelength that contains 440～480nm.In addition, even also deterioration can not take place owing to this alpha-siaion is exposed under the high temperature, and thermotolerance is good, and the permanent stability under oxidizing atmosphere and moisture environment are good, and these advantages make lighting fixtures possess high brightness and long-life characteristic.
Lighting fixtures of the present invention adopts at least a kind of illuminating source and fluor of the present invention to constitute.As lighting fixtures of the present invention; Comprise LED, luminescent lamp etc.; The known method of record such as japanese patent laid-open 5-152609 communique for example capable of using, japanese patent laid-open 7-99345 communique, No. 2927279 communique of Japanese Patent adopts fluor of the present invention to make LED.In this case; Illuminating source preferably uses the ultraviolet LED or the blue led of the light of the wavelength that sends 350～500nm; The blue led of light of the wavelength of 440～480nm is sent in special good being to use, and the luminous element as them comprises the element that is formed by nitride-based semiconductors such as GaN or InGaN; Form through adjustment, can form the illuminating source of the light that sends provision wavelengths.
In addition, fluor of the present invention except the method for in this lighting fixtures, using separately, through with other fluor with characteristics of luminescence and usefulness, also can constitute the lighting fixtures that sends desirable color.When particularly being excitaton source with the blue led, fluor of the present invention with send fluor when combination that spike length is green～sodium yellow of 500～550nm, can send the white light of colour temperature broad.As this fluor, the β type Sialon of Eu of can having given an example solid solution.In addition, through with CaSiAlN
3: the combination of red-emitting phosphors such as Eu, can realize the raising of color developing.
Fig. 2 is the schematic cross-section as the bullet cut lED of an example of luminous element of the present invention.Among Fig. 2,1 resin material for the fluor of packing into, 2 is semiconductor element portion, and 3 is lead frame, and 4 is lead, and 5 is the bullet cut transparent resin.Fluor of the present invention constitutes White LED with the state of the resin material 1 of being sneaked into the fluor of packing into and 2 combinations of semiconductor element portion.
Fig. 3 is another routine schematic cross-section of luminous element of the present invention.In this luminous element, cover the semiconductor element portion 2 of the bottom that is set at container 15, seal the upper surface of this resin layer 7 with sealing resin 8 with the resin layer 7 of having imbedded fluor 6 of the present invention.
Embodiment
Below, based on embodiment and comparative example the present invention is elaborated.
(embodiment 1)
(embodiment 1-1)
The proportioning of the raw material powder of the alpha-siaion of present embodiment is formed; Alpha-silicon nitride powders (electrochemical industry system; The 9FW level) 83.0 mass parts, aluminium nitride powder (ト Network ヤ マ system; The F level) 10.5 mass parts, europium sesquioxide powder (SHIN-ETSU HANTOTAI's chemical industry system, RU level) 1.5 mass parts and sulfurated lime powder (pure pharmaceutical worker already makes with light) 5.5 mass parts.
Then, in alcohol solvent, carry out using in 3 hours the wet-type ball mill of silicon nitride jar and abrading-ball to mix to the above-mentioned raw materials powder, filter, drying obtains mixed powder.The oxygen amount of using LECO corporate system oxygen analyzer to record mixed powder is 1.2 quality %.The 100g mixed powder is packed in the SP 1 system crucible of internal diameter 100mm, high 60mm, with the electric furnace of graphite heating in atmospheric nitrogen atmosphere in 1750 ℃ of heat treated of carrying out 12 hours.With the broken gained resultant of agate mortar, make it pass through the sieve of mesh 45 μ m.Utilize aforesaid operations, obtain synthetic powder as the fluor of alpha-siaion.
Be Ca the forming of alpha-siaion powder that is got by the assay-office value calculating of gained powder
0.48Eu
0.05Si
10.4Al
1.6O
0.5N
15.5, form X+Y=0.53, Y/ (X+Y)=0.09.By forming the oxygen amount of calculating is 1.36 quality %.The oxygen amount of using LECO corporate system oxygen analyzer to record the alpha-siaion fluor that is obtained is 1.40 quality %.In addition, with Hitachi system fluorescent spectrophotometer assay fluorescent characteristic, the spike length of the luminescent spectrum that records with excitation wavelength 400nm is 580nm.
As with the comparison of the characteristics of luminescence of other embodiment, comparative example; The long luminous intensity down of the spike of present embodiment is decided to be 100, the luminous intensity under relatively relatively the spike of the luminescent spectrum that records of the excitation wavelength with 400nm of other embodiment, comparative example is grown.
(embodiment 1-2)
Except with 2.8 mass parts sulfurated lime powder and 3.8 mass parts lime carbonate (the following CaCO that abbreviates as sometimes
3) sulfurated lime (the following CaS that abbreviates as sometimes) in the raw material powder of powder (Northeast chemistry system, special grade chemical) alternate embodiment 1-1 is beyond powder 5.5 mass parts, other and embodiment 1-1 are same, make the alpha-siaion fluor.In addition, at this moment CaS/CaCO
3Mol ratio be 1.The oxygen amount of raw materials mix powder is 3.4 quality %.
The composition of gained alpha-siaion powder is Ca
0.48Eu
0.05Si
10.4Al
1.6O
0.5N
15.5, form X+Y=0.53, Y/ (X+Y)=0.09.By forming the oxygen amount of calculating is 1.36 quality %.The oxygen amount of using LECO corporate system oxygen analyzer to record the alpha-siaion fluor that is obtained is 1.71 quality %.In addition, measure fluorescent characteristic equally with embodiment 1-1, if the luminous intensity of embodiment 1-1 is decided to be 100, then the relative value of luminous intensity is 85.
(comparative example 1-1)
Except with beyond sulfurated lime powder 5.5 mass parts in the raw material powder of 7.6 mass parts calcium carbonate powderss (Northeast chemistry system, special grade chemical) alternate embodiment 1-1, other and embodiment 1-1 are same, make the fluor of alpha-siaion.The oxygen amount of raw materials mix powder is 5.6 quality %.
The composition of gained alpha-siaion is Ca
0.48Eu
0.05Si
10.4Al
1.6O
0.5N
15.5, form X+Y=0.53, Y/ (X+Y)=0.09.By forming the oxygen amount of calculating is 1.36 quality %.The oxygen amount of using LECO corporate system oxygen analyzer to record the alpha-siaion fluor that is obtained is 1.80 quality %.In addition, the relative value of luminous intensity is 65.
(embodiment 1-3)
The alpha-siaion fluor of embodiment 1-2 gained is scattered in 48% hydrofluoric acid: 60% nitric acid: in the mixing solutions of zero(ppm) water=40: 10: 50 (volume %); Kept 2 hours in 50 ℃; Filter with distilled water wash, redispersion is in the vitriol oil: in the mixing solutions of zero(ppm) water=50: 50 (volume %), kept 2 hours in 90 ℃; Filter drying with distilled water wash.The oxygen amount of gained powder is 1.55 quality %.The relative value of luminous intensity is 90.
(comparative example 1-2, embodiment 1-4)
The proportioning of raw material powder is formed; Alpha-silicon nitride powders (electrochemical industry system; The 9FW level) 33.5 mass parts, aluminium nitride powder (ト Network ヤ マ system; The F level) 29.5 mass parts, europium sesquioxide powder (SHIN-ETSU HANTOTAI's chemical industry system, RU level) 2.5 mass parts and CaCl2 powder (with the pure industry system of light) 35.0 mass parts.
Then, in xylene solvent, carry out using in 3 hours the wet-type ball mill of silicon nitride jar and abrading-ball to mix to the above-mentioned raw materials powder, filter, drying obtains mixed powder.The 100g mixed powder is packed in the SP 1 system crucible of internal diameter 100mm, high 60mm, with the electric furnace of graphite heating in the atmospheric nitrogen atmosphere of pressure 0.9MPa in 1800 ℃ of heat treated of carrying out 12 hours.With the broken gained resultant of agate mortar, make its sieve that passes through mesh 45 μ m, obtain CaAlSiN
3: the Eu fluorophor powder.
The spike length of the luminescent spectrum of measuring with the excitation wavelength of 400nm is 650nm.Below embodiment and comparative example in, be 100 (comparative example 1-2) with the long luminous intensity down of the spike of present embodiment, relatively relatively with the luminous intensity under the spike length of the luminescent spectrum of the excitation wavelength mensuration of 400nm.
With 5.0g gained CaAlSiN
3: the Eu fluorophor powder is well-dispersed in and is dissolved with 0.5g magnesium ethylate (chemical formula: Mg (OC
2H
5)
2) Virahol 50ml.Fully dripping 15% ammonia soln 50ml in the dispersed with stirring liquid.Filtration washing gained slurry, drying in 1100 ℃ of calcinings of in nitrogen atmosphere, carrying out 1 hour, obtains the fluor of band Natural manganese dioxide tunicle.
The result who gets fluor with transmission electron microscope observation post is that the thickness of magnesium oxide films is about 60nm.The result who measures fluorescence spectrum is that luminescent spectrum intensity is 115 (embodiment 1-4).
In addition, the specific refractory power of using Otsuka Electronics Co., Ltd.'s system reflection beam splitting film thickness gauge to record the magnesium oxide films that obtains with above-mentioned same operation is 1.73.
(comparative example 1-3)
Except the amount of magnesium ethylate is the 1.0g, other and embodiment 1-4 are same, obtain the fluor of band Natural manganese dioxide tunicle.The result who gets fluor with transmission electron microscope observation post is that the thickness of magnesium oxide films is about 110nm.The mensuration result of fluorescence spectrum is, it is 96 that comparative example 1-2 is decided to be 100 o'clock luminescent spectrum intensity.
(embodiment 1-5)
Present embodiment is to have formed the example as the pellumina of transparent film on alpha-siaion fluor surface.In 0.1M boric acid 0.1M potassium chloride solution 50ml, add 0.1M aqueous sodium hydroxide solution 32ml, use distilled water diluting to be 100ml.In this aqueous solution, drop into the alpha-siaion fluorophor powder that 5.0g and embodiment 1-1 make equally, it is fully disperseed.
When adopting aqueous sodium hydroxide solution that the pH of aforementioned slurry is maintained 9.0～10.5 scope, drip 0.1M aluminum sulfate aqueous solution 10ml, obtain to have adhered to the fluorophor particle of aluminum hydroxide particle at the particle surface of slurry.Behind dry this fluorophor particle of washing, in air,, obtain the fluorophor powder that the surface is formed with alumina layer in 600 ℃ of preroasting that carry out 2 hours.The result who observes fluorophor particle with transmission electron microscope is that the thickness of alumina layer is about 50nm.Adopt the result of fluorescent spectrophotometer assay fluorescence spectrum to be, it is 108 that embodiment 1-1 is decided to be 100 o'clock luminous intensity relative value.
The specific refractory power that likewise records by the alumina layer that obtains with above-mentioned same operation with embodiment 1-4 is 1.70.
(embodiment 1-6)
Present embodiment is the example that has formed silicon dioxide film on the surface of alpha-siaion fluor.In Virahol 50ml that the oxonitride phosphor powder 5.0g that obtains with the same operation of embodiment 1-1 is well-dispersed in be dissolved with the 1.0g tetraethoxysilane and the mixed solution of zero(ppm) water 20ml.Fully dripping 15% ammonia soln 50ml in the dispersed with stirring liquid.Then, while stirred reflux 2 hours.The dry gained slurry of filtration washing in 600 ℃ of calcinings of in nitrogen atmosphere, carrying out 1 hour, obtains the fluor of band amorphous silicon di-oxide tunicle.
The result who gets fluor with transmission electron microscope observation post is that the thickness of silicon dioxide film is about 70nm.The result who measures fluorescence spectrum is, it is 113 that embodiment 1-1 is decided to be 100 o'clock luminescent spectrum intensity.
In addition, the specific refractory power by the silicon dioxide film that obtains with above-mentioned same operation that likewise records with embodiment 1-4 is 1.48.
(embodiment 1-7)
(silicone of SHIN-ETSU HANTOTAI system KBE402) adds in the 100g water oxonitride phosphor of the band alumina coating that the same operation of 10g and embodiment 1-5 is obtained together, in stirring, places an evening with the 1.0g epoxy silane coupling agent.Then; The oxonitride phosphor and the 5.0g epoxy resin (サ Application ユ レ Star Network system NLD-SL-2101) that have carried out handling through silane coupling agent behind the 0.5g filtration drying is mixing; On the blue led of emission wavelength 470nm, pour into; Vacuum outgas is heating and curing in 110 ℃, makes surface mounting LED.In this surface mounting LED, feed the electric current of 10mA, measure the luminescent spectrum of the light that sends, the intensity under the 580nm is decided to be 100.
(embodiment 1-8)
Adopt the oxonitride phosphor of the band silicon-dioxide tunicle that obtains with the same operation of embodiment 1-6, make surface mounting LED equally, measure luminescent spectrum with embodiment 1-7.
It is 95 that intensity under the 580nm is decided to be at 100 o'clock at embodiment 1-7.
(embodiment 1-9)
The epoxy resin of putting down in writing with epoxy resin (specific refractory power 1.6) the alternate embodiment 1-7 that has used fluorenes class epoxy compounds pours into; Behind the epoxy resin cure, (industry ocean, Tokyo is made of paper, INT350 at the fluorine-containing Liniment of surface coated; Specific refractory power 1.36), the fluoropolymer resin layer of about 1 μ m is set.It is 108 that luminous intensity under the 580nm of the luminescent spectrum of this luminous element is decided to be at 100 o'clock at embodiment 1-7.
(embodiment 1-10)
Nitride phosphor and 1.0g epoxy silane coupling agent that 10g is obtained with the same operation of embodiment 1-4 add in the 100ml zero(ppm) water, when stirring, place an evening.Then, filtration drying is measured luminescent spectrum, and consequently, it is 104 that the luminous intensity under the 650nm is decided to be at 100 o'clock at embodiment 1-4.
(comparative example 1-4)
Adopt obtain with the same operation of embodiment 1-1 not with the oxonitride phosphor of aluminum oxide epithelium, same with embodiment 1-7, make surface mounting LED.It is 75 that intensity under the 580nm of the luminescent spectrum of this LED is decided to be at 100 o'clock at embodiment 1-7.
(comparative example 1-5)
Except raw material powder is 51.0 mass parts alpha-silicon nitride powders, 30.0 mass parts aluminium nitride powders, 3.1 mass parts europium sesquioxide powder (SHIN-ETSU HANTOTAI's chemical industry systems; The RU level), beyond the proportioning of 17.0 mass parts sulfurated lime powder is formed; Other and embodiment 1-1 operate equally, make oxonitride phosphor.Result with X-ray diffraction device analysis gained powder is to measure a plurality of peaks that can't belong to alpha-siaion.If the analytical value according to metal ingredient is calculated alpha-siaion, then general formula is Ca
1.54Eu
0.10Si
7.2Al
4.8O
1.5N
14.5, form X+Y=1.64.It is 50 that the relative value of the luminous intensity under the 580nm is decided to be at 100 o'clock at embodiment 1-1.
(embodiment 1-11)
With silicon nitride system jar and abrading-ball; With alpha-silicon nitride powders (electrochemical industry system, 9FW level) 90.1 mass parts, aluminium nitride powder (ト Network ヤ マ system, F level) 9.0 mass parts and europium sesquioxide powder (SHIN-ETSU HANTOTAI's chemical industry system; The RU level) 0.9 mass parts was mixed in alcohol solvent 2 hours; Filter, drying obtains mixed powder.With the electric furnace of graphite heating in the nitrogen atmosphere of 0.9MPa in 1900 ℃ of heat treated of carrying out 12 hours, with the broken gained resultant of agate mortar, make it pass through the sieve of mesh 45 μ m.Utilize aforesaid operations, obtain synthetic powder as the fluor of β type Sialon.Adopt the result of Hitachi's fluorescent spectrophotometer assay fluorescent characteristic to be, the spike length of the luminescent spectrum that records with the excitation wavelength of 400nm is 540nm.
Likewise this powder is handled with embodiment 1-5, behind the tunicle of surface formation aluminum oxide, measured fluorescent characteristic.The luminous intensity of fluor powder that is not decided to be 100 o'clock band tunicle with the luminous intensity under the 540nm of the β type Sialon fluor powder of tunicle is 110.
(embodiment 2)
(embodiment 2-1)
As raw material powder; Use Deuki Kagaku Kogyo Co., Ltd's system alpha-form si nitride powder (NP200 level), ト Network ヤ マ Co., Ltd. system aluminium nitride powder (F level), Kanto Kagaku K. K.'s system calcium carbonate powders (special grade chemical) and the pure medicine of light Co., Ltd. system Calcium Fluoride (Fluorspan) powder (special grade chemical) and Shin-Etsu Chemial Co., Ltd's oxygenerating europium powder (RU level); Single-phase in order to form alpha-siaion after synthetic, prepare burden according to proportioning shown in the table 1.
Table 1
With the Virahol is solvent, adopts plastics system jar and silicon nitride system abrading-ball, raw materials mixed is carried out wet-type ball mill with powder mix, and utilizes rotatory evaporator to remove and desolvates, and obtains mixed powder.
Make volume density reach about 0.3g/cm in pack into the fine and close SP 1 matter crucible (Deuki Kagaku Kogyo Co., Ltd's system, N-1 level) of ten minutes of internal diameter 80mm, high 50mm of the about 50g of aforementioned mixed powder
3Give the lid of identical material on this crucible cover, in the electric furnace of graphite heating, in the atmospheric atmosphere of nitrogen, carry out heat treated.Top temperature and hold-time during heating are shown in table 1.Pass through the sieve of mesh 75 μ m with the broken gained test portion of agate mortar until it.
For the powder of above operation gained, utilize X-ray diffraction (XRD) method crystallization phases evaluation and utilize the quantitative evaluation of the crystallization phases that Rietveld analyzes, and the particle size distribution that utilizes the offspring of laser diffraction and scattering method.In addition; Utilize scanning electron microscope (SEM) to observe powder; By footpath value that is equivalent to circular diameter and the long-width ratio (major axis footpath/short shaft diameter) that gained is observed the determining image primary particle, calculate the footpath value distribution (the primary particle number of the footpath value that is equivalent to circular diameter of 3～10 μ m accounts for the ratio of whole primary particle numbers) and the mean aspect ratio that are equivalent to circular diameter.Primary particle to more than at least 500 is estimated.
Fluorescence spectrum when adopting spectrofluorophotometer mensuration blue light to excite (wavelength 460nm), it is long to obtain spectrographic peak intensity and spike.Because peak intensity changes because of determinator and condition,, carry out the embodiment of mensuration under the same terms and the comparison of comparative example so unit is an A.U..
Utilize the ICP spectroscopic analysis to measure the boron amount in the synthetic powder, utilize following method to measure the fluorine amount.The 0.5g test portion imported in 1200 ℃ the reaction tubes, utilizes 95～96 ℃ steam hydrolysis, the gas absorption that produces is gone into 0.05 quality %NaOH solution 10ml after, utilize ion-chromatographic determination fluorine amount.Above-mentioned evaluation result is shown in table 2.
Table 2
The result of XRD determining is, synthetic powder is that alpha-siaion is single-phase, and median size (offspring) is 10 μ m.The result that SEM observes is to be the approximate a plurality of primary particle sintering particle shape together that waits the axle shape of micron-scale.The footpath value that is equivalent to circular diameter in the primary particle is that the ratio of the particle of 3～10 μ m is 92%, and mean aspect ratio is 1.5.Boron content is 590ppm, and fluorine content is 40ppm.If the blue light by wavelength 460nm excites, then send the yellow orange coloured light of the long 587nm of spike.
(embodiment 2-2,2-3)
According to method and the order same, carry out embodiment 2-2 and 2-3 with embodiment 2-1.The raw material powder proportioning is formed and synthesis condition is shown in table 1, and the evaluation result of synthetics is shown in table 2.
(comparative example 2-1～2-3)
Method and order according to same with embodiment 2-1 compare routine 2-1～2-3.But, among the comparative example 2-2, except the raw material powder of embodiment 2-1, also added with respect to all raw material powders be 1 quality % with the pure medicine of light Co., Ltd. oxygenerating boron powder.
Among the comparative example 2-1, the size of the primary particle of formation synthetic powder is in the relative broad range of inferior μ m～number μ m, and the footpath value that is equivalent to circular diameter is that the ratio of particle in primary particle of 3～10 μ m is 40%.The spike of luminescent spectrum is long for 590nm, and is approaching with embodiment 2-1, but luminous intensity has only about half.Among the comparative example 2-2, boron content is 4520ppm, and the spike of luminescent spectrum is long to be 588nm, and luminous intensity is about 70% of embodiment 2-1.Among the comparative example 2-3, fluorine content is 1200ppm, and the X-ray diffraction result is to confirm beyond the alpha-siaion to also have the oxygen fluoride of unreacted silicon nitride, aluminium nitride AlN and europium to exist.The SEM observations is, primary particle is made up of with most submicron particles the particle of the micron-scale of minority, and the footpath value that is equivalent to circular diameter is that the ratio of the primary particle of 3～10 μ m is 20%, and is lower.Luminous intensity is about 60% of embodiment 2-1.
(embodiment 2-4)
(silicone Co., Ltd. of SHIN-ETSU HANTOTAI system KBE402) adds in the 100g water together, when stirring, places an evening for alpha-siaion fluor that 10g embodiment 2-1 is obtained and 1.0g epoxy silane coupling agent.Then; The alpha-siaion fluor that has carried out handling through silane coupling agent behind an amount of filtration drying is mixing with 10g epoxy resin (サ Application ユ レ Star Network Co., Ltd. makes NLD-SL-2101); On the blue led of emission wavelength 460nm, pour into; Vacuum outgas is heating and curing aforementioned resin in 110 ℃, makes surface mounting LED.
Shown in Figure 4 is the simple knot composition of White LED (aforementioned surfaces mount type LED).That is White LED, shown in Figure 4 constitutes through following operation.Promptly; Make blue led sheet 11 and electroconductibility terminal 16 be connected and be arranged at the bottom of container 15; After blue led sheet 11 being connected in other electroconductibility terminal 17 with lead 3; The mixing thing of perfusion alpha-siaion fluor 12 and sealing resin (epoxy resin) 14 on blue led sheet 11, the sealing resin 14 that is heating and curing makes White LED.In this surface mounting LED, feed the electric current of 10mA, measure the luminescent spectrum of the light that sends.The characteristics of luminescence and average colour developing evaluation of estimate are shown in table 3.Obtain the lighting fixtures of the correlated(color)temperature low (electricbulb look) under the high brightness.
(embodiment 2-5)
As fluor; The fluor of an amount of mix embodiment 2-1 and excite and send these 2 kinds of fluor of β type Sialon fluor that mixed Eu of the long yellow-green light for 535nm of spike through wavelength 460nm; Method according to same with embodiment 2-4 makes surface mounting LED.The characteristics of luminescence and average colour developing are estimated number and are shown in table 3.Obtain for daylight, color developing is higher than the lighting fixtures of embodiment 2-4.
Table 3
(embodiment 3)
(embodiment 3-1)
As raw material powder; Use Deuki Kagaku Kogyo Co., Ltd's system alpha-form si nitride powder (9FW level), ト Network ヤ マ Co., Ltd. system aluminium nitride powder (F level), Kanto Kagaku K. K.'s system calcium carbonate powders (special grade chemical) and the pure medicine of light Co., Ltd. system Calcium Fluoride (Fluorspan) powder (special grade chemical) and Shin-Etsu Chemial Co., Ltd's oxygenerating europium powder (RU level), mix (with reference to table 4) by forming the monophasic proportioning of alpha-siaion after synthetic.
Table 4
In alcohol solvent, the above-mentioned raw materials powder is carried out the wet-type ball mill mixing of 3 hours use silicon nitride jar and abrading-ball, with filtrations such as rotatory evaporators, drying obtains mixed powder.
The 100g mixed powder is packed in the SP 1 system crucible of internal diameter 100mm, high 85mm, in the electric furnace of graphite heating, in atmospheric nitrogen atmosphere, carry out 12 hours heat treated with 1700 ℃ temperature.With the broken gained resultant of agate mortar, make resultant pass through the sieve of mesh 45 μ m.Obtain synthetic powder through aforesaid operations.
The result of the XRD determining of gained powder (using マ Star Network サ イ エ Application ス corporate system MXP3 as tester) is that synthetic powder is that alpha-siaion is single-phase.
In addition, adopt the Ha イ テ of Hitachi Network ノ ロ ジ-ズ Co., Ltd. system spectrofluorophotometer (F4500), the fluorescence spectrum when the mensuration blue light excites (wavelength 460nm), it is long to obtain spectrographic peak intensity and spike.Because peak intensity changes because of determinator and condition,, carry out the embodiment of mensuration under the same terms and the comparison of comparative example so unit is arbitrarily.Above-mentioned evaluation result is shown in table 5.
Table 5
Implement to adopt electrical industry system fluorescent X-ray of science (ZSX100e) and LECO corporate system O/N to analyze the compositional analysis of (TC-436), trying to achieve Eu content is 0.175at%.
Implement the particle size distribution (adopting コ-Le タ-corporate system LS230) of the particle of employing laser diffraction and scattering method as determining instrument.Median size (offspring) is 11.8 μ m.
Adopt the ICP luminescence analysis to carry out the impurity analysis of synthetic powder, the total amount of Fe, Co, Ni is 300ppm.
The measuring method that the lattice parameter that adopts the XRD diffraction is measured does not have special qualification.For example, sample and internal standard substance are mixed together pulverizing, carry out method for measuring with the X-ray diffraction device.Internal standard substance is generally aluminum oxide, Natural manganese dioxide, silicon-dioxide etc., preferably with the nonoverlapping compound in the peak of sample.After X-ray diffraction was measured, the analysis software of employing lattice parameter carried out the precise treatment of lattice parameter.As analysis software, the リ ガ Network corporate system of can giving an example JADE etc.
Utilize the result of the lattice parameter mensuration of XRD diffraction to be, lattice parameter a is 0.781nm, and lattice parameter c is 0.567nm.It is benchmark that lattice parameter is measured with JIS K0131.
(embodiment 3-2～3-5)
According to method and the order same with embodiment 3-1, mixing raw material makes the m value of gained alpha-siaion reach for 1.25～2 (with reference to table 4).Mixed raw material is carried out the processing same with embodiment 3-1, obtain various synthetic powders.
The evaluation result of these synthetic powders is shown in table 5.About the characteristics of luminescence, embodiment 3-4 culminates, and peak intensity is the highest.During lattice parameter was measured, it is big that the numerical value of lattice parameter a, c all becomes.
(comparative example 3-1～3-3)
According to the method and order mixing raw material same with embodiment 3-1; Make the m value among comparative example 3-1, the 3-2 be respectively 0.8 and 2.25, the m value among the comparative example 3-3 is 1.75, and Eu content is more than 0.35at%; Handle equally with embodiment 3-1, obtain synthetic powder.
After carrying out pulverizing in 1 minute with the synthetic powder that has used iron jar vibrating mill that comparative example 3-2 is obtained,, make resultant pass through the sieve of mesh 45 μ m with the agate mortar fragmentation.
These synthetic powders are estimated, and the m value of comparative example 3-1 is 0.8, compares with the m value 1.0 of embodiment 3-1; The characteristics of luminescence descends, and the lattice parameter value also diminishes simultaneously, and the m value of comparative example 3-2 is 2.25; Compare with the m value 2 of embodiment 3-5, the characteristics of luminescence descends, but the lattice parameter value reaches maximum.
In addition, the characteristics of luminescence of the synthetic powder of comparative example 3-3 descends, but the lattice parameter value is identical with embodiment 3-4.
The possibility of utilizing on the industry
Fluor of the present invention has the scope that excites of ultraviolet ray to the broad of visible light; Send visible light; So can be used for luminous element; White LED particularly is positioned at 100～500nm, better is to be positioned at the ultraviolet ray of 240～480nm or the excitation light source combination of visible light that through the maximum strength with emission wavelength the fluor that can be used as luminous element or lighting fixtures uses.
Here, quoted of the announcement of the full content of Japanese patent application 2005-146917 number of filing an application on May 19th, Japanese patent application 2005-118271 number 1 of on April 15th, Japanese patent application 2005-052270 number 1 of filing an application on February 28th, 2005 and Japanese patent application 2005-304268 number specification sheets, claims and the summary of filing an application on October 19th, 2005 as specification sheets of the present invention.
Claims (6)
1. powdery fluorescent body is characterized in that, by general formula: (M1)
X(M2)
Y(Si)
12-(m+n)(Al)
M+n(O)
n(N)
16-nThe alpha-siaion of expression forms, and in the formula, M1 is selected from Li, Mg, Ca, Y and except that the element more than a kind of La and the lanthanum family metal the Ce; M2 is the element more than a kind that is selected from Ce, Pr, Eu, Tb, Yb and Er; 0.3≤X+Y≤1.5,0＜Y≤0.7,0.6≤m≤3.0; 0≤n≤1.5, X+Y=m/2; Oxygen level in the powder of aforementioned alpha-siaion than calculate based on aforementioned formula the big and maximum 0.4 quality % that is no more than this value of value; Aforementioned formula be (Ca, Eu)
M/2(Si)
12-(m+n)(Al)
M+n(O)
n(N)
16-n, Eu content is 0.1～0.35at%, and lattice parameter a is 0.780～0.790nm, and lattice parameter c is 0.560～0.580nm.
2. fluor as claimed in claim 1; It is characterized in that at least a portion surface of the powder particle of Sialon has transparent film, the refractive index n of this transparent film is 1.2～2.5; Be formed with the transparent film of thick (10～180)/n; Thickness unit is a nanometer, and n is the specific refractory power of transparent film, and its value is 1.2～2.5.
3. fluor as claimed in claim 1 is characterized in that, contains the fluorine of 5～300ppm.
4. fluor as claimed in claim 1 is characterized in that, contains the boron of 10～3000ppm.
5. fluor as claimed in claim 1 is characterized in that, the median size of the powder particle of aforementioned alpha-siaion is 1～20 μ m.
6. fluor as claimed in claim 1 is characterized in that, the element impurity in addition that constitutes aforementioned alpha-siaion is below 1 quality %.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
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| JP2005052270 | 2005-02-28 | ||
| JP052270/2005 | 2005-02-28 | ||
| JP118271/2005 | 2005-04-15 | ||
| JP2005118271A JP4512869B2 (en) | 2005-02-28 | 2005-04-15 | Phosphor, method for producing the same, and light emitting device using the same |
| JP2005146917A JP4538739B2 (en) | 2005-05-19 | 2005-05-19 | α-type sialon phosphor and lighting equipment using the same |
| JP146917/2005 | 2005-05-19 | ||
| JP2005304268A JP4364189B2 (en) | 2005-10-19 | 2005-10-19 | α-type sialon, phosphor comprising α-type sialon, and lighting apparatus using the same |
| JP304268/2005 | 2005-10-19 | ||
| PCT/JP2006/303730 WO2006093135A1 (en) | 2005-02-28 | 2006-02-28 | Fluorescent substance and process for producing the same, and luminescent element using the same |
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| CN200910208339A Division CN101712868A (en) | 2005-02-28 | 2006-02-28 | Fluorescent substance and process for producing the same, and luminescent element using the same |
| CN200910208341A Division CN101712870A (en) | 2005-02-28 | 2006-02-28 | Fluorescent substance and process for producing the same, and luminescent element using the same |
| CN2009102083385A Division CN101982891A (en) | 2005-02-28 | 2006-02-28 | Fluorescent substance and process for producing the same, and luminescent element using the same |
| CN2011104607734A Division CN102585810A (en) | 2005-02-28 | 2006-02-28 | Fluorescent substance and process for producing the same, and luminescent element using the same |
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| JP2020066677A (en) * | 2018-10-24 | 2020-04-30 | デンカ株式会社 | Surface coat phosphor particle, composite, light-emitting device, and production method of surface coat phosphor particle |
| JP6787417B2 (en) * | 2019-02-08 | 2020-11-18 | 日亜化学工業株式会社 | Nitride phosphor manufacturing method and nitride phosphor |
| JP6667026B1 (en) * | 2019-03-29 | 2020-03-18 | デンカ株式会社 | Phosphor particles, composite, light emitting device, and method for producing phosphor particles |
| KR20220049533A (en) * | 2019-08-20 | 2022-04-21 | 덴카 주식회사 | β-Sialon phosphor and light emitting device |
| US11453821B2 (en) * | 2019-12-05 | 2022-09-27 | Lumileds Llc | Narrow band emitting SiAlON phosphor |
| CN112573492B (en) * | 2020-11-24 | 2024-04-26 | 兰州冉华实德新材料有限公司 | Strontium europium nitride solid solution powder and preparation method thereof |
| CN114058202A (en) * | 2021-12-02 | 2022-02-18 | 兰州大学 | Orange-yellow fluorescence-enhanced ceramic simulating coating based on alpha-SiAlON: Eu and preparation method thereof |
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| JP2004161807A (en) * | 2002-11-08 | 2004-06-10 | Nichia Chem Ind Ltd | Nitride phosphor and light-emitting device |
| US20040155225A1 (en) * | 2003-02-06 | 2004-08-12 | Ube Industries, Ltd., A Corporation Of Japan | Sialon-based oxynitride phosphor, process for its production, and use thereof |
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| JPH11214752A (en) * | 1998-01-21 | 1999-08-06 | Matsushita Electron Corp | Semiconductor light-emitting device |
| DE10133352A1 (en) * | 2001-07-16 | 2003-02-06 | Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh | Lighting unit with at least one LED as a light source |
| JP4207489B2 (en) * | 2002-08-06 | 2009-01-14 | 株式会社豊田中央研究所 | α-sialon phosphor |
| JP4052136B2 (en) * | 2003-02-06 | 2008-02-27 | 宇部興産株式会社 | Sialon oxynitride phosphor and method for producing the same |
| JP4661032B2 (en) * | 2003-06-26 | 2011-03-30 | 日亜化学工業株式会社 | Light emitting device and manufacturing method thereof |
| JP4165318B2 (en) * | 2003-07-16 | 2008-10-15 | 宇部興産株式会社 | Sialon phosphor and method for producing the same |
| JP4512869B2 (en) * | 2005-02-28 | 2010-07-28 | 電気化学工業株式会社 | Phosphor, method for producing the same, and light emitting device using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004161807A (en) * | 2002-11-08 | 2004-06-10 | Nichia Chem Ind Ltd | Nitride phosphor and light-emitting device |
| US20040155225A1 (en) * | 2003-02-06 | 2004-08-12 | Ube Industries, Ltd., A Corporation Of Japan | Sialon-based oxynitride phosphor, process for its production, and use thereof |
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| CN101128564A (en) | 2008-02-20 |
| JP5193967B2 (en) | 2013-05-08 |
| JP2009293035A (en) | 2009-12-17 |
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