CN105176527A - Fluorophor and light-emitting device - Google Patents
Fluorophor and light-emitting device Download PDFInfo
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- CN105176527A CN105176527A CN201510704966.8A CN201510704966A CN105176527A CN 105176527 A CN105176527 A CN 105176527A CN 201510704966 A CN201510704966 A CN 201510704966A CN 105176527 A CN105176527 A CN 105176527A
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Abstract
The invention provides a fluorophor. The fluorophor is prepared from compositions with the composition formula as indicated in a following formula (I), wherein M represents a cluster constituted by elements selected from magnesium, barium, beryllium and zinc, A represents a cluster constituted by elements selected from aluminum, gallium, indium, scandium, yttrium, lanthanum, gadolinium and lutetium, B represents a cluster constituted by elements selected from silicon, germanium, tin, titanium, zirconium and hafnium, Z represents a cluster constituted by elements selected from europium and cerium, p is greater than 0 and less than 1, q is greater than 0 and less than 1, m is greater than or equal to 0 and less than 1, t is greater than or equal to 1 and less than or equal to 0.3, r is greater than or equal to 0.00001 and less than or equal to 0.1, a is equal to 1.0, b is greater than or equal to 8 and less than or equal to 1.2, n is greater than or equal to 2.7 and less than or equal to 3.1, the dissolution content of normalized strontium of the fluorophor ranges from 1 ppm to 20 ppm, and the fluorophor which reaches the high illuminance within the wavelength range from 600 nm to 680 nm is obtained. In addition, the invention further provides a light-emitting device having high illuminance. The formula (I) is Ca<p>Sr<q>M<m>-A<a>-B<b>-O<t>-N<m>: Z<r>.
Description
The application is a divisional application, and the application number of corresponding female case is 201010540094.3, and the applying date is on October 27th, 2010, and denomination of invention is " fluor and light-emitting device ", and application people is Qimei Industry Co., Ltd..
Technical field
The present invention relates to the nitride phosphor used in the lighting units such as indicating meter, liquid crystal backlight, luminescent lamp, photodiode, especially relate to the light-emitting device that this nitride phosphor forms and uses this fluor.
Background technology
In recent years, the light-emitting device of semiconductor light emitting is used to be widely used, particularly photodiode is successfully developed, the luminaire such as CCFL, incandescent light that this light-emitting device is more known, have that luminous efficiency is high, volume is little, the advantage such as low consumption electric power and low cost, therefore can be used as various light source to use.And semiconductor light-emitting apparatus comprises semiconductor luminous assembly and fluor, the light that fluor Absorbable rod conversion semiconductor luminescence component send, the light that the light sent by semiconductor luminous assembly and Phosphor-conversion send is used in combination.This kind of light-emitting device can be used as the various field such as luminescent lamp, car lighting, indicating meter, LCD backlight display and uses, and wherein, uses the most extensive with white light emitting device.Existing white light emitting device system employing cerium is the YAG fluor (Y in active centre
3al
5o
12: Ce) and the semiconductor luminous assembly that collocation sends blue light formed.But, use Y
3al
5o
12: Ce fluor is also arranged in pairs or groups the mixed light that the semiconductor luminous assembly that sends blue light sends, and its tristimulus coordinates is positioned at tristimulus coordinates and the Y of the semiconductor luminous assembly sending blue light
3al
5o
12: the tristimulus coordinates of Ce fluor connects online, and thus, the mixed light sent is the white light lacking red light, and color rendering and colorimetric purity are obviously not enough.In addition, Y
3al
5o
12: the better excitation spectrum region of Ce and the light-emitting zone of semiconductor luminous assembly are also inconsistent, and therefore, the efficiency of conversion of exciting light is not good, not easily obtains the white light source of high briliancy.For solving this kind of phenomenon that tone is bad and glorious degrees is low, active development will be mixed into the fluor that can send ruddiness in YAG:Ce fluor in recent years, and improvement can send the quality of the fluor of ruddiness, to improve glorious degrees.
But absorb blue light and then send the fluor of red light or partially red light comparatively rare, the development research of current industry is based on nitride, oxynitride fluor.There will be a known and use the Sr that europium (Eu) is active centre
2si
5n
8: Eu fluor, CaAlSiN
3: Eu fluor and general expression are M
gsi
12-(m+n)al
m+no
nn
16-n: the Sialon phosphor of Eu.But, Sr
2si
5n
8: Eu fluor due to the thermotolerance of crystal own not good, have the shortcoming that briliancy and color rendering decline during life-time service; Although Sialon phosphor itself is without endurance issues, light-emitting phosphor briliancy is obviously not enough, and business is not popularized on using.CaAlSiN
3: although Eu fluor has preferably weather resistance, and is good briliancy compared with Sialon phosphor, and industry still expects the glorious degrees that further can improve fluor, can have higher luminous efficiency to make light-emitting device.
Summary of the invention
In view of the above problems, therefore the object of the present invention is to provide the fluorescent material of a high briliancy, can be used for arranging in pairs or groups semiconductor luminous assembly and making the light-emitting device of a high briliancy.
Therefore, contriver etc. are for the result of the problems referred to above point carefulness research, and particularly novel red-emitting phosphors carries out research and probe.Contriver with keen determination result of study learns, Ca
psr
qalSiN
3: in Eu (p > 0, q > 0) fluor, the nitridation of raw material strontium nitride has significant impact to glorious degrees.And according to contriver's result of study, condition during strontium nitride synthesis can affect synthesized fluor regular strontium stripping content, and find that regular strontium stripping content is for Ca
psr
qalSiN
3: the glorious degrees of Eu (p > 0, q > 0) fluor has to be affected especially significantly.Therefore the present invention's spirit is be controlled in certain limit by the regular strontium stripping content of fluor, thus reaches the luminosity of high briliancy, and is combined as light-emitting device by this fluor semiconductor luminous assembly of arranging in pairs or groups.
For meeting aforementioned expection object, system of the present invention provides a kind of fluor, and comprising composition formula is Ca
psr
qm
m-A
a-B
b-O
t-N
n: Z
rconstituent, wherein, the group that M forms for being selected from magnesium, barium, beryllium and zinc, the group that A forms for being selected from aluminium, gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating, the group that B forms for being selected from silicon, germanium, tin, titanium, zirconium and hafnium, the group that Z element forms for being selected from europium and cerium, 0 < p < 1,0 < q < 1,0≤m < 1,0≤t≤0.3,0.00001≤r≤0.1, a=1,0.8≤b≤1.2,2.7≤n≤3.1; And the regular strontium stripping content of this fluor is 1 ~ 20ppm; Aforementioned regular strontium stripping content system measures with following method: the fluor getting conductance 200 below μ s/cm is washed to conductance 200 below μ s/cm, pure water is added than the part by weight that pure water is 1:100 according to fluor, form the mixing solutions of fluor and water, this container of sealing after mixing, after heating in 80 DEG C, 40 hours, cool this mixing solutions to room temperature, get the aqueous phase of this mixing solutions, measure its regular strontium stripping content.
The present invention also provides following fluor:
Above-mentioned fluor, wherein, regular strontium stripping content is 3 ~ 17ppm/ mole.
Above-mentioned fluor, wherein, is preferably 0.05≤p≤0.9,0.1≤q≤0.95.
Above-mentioned fluor, wherein:
The group that M forms for being selected from magnesium and zinc;
The group that A forms for being selected from aluminium and gallium;
The group that B forms for being selected from silicon and germanium.
Above-mentioned fluor, wherein, when being preferably use 455nm light source irradiation, light-emitting phosphor wavelength is 600 ~ 680nm, and the CIE1931 tristimulus coordinates (x, y) of its luminous tone is, 0.45≤x≤0.72,0.2≤y≤0.5.
Above-mentioned fluor, when being more preferred from use 455nm light source irradiation, the cie color coordinate (x, y) of light-emitting phosphor tone is 0.6≤x≤0.7,0.3≤y≤0.4.
The present invention also provides a kind of light-emitting device, comprises:
Semiconductor luminescence component; And
Foregoing fluor, wherein, the optical excitation that this fluor can send by this semiconductor luminous assembly, and conversion sends the light being different from exciting light.
Foregoing light-emitting device, wherein, this semiconductor luminous assembly can send the light of 300 ~ 550nm wavelength.
The present invention mainly by controlling the regular strontium stripping content of fluor in certain limit, thus obtains the fluor of high briliancy.The present invention also by this fluor collocation semiconductor luminous assembly, and can obtain the light-emitting device of high briliancy.
Accompanying drawing explanation
Fig. 1 is the using state schematic diagram of briliancy measuring apparatus;
Fig. 2 is the skeleton view of light emitting device embodiment of the present invention.
Nomenclature
11 casings; 12 sample cells; 13 light sources; 14 photoconduction skirts; 15 speculums; 16 brightness photometers;
21 semiconductor luminous assemblies; 211 pedestals; 212 loading ends; 213 LED crystal particle;
214 wires; 215 wires; 22 fluorescent layers; 221 fluor; 23 encapsulated layers.
Embodiment
In order to effect of the present invention is described, spy illustrates with the following example, and it is only better possible embodiments of the present invention, and is not used to limit the present invention, therefore all modifications of doing according to scope of the present invention or change, all ought to be included in this case patent application the scope of the claims.
A kind of fluor of the present invention, comprising composition formula is Ca
psr
qm
m-A
a-B
b-O
t-N
n: Z
rconstituent, wherein, the group that M forms for being selected from magnesium, barium, beryllium and zinc, the group that A forms for being selected from aluminium, gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating, the group that B forms for being selected from silicon, germanium, tin, titanium, zirconium and hafnium, the group that Z element forms for being selected from europium and cerium, 0 < p < 1,0 < q < 1,0≤m < 1,0≤t≤0.3,0.00001≤r≤0.1, a=1,0.8≤b≤1.2,2.7≤n≤3.1; And the regular strontium stripping content of this fluor is 1 ~ 20ppm; Aforementioned regular strontium stripping content measures by the following method: the fluor getting conductance 200 below μ s/cm, pure water is added than the part by weight that pure water is 1:100 according to fluor, form the mixing solutions of fluor and water, this container of sealing after mixing, after heating in 80 DEG C, 40 hours, cool this mixing solutions to room temperature, get the aqueous phase of this mixing solutions, measure its regular strontium stripping content.
In aforementioned phosphors, the group that M forms for being selected from magnesium, barium, beryllium and zinc.The group that A forms for being selected from aluminium, gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating, such as, A can be separately aluminium element, also can be the mixture of the element such as aluminium, gallium.The group that B forms for being selected from silicon, germanium, tin, titanium, zirconium and hafnium, such as, B can be separately element silicon, also can be the mixture of the element such as silicon, germanium.The group that Z element forms for being selected from europium and cerium.Ca is calcium constituent, Sr is strontium element, O is oxygen element, N is nitrogen element.
Composition formula Ca
psr
qm
m-A
a-B
b-O
t-N
n: Z
rin, 0 < p < 1,0 < q < 1,0≤m < 1.
Wherein:
M is preferably 0≤m < 1, is more preferred from 0≤m≤0.1, and the best is 0≤m≤0.05.
a＝1。More preferably, when A is aluminium, glorious degrees is better.
B is preferably 0.8≤b≤1.2, is more preferred from 0.9≤a≤1.1.More preferably, when B is silicon, and when b value is 1, glorious degrees is better.
T is preferably 0≤t≤0.3, is more preferred from 0≤t≤0.1.
N is preferably 2.7≤n≤3.1, is more preferred from 2.8≤n≤3.1.
When m, a, b, t are in aforementioned scope of the present invention, glorious degrees is good.
R is preferably 0.00001≤r≤0.1.More preferably, when Z element is europium (Eu), glorious degrees is better.When r value is less than 0.00001, because the Eu quantity of luminescence center is few, therefore glorious degrees reduces; When r value is greater than 0.1, cause the phenomenon of concentration delustring due to the interatomic mutual interference of Eu, so that briliancy lowers.More preferably, when r value is 0.002 ~ 0.03, glorious degrees is better.
In addition, in fluor composition of the present invention, simultaneously containing calcium, strontium element, wherein, 0 < p < 1,0 < q < 1, aforementioned p value is better with 0.02 ~ 0.95, q value is better with 0.05 ~ 0.98, is more preferred from p=0.05 ~ 0.9, q=0.1 ~ 0.95.In the relativeness of calcium, strontium element, be preferably 0 < (p+q) < 1, (p/q)=0.1 ~ 10.Particularly the regular strontium stripping content of fluor of the present invention is 1 ~ 20ppm, finds that the light-emitting phosphor briliancy meeting this scope can obviously promote.
When measuring regular strontium stripping content, get the fluor of conductance 200 below μ s/cm, refer to that fluor detects via following conductance detection method, its conductance is 200 below μ s/cm.Fluor conductance detection method is as follows: get the fluor that pure water (conductance is less than 1 μ s/cm) and fluor be mixed to form fluor content 1 % by weight and detect mixed solution, this detection mixed solution stirs 30 minutes under 80 DEG C of water-baths, then leave standstill to room temperature, get the upper strata settled solution detecting mixed solution and carry out conductance measurement.If the zeta potential measured is 200 below μ s/cm, then this fluor is the fluor of conductance 200 below μ s/cm; If observed value is 200 more than μ s/cm, then first carry out fluor cleanup acid treatment until zeta potential is 200 below μ s/cm.Fluor cleanup acid treatment method is as follows: salpeter solution and the fluor of getting 0.5 % by weight are mixed to form the fluor pickling mixed solution of fluor content 1 % by weight, this pickling mixed solution under room temperature via ultrasonic vibrating 30 minutes, fluor after filtering adds the pure water of 100 times, in 80 DEG C of water-bath lower seal stirring and washing 30 minutes, row filters again, aforementioned pure water cleaning repeats four times again with the step of filtering, and finally filters the fluor obtained and measures zeta potential according to above-mentioned conductance detection method again.
The fluor of conductance 200 below μ s/cm and pure water form the mixing solutions of fluor and water according to the weight ratio of 1:100, and this mixing solutions uses container to seal, and prevent moisture content in heat-processed to scatter and disappear, and heating unit is baking oven.After heating in 80 DEG C, 40 hours, cool the mixing solutions of this fluor and water to room temperature.
Normalization (normalize) strontium stripping content refers to that the content of strontium measured in the aqueous phase of mixing solutions after foregoing routine is divided by this composition formula Ca
psr
qm
m-A
a-B
b-O
t-N
n: Z
rin q value after the result that obtains.
The better system of fluor of the present invention is when using 455nm this fluor of light source irradiation, this fluor is stimulated and the luminous predominant wavelength of luminescence is 600 ~ 680nm, the CIE1931 tristimulus coordinates (x, y) of its luminous tone is 0.45≤x≤0.72,0.2≤y≤0.5.Luminous predominant wavelength refers to the wavelength that luminous intensity is maximum.
One of the invention process form is 0 < p < 1,0 < q < 1,0≤m≤0.05,0≤t≤0.3,0.00001≤r≤0.1, p+q+m+r=[1/ (1+t)], a=1, b=(1-t)/(1+t), n=(3-t)/(1+t); And the regular strontium stripping content of this fluor is 1 ~ 20ppm.And by the consideration of glorious degrees, fluor consist of Ca
psr
qm
m-A
a-B
b-O
t-N
n: Z
rand can single-phase form exist, but, because of factor impacts such as pollution, volatility of raw material in impurity, treating processes in the interpolation of fusing assistant, raw material in building-up process, other crystallization phasess or noncrystalline phase (amorphousphase) may be there is simultaneously, as long as under the prerequisite not affecting glorious degrees, still spirit according to the invention.
Implement the compositional analysis result of this example fluor, find each element m, a, b, t, n value calculated from compositional analysis result, have deviation a little with compared to m, a, b, t, n value calculated from used material allocation ratio.This phenomenon can think have a small amount of feed material degradation or evaporation in burning till, or caused because of analytical error.Be the deviation of t value especially, can think such as: be just contained in the oxygen in raw material from the outset, or the oxygen that adhering on surface, or when raw material weighing, time of mixing and when burning till, the oxygen be mixed into because of raw material surface oxidation, and after burning till, be adsorbed in phosphor surface moisture or oxygen etc. caused.In addition, when burning till in the environment containing nitrogen and/or ammonia, the oxygen when burning till in raw material also may depart from and replace by nitrogen, judge that some deviations will occur for t, n.
When fluor of the present invention manufactures, the raw material of strontium element uses nitride better.The manufacture method of nitride is, selects required divalent metal to burn till under the atmosphere of high-purity nitrogen.Firing atmosphere is good with high-purity nitrogen, and high-purity nitrogen mean that purity reaches more than 99.99%.And nitrogen flow rate must control the state into high flow rate, such as 70 ~ 90 liters/min is good, and 80 ~ 90 liters/min better.Too high or too low nitrogen flow rate all cannot synthesize suitable strontium nitride, has regular strontium stripping content in specified range of the present invention to make the fluor of follow-up synthesis.Firing temperature is preferably between 600 ~ 1000 DEG C, is more preferred between 700 ~ 900 DEG C.Firing temperature is less than 600 DEG C or all cannot obtain required strontium nitride more than 1000 DEG C.Firing time was preferably between 3 ~ 24 hours, was more preferred between 5 ~ 24 hours.Firing time is long or very few, all cannot obtain required suitable nitride.And the heat-up rate burnt till needs special control, namely time lower than this melting point metal less than 150 DEG C, heat-up rate needs comparatively slow, the heat-up rate of such as 5 DEG C/minute is good, the heat-up rate of 3 DEG C/minute is better, when reason is for carrying out nitride metal reaction, if heat-up rate is too fast near melting point metal, then easily there is surface metal rapid melting and carry out nitrogenizing reaction, and required suitable strontium nitride cannot be obtained.The container burnt till uses BN (boron nitride) crucible, silicon nitride crucible is good, wherein best with BN (boron nitride) crucible.The nitrogenizing reaction formula of strontium is as follows:
3Sr+N
2→Sr
3N
2
When fluor of the present invention manufactures, the raw material of element A (+III valency), B element (+IV valency) can use respective nitride, oxide compound, any type of compound.Such as, can nitride (AN)/oxide compound (A of element A used in combination
2o
3) or element A, B element nitride (AN, B
3n
4).So-called " oxide compound ", be not limited to only be oxidized the compound closed, other can decompose as carbonate, oxalate etc. in burning till, and have the scope that the compound containing this element and oxygen forming in fact oxide compound also belongs to aforementioned " oxide compound "; The situation of nitride, also refers to have this element and nitrogen compound.
Phosphor raw material of the present invention can be various multi-form precursor, for simplicity, illustrates below using nitride raw material as embodiment.Though each nitride raw material of element A, B element can be marketable material, but because purity is more high better, the raw material therefore preferably preparing more than 3N is good.The particle diameter of each raw particles, from the viewpoint promoting reaction, is preferably micropartical, but with the particle diameter of raw material, the difference of shape, obtain the particle diameter of fluor, shape also will change to some extent.As long as therefore coordinate final institute to obtain the particle diameter of fluor requirement, the nitride raw material that preparation has approximate particle diameter just can.The raw material of Eu element is good with commercially available oxide compound, nitride raw material or metallic monomer, and purity is more high better, preferably prepares more than 3N, is good especially with the raw material of more than 4N.
The hybrid mode of raw material, can be drying process, damp process.The numerous embodiments such as such as dry type ball milled or the wet ball-milling method adding liquid, are not limited to single mode.Take, mixed C a
3n
2, Sr
3n
2time, because these compounds are more oxidized, it is comparatively suitable thus to carry out operating in the glove box under inert environment.In addition, because the nitride of each starting material element is easier to the impact by moisture, thus non-active gas preferably uses the gas through fully removing moisture.Mixing device can use usual the used device such as ball mill or mortar.
Can weigh according to certain proportion when preparing fluor, mix each raw material, insert in crucible, insert high temperature kiln roasting together.The stove used when burning till, because firing temperature is high temperature, therefore is preferably metallic resistance type of heating or graphite resistance type of heating.As the method for burning till, preferably normal pressure sintering method or air pressure (with gas pressurization) sintering method etc. are from the outside process for calcining not applying mechanicalness pressurization.Crucible is preferably not containing the high purity material of impurity, as Al
2o
3crucible, Si
3n
4crucible, AlN crucible, match grand crucible, crucible that BN (boron nitride) crucible etc. can use in inert environment, but preferably use BN crucible, because the impurity being derived from crucible can be avoided to be mixed into.Firing atmosphere is non-oxidizing gas, such as, can be the arbitrary combination of nitrogen, hydrogen, ammonia, argon etc. or These gases.The firing temperature of fluor is more than 1200 DEG C less than 2200 DEG C, is more preferred from more than 1400 DEG C less than 2000 DEG C, and heat-up rate is 3 ~ 15 DEG C/min.The trickleer fluor of particle diameter can be obtained compared with burning till under low temperature, burning till under higher temperatures and can obtain the larger fluor of particle diameter.Firing time is different and difference to some extent according to raw material type, the General reactions time be 1 ~ 10 hour better.Pressure when burning till under inert environment, preferably burns till at below 0.5MPa (especially with below 0.1MPa for good).After having burnt till, be cooled to room temperature, the mode such as ball milling or industrial size reduction machinery can be used to pulverize, after through steps such as filtration, drying, classifications, fluor of the present invention can be obtained.
In order to obtain the fluor of high briliancy, fluor is in time burning till, and because of the impact of the factor such as impurity, treating processes pollution in the interpolation of fusing assistant, raw material, the foreign matter content be included in described fluor composition should be little as much as possible.When particularly the element such as fluorine element, boron, chlorine element, carbon exists in a large number, will suppress luminous.Therefore can select the raw material of higher degree, and control synthesis step is avoided polluting, and makes the content of aforementioned elements be less than 1000ppm respectively.
When fluor of the present invention uses with the form of powder, the median size of this fluor powder is preferably below 20 μm.Reason is because the luminescence of fluor powder mainly betides on particle surface, if median size (so-called in the present invention " median size " refers to volume medium particle diameter (D50)) is below 20 μm, the surface-area of fluor powder per unit weight can be guaranteed, avoid briliancy to reduce.In addition, when this fluor powder coats the upper situation of luminescence component, the density of this fluor powder can be improved, with regard to this viewpoint, briliancy also can be avoided to reduce.In addition, according to the discussion of contriver, from the luminous efficiency viewpoint of fluorophor powder, learn that median size is to be greater than 1 μm for better.According to above-mentioned, the median size of fluor powder of the present invention preferably more than 1 μm and less than 20 μm, especially with more than 3.0 μm and the particle diameter of less than 15 μm is good.Herein so-called " median size (D50) ", be utilize BeckmanCoulter Inc. Multisizer-3, carry out with Ku Ertefa the value measuring gained.
Fluor of the present invention is applicable to fluorescent display tube (VFD), Field Emission Display (FED), plasma display panel (PDP), cathode tube (CRT), photodiode (LED) etc.Especially, when use 455nm light source irradiation fluor of the present invention, the luminous predominant wavelength of fluor is 600 ~ 680nm, the CIE1931 tristimulus coordinates (x, y) of luminous tone is, 0.45≤x≤0.72,0.2≤y≤0.5, and glorious degrees is high, therefore, fluor of the present invention is specially adapted to photodiode.
Light-emitting device of the present invention comprises semiconductor luminous assembly and fluor of the present invention.Semiconductor luminous assembly is to send the light person of 300 ~ 550nm wavelength for better, especially better with the blue semiconductor luminescence component of ultraviolet (or purple) semiconductor luminous assembly or 420 ~ 500nm that send 330 ~ 420nm.As these luminescence components, semiconductor luminous assembly can be the various semi-conductor such as zinc sulphide or gan, and with luminous efficiency, uses gallium nitride semiconductor better.Gallium nitride light-emitting assembly can be built the methods such as crystallization (HVPE) and on substrate, form nitride-based semiconductor, with In by Metalorganic chemical vapor deposition method (MOCVD) or hydrite vapor phase
αal
βga
1-alpha-betathe semiconductor luminous assembly that N (0≤α, 0≤β, (alpha+beta) < 1) is formed is best.Semiconductor construction can be the homophaneous structure such as MIS joint, PIN joint, PN joint, heterojunction structure or two heterojunction structure.In addition, its emission wavelength can be controlled by the material of semiconductor layer or its mixed crystal degree.
In light-emitting device of the present invention, except fluor of the present invention is used alone, also can use together with the fluor with other characteristics of luminescences, to form the light-emitting device that can send wanted color.Such as, use the UV-light semiconductor luminous assembly of 330 ~ 420nm, be excited at this wavelength and send more than 420nm and the blue emitting phophor of below 500nm wavelength, send more than 500nm and the combination of the green-emitting phosphor of below 570nm wavelength and fluor of the present invention.The citing of aforementioned blue fluor can be BaMgAl
10o
17: Eu, green-emitting phosphor can be β-Sialon phosphor.Form according to this, when the uviolizing that semiconductor luminous assembly sends is in fluor, three coloured light of red, green, blue can be sent, be mixed to the light-emitting device of white via it.
In addition, still can use the blue semiconductor luminescence component of 420 ~ 500nm, be excited at this wavelength and send more than 550nm and the combination of the yellow fluorophor of the wavelength of below 600nm and fluor of the present invention.Aforementioned yellow fluorophor, such as, can be (Y, Gd)
3(Al, Ga)
5o
12: Ce.Form according to this, when the blue light that semiconductor luminous assembly sends irradiates in fluor, red, yellow dichroscope can be sent, by the lighting fixtures that the blue light of these and semiconductor luminous assembly itself is mixed to white or is with light bulb color.
In addition, still can use the blue semiconductor luminescence component of 420 ~ 500nm, be excited at this wavelength and send more than 500nm and the combination of the green-emitting phosphor of the wavelength of below 570nm and fluor of the present invention.This kind of green-emitting phosphor citing can be β-Sialon phosphor.Form according to this, when the blue light that semiconductor luminous assembly sends irradiates in fluor, red, green dichroscope can be sent, the blue light of these and semiconductor luminous assembly itself is mixed to the lighting fixtures of white.
[embodiment and comparative example]
Below, be illustrated with regard to the embodiment of the present invention, but the present invention is not limited to this.
Measuring method illustrates:
(1) fluor briliancy and tristimulus coordinates: fluor uses with TOPCON brightness photometer SR-3A
455nm irradiates measurement.It is within ± 0.3% that brightness value measures difference.
(2) light-emitting phosphor predominant wavelength: measure with the FluoroMax-3 of JobinYVON.When luminous predominant wavelength refers to and uses 455nm optical excitation fluor, the wavelength of fluor maximum emission intensity.
(3) analysis of fluor component:
(3-1a) instrument: with the ULTIMA-2 type of JobinYVON inductively electricity slurry atomic emission spectrometry (ICP) measure.
(3-1b) sample pre-treatments: the sample accurately weighing 0.1g, in platinum crucible, adds Na
2cO
3after 1g mixes, with 1200 DEG C of High Temperature Furnaces Heating Apparatus meltings (temperature condition: arrive 1200 DEG C in 2 hours by room temperature, in 1200 DEG C of constant temperature 5 hours), acid solution is added after melts cooling, such as 25mlHCl (36%), and heating for dissolving is to clarification, inserts in 100mlPFA volumetric bottle, with pure water quantitatively to graticule after cooling.
(3-2a) the nitrogen oxygen analyzer of instrument: Horiba.Model EMGA-620W.
(3-2b) measure: fluor 20mg is inserted in tin capsule, is positioned in crucible, measures.
(4) regular strontium stripping is fixed containing measuring:
(4-1a) instrument: with the ULTIMA-2 type of JobinYVON inductively electricity slurry atomic emission spectrometry (ICP) measure.
(4-2a) pre-treatment: the fluor getting conductance 200 below μ s/cm, pure water is added than the part by weight that pure water is 1:100 according to fluor, form the mixing solutions of fluor and water, after heating in 80 DEG C, 40 hours, cool this mixing solutions to the membrane filtration of room temperature via 0.45nm aperture, this aqueous phase solution directly uses ICP to measure.
(5) sc-170 of dionic tester: suntex.
(6) fluor D
50median size is analyzed: measure with BeckmanCoulterMultisizer-3.D
50represent particle accumulation volume that particle diameter is less than this value account for overall particle long-pending 50%.
Embodiment 1
Burn till under strontium metal (2N) needed for preparation is placed in pure nitrogen gas atmosphere, reaction conditions is nitrogen flow rate is 85 liters/min, from room temperature, be warming up to medium temperature, and heat-up rate is 10 DEG C/minute, when medium temperature 620 DEG C, change heat-up rate is 3 DEG C/minute, until 900 DEG C.At being maintained at 900 DEG C, constant temperature burns till 24 hours, after be down to room temperature with 10 DEG C/minute, strontium nitride (Sr can be obtained
3n
2) compound.
The Sr of above-mentioned synthesis
3n
2with commercially available Ca
3n
2(2N), AlN (3N), Si
3n
4(3N), Eu
2o
3(4N), according to Ca
3n
2get 0.2/3 mole, Sr
3n
2get 0.792/3 mole, AlN gets 1 mole, Si
3n
4get 1/3 mole, Eu
2o
3the ratio of getting 0.008/2 mole weighs each raw material powder, and uses mortar to mix in glove box in a nitrogen environment.In raw material mixed powder, the molar ratio of each element is in table 2.Aforementioned base materials mixed powder is inserted in boron nitride crucible, and this crucible is inserted High Temperature Furnaces Heating Apparatus, furnace atmosphere is the environment of high-purity nitrogen, gas flow 80 liters/min, heat-up rate according to 10 DEG C/min is warming up to 1800 DEG C, and keeps 12 hours and burn till at 1800 DEG C, the rear speed complying with 10 DEG C/min be down to room temperature, and via steps such as pulverizing, ball milling, filtration, drying, classifications, fluor of the present invention can be obtained.Median size (D
50) analytical results is 8.3 μm.The analysis of nitrogen oxygen and icp analysis result are Ca:4.75 % by weight, Sr:33.79 % by weight, Al:16.20 % by weight, Si:16.90 % by weight, N:24.02 % by weight, O:1.56 % by weight, Eu:0.73 % by weight, therefore when with 1 mole of Al for benchmark time, an actual sets accepted way of doing sth is Ca
0.1974sr
0.6423al
1si
1.0022n
2.8562o
0.1624: Eu
0.0080, that is Ca
psr
qm
m-A
a-B
b-O
t-N
n: Eu
r, p=0.1974, q=0.6423, m=0, t=0.1624, r=0.0080, a=1, b=1.0022, n=2.8562 in formula.Get the fluor 0.1 gram that conductance is less than 200 below μ s/cm, pure water is added than the part by weight that pure water is 1 to 100 according to fluor, this Glass Containers of sealing after mixing, after heating in 80 DEG C, 40 hours, be cooled to room temperature, the content of strontium detected in the aqueous phase of this mixing solutions is 1.0ppm, and regular content of strontium is 1.0/0.6423=1.6ppm.Again, after this fluor excites with 455nm light, recording its luminous predominant wavelength is 616nm, CIE1931 chromaticity coordinates x=0.634, y=0.364, and glorious degrees is 165% (asking for an interview table 3).Embodiment in the present invention and the glorious degrees of comparative example mean for the glorious degrees (100%) of following comparative example 7 fluor.
Embodiment 2 ~ 4 and comparative example 1 ~ 3
Strontium nitride synthesis condition carries out according to table 1 condition, and in raw material mixed powder, the molar ratio of each element is in table 2, and all the other programs are with embodiment 1.The test result of fluor physical property is with reference to table 3.Can be found, by the firing condition of adjustment strontium nitride, when regular strontium stripping content is within the scope of 1 ~ 20ppm, to there is preferably brightness value by the experimental result of table 3.
Embodiment 5 ~ 8 and comparative example 4 ~ 6
Strontium nitride synthesis condition carries out according to table 1 condition, and in raw material mixed powder, the molar ratio of each element is in table 2, and all the other programs are with embodiment 1.Fluor physical property measurement result is with reference to table 3.Can be obtained and above-mentioned identical conclusion by experimental result.When normalization strontium stripping content is within the scope of 1 ~ 20ppm, there is preferably brightness value.
Embodiment 9 ~ 11 and comparative example 7 ~ 8
Strontium nitride synthesis condition carries out according to table 1 condition, and in raw material mixed powder, the molar ratio of each element is in table 2, and in table 2, Y uses Y
2o
3(3N), Ge uses GeO
2(3N), Zn uses ZnO (3N), and all the other programs are with embodiment 1.Fluor physical property measurement result is with reference to table 3.Can be obtained and above-mentioned identical conclusion by experimental result.When normalization strontium stripping content is within the scope of 1 ~ 20ppm, there is preferably brightness value.
Table 1
Note: in table 1, "-" represents that medium temperature equals holding temperature.
Table 2
Table 3
The briliancy of fluor of the present invention measures via a briliancy measuring apparatus and obtains, as shown in Figure 1, this briliancy measuring apparatus comprises the casing 11 of a black, sample groove 12, one light source 13, one photoconduction skirt 14, one speculum 15 and a brightness photometer 16, wherein, this sample cell 12 is seated in this casing 11, this light source 13 is that vertical this sample cell 12 about 5 centimeters is highly arranged, this photoconduction skirt 14 diameter is about 2 centimeters and arranges with this light source 13 angle at 45 °, this speculum 15 is arranged in this photoconduction skirt 14, and with this sample cell 12 apart from about 8 centimeters, and this brightness photometer 16 is about 40 centimeters with the distance of this speculum 15, after the fluor being placed in this sample cell 12 irradiates via this light source 13, the fluorescence that fluor sends can be directed to this brightness photometer 16 via the exposure level of this photoconduction skirt 14 and speculum 15 and carry out briliancy measurement.
Specifically, in foregoing embodiments of the present invention and comparative example, the briliancy measurement of fluor gets testing sample 1.3 grams to insert in sample cell 12, and make sample be uniformly distributed in this sample cell 12 through flattening, then this sample cell 12 is placed in this casing 11, the light source 13 vertical irradiation sample that uses emission wavelength to be 455nm, and this brightness photometer 16 (TOPCON system, model is SR-3A) is the fluorescent intensity using field1 ° of sense mode to detect this fluor to send after light source irradiation.
Be noted that the predominant wavelength of the luminescent spectrum of this fluor refers to the wavelength that luminous intensity is maximum.
Then, obtained light-emitting device of the present invention after the fluor sample of aforementioned various embodiments of the present invention and semiconductor luminous assembly being carried out encapsulation.
Consult Fig. 2, light emitting device embodiment of the present invention comprises semiconductor luminescence component 21, fluorescent layer 22 and an encapsulated layer 23.
Wherein, this semiconductor luminous assembly 21 comprises one and can to conduct electricity and the pedestal 211, of loading end 212 had without exception in matrix is arranged at this matrix loading end 212 and LED crystal particle 213, wire 214 be electrically connected with this pedestal 211 is electrically connected with this LED crystal particle 213, a wire 215 is electrically connected with this wire 214; Wherein, this pedestal 211 and this wire 215 can coordinate provides electric energy to this LED crystal particle 213 from the external world, and this LED crystal particle 213 can convert the electric energy of acceptance to luminous energy and outwards send.The present embodiment is by a commercially available emission wavelength 455nm, the blue LED crystal grain 213 (manufacturers: strange power photoelectricity) of InGaN is with conductive silver glue (model: BQ6886, manufacturers: UNINWELL) bind on the loading end 212 of this pedestal 211, this wire 214 and this wire 215 of being electrically connected with this LED crystal particle 213 is then extended from this LED crystal particle 213 end face.
Aforementioned fluorescent layer 22 this LED crystal particle 213 coated.Fluor 221 contained in fluorescent layer 22 is after being subject to the exciting of light that this LED crystal particle 213 sends, the light sending and differ from excitation wavelength can be changed, in the present embodiment, this fluorescent layer 22 is that the polysilane epoxy resins containing 35 % by weight fluor 221 is coated on this LED crystal particle 213 outside surface, and is formed after drying sclerosis.
The wire 215 of the pedestal 211 of this encapsulated layer 23 this semiconductor luminous assembly 21 part coated, wire 214, part and this fluorescent layer 22.
In sum, the present invention by the ratio of element each in phosphor structures, and coordinates the regular strontium stripping content controlling fluor between 1 ~ 20ppm, can obtain the high briliancy fluor that a luminous predominant wavelength is 600 ~ 680nm.And this fluor collocation semiconductor luminous assembly, the light-emitting device of high briliancy can be obtained simultaneously.
Only as described above, be only preferred embodiment of the present invention, when not limiting scope of the invention process with this, the simple equivalence namely generally done according to the present patent application the scope of the claims and invention description content changes and modifies, and all still remains within the scope of the patent.
Claims (8)
1. a fluor, is characterized in that, comprising composition formula is Ca
psr
qm
m-A
a-B
b-O
t-N
n: Z
rconstituent, wherein, the group that M forms for being selected from magnesium, barium, beryllium and zinc, the group that A forms for being selected from aluminium, gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating, the group that B forms for being selected from silicon, germanium, tin, titanium, zirconium and hafnium, the group that Z element forms for being selected from europium and cerium, 0 < p < 0.45,0.542 < q < 1,0≤m < 1,0≤t≤0.3,0.00001≤r≤0.1, a=1,0.8≤b≤1.2,2.7≤n≤3.1; And the regular strontium stripping content of described fluor is 1 ~ 20ppm; Described regular strontium stripping content measures by the following method: the fluor getting conductance 200 below μ s/cm, according to fluor: pure water is the weight ratio interpolation pure water of 1: 100, form the mixing solutions of fluor and water, after heating in 80 DEG C, 40 hours, cool described mixing solutions to room temperature, the aqueous phase getting described mixing solutions measures its regular strontium stripping content.
2. fluor according to claim 1, is characterized in that, described regular strontium stripping content is 3 ~ 17ppm.
3. fluor according to claim 1, is characterized in that, wherein 0 < p≤0.2,0.792≤q < 1.
4. fluor according to claim 1, is characterized in that, wherein the group that forms for being selected from magnesium and zinc of M; The group that A forms for being selected from aluminium and gallium; The group that B forms for being selected from silicon and germanium.
5. fluor according to claim 1, it is characterized in that, use fluor described in 455nm light source irradiation, described fluor is stimulated and the luminous predominant wavelength of luminescence is 600 ~ 680nm, CIE1931 tristimulus coordinates (the x of its luminous tone, y) be, 0.45≤x≤0.72,0.2≤y≤0.5.
6. fluor according to claim 5, is characterized in that, use fluor described in 455nm light source irradiation, the cie color coordinate (x, y) of the luminous tone of described fluor is, 0.6≤x≤0.7,0.3≤y≤0.4.
7. a light-emitting device, is characterized in that, comprises:
Semiconductor luminescence component; And
One fluor, the optical excitation that described fluor sends by described semiconductor luminous assembly, and conversion sends the light being different from exciting light, wherein, described fluor is arbitrary described fluor in claim 1 to 6.
8. light-emitting device according to claim 7, is characterized in that, described semiconductor luminous assembly sends the light of 300 ~ 550nm wavelength.
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| US20080283864A1 (en) * | 2007-05-16 | 2008-11-20 | Letoquin Ronan P | Single Crystal Phosphor Light Conversion Structures for Light Emitting Devices |
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| WO2006132188A1 (en) * | 2005-06-06 | 2006-12-14 | National Institute For Materials Science | Method for producing inorganic crystal |
| US20080283864A1 (en) * | 2007-05-16 | 2008-11-20 | Letoquin Ronan P | Single Crystal Phosphor Light Conversion Structures for Light Emitting Devices |
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