CN102464979A - Fluorophor and light emitting device - Google Patents
Fluorophor and light emitting device Download PDFInfo
- Publication number
- CN102464979A CN102464979A CN2010105491552A CN201010549155A CN102464979A CN 102464979 A CN102464979 A CN 102464979A CN 2010105491552 A CN2010105491552 A CN 2010105491552A CN 201010549155 A CN201010549155 A CN 201010549155A CN 102464979 A CN102464979 A CN 102464979A
- Authority
- CN
- China
- Prior art keywords
- fluor
- regular
- light
- strontium
- stripping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to a fluorophor, comprising components with a composition formula shown as a formula (I) as follows: CapSrqMm-Aa-Bb-Ot-Nn: Zr......(I), wherein M is selected from a group constituted by magnesium, barium, beryllium and zinc, A is selected from a group constituted by aluminum, gallium, indium, scandium, yttrium, lanthanum, gadolinium and lutetium, B is selected from a group constituted by silicon, germanium, tin, titanium, zirconium and hafnium, an element Z is selected from a group constituted by europium and cerium, p is more than 0 and smaller than 1, q is not smaller than 0 and smaller than 1, m is not smaller than 0 and smaller than 1, t is not smaller than 0 and not more than 0.3, r is not smaller than 0.00001 and not more than 0.1, a is 1, b is not smaller than 0.8 and not more than 1.2, and n is not smaller than 2.7 and not more than 3.1; furthermore, the dissolution content of normalized calcium in the fluorophor is 1-25ppm, and the fluorophor achieves high luminance in the wavelength range of 600-680nm. In addition, the invention simultaneously provides a light emitting device with high luminance.
Description
Technical field
The present invention relates to about indicating meter, liquid crystal with employed nitride phosphor in the lighting units such as backlight, luminescent lamp, photodiode.The invention relates to this nitride phosphor and form and use the light-emitting device of this fluor.
Background technology
In recent years; Use the light-emitting device of semiconductor light emitting to be widely used; Particularly photodiode is by successfully exploitation; This light-emitting device is than luminaires such as the CCFL of convention, incandescent light, has that luminous efficiency height, volume are little, advantages such as low consumption electric power and low cost, therefore can use as various light sources.And semiconductor light-emitting apparatus comprises semiconductor luminous assembly and fluor, and fluor can absorb and change the light that semiconductor luminous assembly sends, the light mixing use of sending by light that semiconductor luminous assembly sent and fluor conversion.This kind light-emitting device can be used as various fields such as luminescent lamp, car lighting, indicating meter, LCD backlight demonstration and uses, and wherein, uses the most extensive with white luminous device.Existing white luminous device is that the employing cerium is the YAG fluor (Y in active site
3Al
5O
12: Ce) and the collocation semiconductor luminous assembly that sends blue light form.Yet, use Y
3Al
5O
12: the mixed light that semiconductor luminous assembly sent of blue light is sent in Ce fluor and collocation, and its tristimulus coordinates is positioned at the tristimulus coordinates and the Y of the semiconductor luminous assembly that sends blue light
3Al
5O1
2: the tristimulus coordinates of Ce fluor connects online, thereby the mixed light that is sent is for lacking the white light of red light, and color rendering and colorimetric purity are obviously not enough.In addition, Y
3Al
5O
12: the preferable excitation spectrum zone of Ce and the light-emitting zone of semiconductor luminous assembly and inconsistent, therefore, the efficiency of conversion of exciting light is not good, and the white light source of high briliancy is difficult for obtaining.For solve this kind tone bad with the low phenomenon of glorious degrees, active development is sneaking into the fluor that can send ruddiness in the YAG:Ce fluor in recent years, and improvement can send the quality of the fluor of ruddiness, to improve glorious degrees.
Yet, absorbing blue light and then send red light or the fluor of red light is comparatively rare partially, the development research of industry is main with nitride, oxynitride fluor at present.Known have use the Sr of europium (Eu) as the active site
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.Yet, Sr
2Si
5N
8: the Eu fluor has the shortcoming of briliancy and color rendering decline because the thermotolerance of crystal own is not good during life-time service; Though the no endurance issues of Sialon phosphor itself, light-emitting phosphor briliancy are obviously not enough, do not popularize on commercial the use.CaAlSiN
3: though the Eu fluor has preferable weather resistance, and is good briliancy than Sialon phosphor, and industry still expects further to improve the glorious degrees of fluor, so that light-emitting device can have higher luminous efficiency.
Summary of the invention
Therefore in view of the above problems, 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 the light-emitting device of making a high briliancy.
For satisfying aforementioned intended purposes, 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, M is selected from the group that magnesium, barium, beryllium and zinc are formed, A is selected from the group that aluminium, gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating are formed; B is selected from the group that silicon, germanium, tin, titanium, zirconium and hafnium are formed, and the Z element is to be selected from the group that europium and cerium are formed, 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 calcium stripping content of this fluor is 1～25ppm; Aforementioned regular calcium stripping content adopts with following method to be measured: the fluor of getting below the conductance 200 μ s/cm is washed to conductance 200 μ s/cm; Is that 1: 100 weight ratio is added pure water according to fluor than pure water, forms the mixing solutions of fluor and water, mixes the back and seals this container; After heating in 80 ℃, 40 hours; Cool off this mixing solutions to room temperature, get the water of this mixing solutions, measure its regular calcium stripping content.
The present invention also provides following fluor:
Above-mentioned fluor, wherein, the stripping content of regular calcium is 5～20ppm.
Above-mentioned fluor, wherein, q=0.
Above-mentioned fluor, wherein, 0＜p＜1,0＜q＜1.
Above-mentioned fluor; Wherein, Normalization calcium stripping content is 1～25ppm, and the regular strontium stripping content stripping content that further can be the aforementioned regular strontium of 1～20ppm adopts with following method and measures: getting the fluor below the conductance 200 μ s/cm, is that 1: 100 weight ratio is added pure water according to fluor than pure water; Form the mixing solutions of fluor and water; After heating in 80 ℃, 40 hours, cool off this mixing solutions to room temperature, the water of getting this mixing solutions is measured the stripping content of its regular strontium.
Above-mentioned fluor, wherein, the stripping content of regular calcium is 5～20ppm, and the stripping content of regular strontium is 3～17ppm.
Above-mentioned fluor, wherein, 0.05≤p≤0.9,0.1≤q≤0.95.
Above-mentioned fluor, wherein:
M is selected from the group that magnesium and zinc are formed;
A is selected from the group that aluminium and gallium are formed;
B is selected from the group that silicon and germanium are formed.
Above-mentioned fluor wherein, is preferably when using the 455nm light source irradiation, and the light-emitting phosphor wavelength is 600～680nm, and (x y) is 0.45≤x≤0.72,0.2≤y≤0.5 to 1931 tristimulus coordinatess of its luminous tone.
Above-mentioned fluor is more preferred from when using the 455nm light source irradiation, and (x y) is 0.6≤x≤0.7,0.3≤y≤0.4 to the cie color coordinate of light-emitting phosphor tone.
The present invention also provides a kind of light-emitting device, comprises:
The semiconductor luminescence component; And
Foregoing fluor, wherein, the optical excitation that this fluor can be sent by this semiconductor luminous assembly, and the light that is different from exciting light is sent in conversion.
Foregoing light-emitting device, wherein, this semiconductor luminous assembly can send the light of 300～550nm wavelength.
The present invention mainly by the stripping content of regular calcium of control fluor in certain limit; And obtain the fluor of high briliancy; The present invention further can be by controlling regular calcium stripping content and regular strontium stripping content in certain limit simultaneously, thereby obtain the fluor of high briliancy.The present invention also can be with this fluor collocation semiconductor luminous assembly, and obtains the light-emitting device of high briliancy.
Description of drawings
Fig. 1 is the user mode synoptic 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 particles; 214 wires; 215 leads; 22 fluorescent layers;
221 fluor; 23 encapsulated layers.
Embodiment
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are merely the usefulness that illustrates, and should not be interpreted as the restriction that the present invention is implemented.
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, M is selected from the group that magnesium, barium, beryllium and zinc are formed, A is selected from the group that aluminium, gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating are formed; B is selected from the group that silicon, germanium, tin, titanium, zirconium and hafnium are formed, and the Z element is to be selected from the group that europium and cerium are formed, 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 stripping content of regular calcium is 1～25ppm in this fluor; Aforementioned regular calcium stripping content adopts with following method to be measured: get the fluor below the conductance 200 μ s/cm; Is that 1: 100 weight ratio is added pure water according to fluor than pure water; Form the mixing solutions of fluor and water, mix this container of back sealing, after heating in 80 ℃, 40 hours; Cool off this mixing solutions to room temperature, get the water of this mixing solutions and measure its regular calcium stripping content.
In the aforementioned phosphors, M is selected from the group that magnesium, barium, beryllium and zinc are formed.A is selected from the group that aluminium, gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating are formed, and for example, A can be separately an aluminium element, also can be the mixture of elements such as aluminium, gallium.B is selected from the group that silicon, germanium, tin, titanium, zirconium and hafnium are formed, and for example, B can be separately an element silicon, also can be the mixture of elements such as silicon, germanium.The Z element is to be selected from the group that europium and cerium are formed.Ca is that calcium constituent, Sr are that strontium element, O are that oxygen element, N are the 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 was aluminium, glorious degrees was better.
B is preferably 0.8≤b≤1.2, is more preferred from 0.9≤a≤1.1.More preferably, when B is a silicon, and the b value is 1 o'clock, and glorious degrees is better.
T is preferably 0≤t≤0.3, is more preferred from 0≤t≤0.2.
N is preferably 2.7≤n≤3.1, is more preferred from 2.8≤n≤3.1.
M, a, b, t are in aforementioned scope of the present invention the time, and glorious degrees is good.
R is preferably 0.00001≤r≤0.1.More preferably, when the Z element was europium (Eu), glorious degrees was better.When the r value less than 0.00001 the time because the Eu quantity of luminescence center is few, so glorious degrees reduces; When the r value greater than 0.1 the time, owing to the interatomic phase mutual interference of Eu causes the phenomenon of concentration delustring, so that briliancy lowers.More preferably, when the r value was 0.002～0.03, glorious degrees was better.
In addition, fluor of the present invention can contain calcium, strontium element in forming simultaneously, wherein, and 0＜p＜1,0≤q＜1.When q=0, also can reach briliancy and promote effect, when non-vanishing as if q, aforementioned p value is preferable with 0.02～0.95, the q value is preferable with 0.05～0.98, is more preferred from p=0.05～0.9, q=0.1～0.95.On the relativeness of calcium, strontium element, be preferably 0＜(p+q)＜1, (p/q)=0.1～10.Regular calcium stripping content is 1～25ppm in the fluor particularly of the present invention, finds that the light-emitting phosphor briliancy that meets this scope can obviously promote.
In addition, fluor of the present invention can contain calcium, strontium element in forming simultaneously; Wherein, when 0＜p＜1,0＜q＜1 o'clock; Being preferably regular calcium stripping content is 1～25ppm, and regular strontium stripping content is 1～20ppm, and being more preferred from regular calcium stripping content is 5～20ppm; And regular strontium stripping content is 3～17ppm, finds that the light-emitting phosphor briliancy that meets this scope can obviously promote.
Fluor below the conductance 200 μ s/cm means fluor and detects via following conductance detection method, and its conductance is the following persons of 200 μ s/cm.The conductance detection method is following: get pure water (conductance is less than 1 μ s/cm) and mix the fluor detection mixed solution that formation fluor content is 1 weight % with fluor; This detects mixed solution and stirred 30 minutes down in 80 ℃ of water-baths; Leave standstill then to room temperature, get the upper strata settled solution that detects mixed solution and carry out the conductance measurement.If the conductance value of measuring is below the 200 μ s/cm, then this fluor is the fluor below the conductance 200 μ s/cm; If observed value is more than the 200 μ s/cm, then carrying out the fluor cleanup acid treatment earlier is below the 200 μ s/cm up to the conductance value.Fluor cleanup acid treatment method is following: the salpeter solution of getting 0.5 weight % mixes the fluor pickling mixed solution that forms fluor content 1 weight % with fluor; This pickling mixed solution shook 30 minutes via ultrasound under room temperature; Fluor after filtering adds 100 times pure water; In 80 ℃ of water-bath lower seal stirring and washing 30 minutes; Row filters again, and aforementioned pure water cleans with filtering step and repeats four times again, filters the fluor that obtains at last and measures the conductance value according to above-mentioned conductance detection method again.
When measuring regular calcium or regular strontium stripping content; The following fluor of conductance 200 μ s/cm is got by system and pure water is complied with 1: 100 the weight ratio formation fluor and the mixing solutions of water; This mixing solutions uses container to seal, and prevent that moisture content scatters and disappears in the heat-processed, and heating unit is a baking oven.After heating in 80 ℃, 40 hours, the mixing solutions that cools off this fluor and water is to room temperature.
The stripping content of normalization (normalize) calcium is meant that the calcium contents that measures is divided by this composition formula Ca through the aqueous phase of mixing solutions after the aforementioned program
pSr
qM
m-A
a-B
b-O
t-N
n: Z
rIn the result that obtains of p value.
The stripping content of normalization (normalize) strontium is meant that the content of strontium that measures is divided by this composition formula Ca through the aqueous phase of mixing solutions after the aforementioned program
pSr
qM
m-A
a-B
b-O
t-N
n: Z
rIn the result that obtains of q value.
When using 455nm light source irradiation fluor of the present invention, this fluor is stimulated and luminous luminous predominant wavelength is 600～680nm, and (x y) is 0.45≤x≤0.72,0.2≤y≤0.5 to CIE 1931 tristimulus coordinatess of its luminous tone.Luminous predominant wavelength means the wavelength that luminous intensity is maximum.
One of preferable enforcement kenel of the present invention is 0＜p＜1,0≤q＜1,0≤m≤0.05,0≤t≤0.1,0.00001≤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 calcium stripping content of this fluor is 1～25ppm.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; Yet, because of the influence of factors such as pollution in impurity, the treating processes in the interpolation of fusing assistant, the raw material, volatility of raw material, possibly have other crystallization phasess or noncrystalline phase (amorphous phase) simultaneously in the building-up process; As long as under the prerequisite that does not influence glorious degrees, spirit still according to the invention.
Implement the compositional analysis result of this example fluor, each element m, a, b, t, n value that discovery is calculated from the compositional analysis result have deviation a little compared to m, a, b, t, the n value calculated from use raw material allotment proportional meter.This phenomenon can be thought has a spot of raw material to decompose in burning till or evaporation, perhaps causes because of analytical error.The deviation of t value particularly; Can think such as: just be contained in the oxygen in the raw material from the outset, or the oxygen of adhering on surface, perhaps when the raw material weighing, when mixing and when burning till; The oxygen of sneaking into because of the raw material surface oxidation, and the institutes such as moisture or oxygen that after burning till, are adsorbed in the fluor surface cause.In addition, when burning till in the environment that is containing nitrogen and/or ammonia, the oxygen when burning till in the raw material also possibly break away from and replaced by nitrogen, judges that some deviations will take place for t, n.
When fluor of the present invention was made, the raw material of calcium, strontium element used nitride preferable.The method of manufacture of nitride is burnt till under the atmosphere of high-purity nitrogen for selecting required divalent metal.Firing atmosphere is good with high-purity nitrogen, and high-purity nitrogen is meaning purity and reaching more than 99.99%.And nitrogen flow rate must be controlled to be the state of high flow rate, when for example CaCl2 burns till flow velocity be 10～70 liters/be divided into goodly, 30～50 liters/minute are better; When strontium nitride burns till flow velocity be 70～90 liters/be divided into goodly, 80～90 liters/minute are better.Too high or too low nitrogen flow rate all can't synthesize suitable nitride, so that follow-up synthetic fluor has regular calcium metal content and regular strontium metal content in the specified range of the present invention.The CaCl2 firing temperature is preferably between 600 ℃～900 ℃, is more preferred between 700～800 ℃.The strontium nitride firing temperature is preferably between 600 ℃～1000 ℃, is more preferred between 700～900 ℃.Firing temperature surpasses or is lower than aforementioned range and then can't obtain required suitable nitride.The CaCl2 firing time was preferably between 3～12 hours, was more preferred between 3～10 hours.The strontium nitride firing time was preferably between 3～24 hours, was more preferred between 5～24 hours.Firing time is long or very few, all can't obtain required suitable nitride.And the heat-up rate that burns till needs special control, promptly is lower than the calcium melting point metal below 200 ℃ the time or be lower than the strontium melting point metal below 150 ℃ the time, and heat-up rate needs comparatively slow; For example 5 ℃/minute heat-up rate is good; 3 ℃/minute heat-up rate is better, and is former because carry out nitride metal when reaction, if heat-up rate is too fast near melting point metal; Then easy generation surface metal melts fast and carries out nitrogenizing reaction, and can't obtain required suitable CaCl2 and strontium nitride.It is good that the container that burns till uses BN (SP 1) crucible, silicon nitride crucible, wherein best with BN (SP 1) crucible.The nitrogenizing reaction formula of calcium, strontium is as follows:
3Ca+N
2→Ca
3N
2；3Sr+N
2→Sr
3N
2
When fluor of the present invention was made, the raw material of A element (+III valency), B element (+IV valency) can use separately nitride, oxide compound, any type of compound.For example, can mix nitride (AN)/oxide compound (A that uses the A element
2O
3) or nitride (AN, the B of A element, B element
3N
4).So-called " oxide compound " only is not limited to and oxygen bonded compound, and other can decomposition during burning till like carbonate, oxalate etc., has the scope that the compound that contains this element and oxygen that constitutes oxide compound in fact also belongs to aforementioned " oxide compound "; The situation of nitride also is meant to have this element and nitrogen compound.
Phosphor raw material of the present invention can be various multi-form precursors, explains as embodiment with the nitride raw material below for simplicity.Though each nitride raw material of A element, B element can be marketable material, but because purity is high more good more, it is good therefore preferably preparing the above raw material of 3N.The particle diameter of each raw material particle is preferably micropartical from promoting the viewpoint of reaction, but with the particle diameter of raw material, the difference of shape, particle diameter, the shape of the fluor that obtains also will change to some extent.Therefore as long as cooperate the particle diameter of the final institute fluor that obtains requirement, the nitride raw material that preparation has an approximate particle diameter just can.The raw material of Eu element is good with commercially available oxide compound, nitride raw material or metal monomer, and purity is high more good more, preferably prepare more than the 3N, and be good with the raw material more than the 4N especially.
The hybrid mode of raw material can be drying process, damp process.For example the numerous embodiments such as wet ball-milling method of dry type ball milled or adding liquid are not limited to single mode.Take by weighing in addition, mixed C a
3N
2, Sr
3N
2The time oxidized because these compounds are prone to, thereby in the glove box under the inert environment, operate comparatively suitable.In addition, because the nitride of each raw material element is easier to receive the influence of moisture, thereby non-active gas preferably uses the gas through abundant removal moisture.Mixing device can use common employed devices such as ball mill or mortar.
Preparation can be according to the certain proportion weighing during fluor, mix each raw material, inserts in the crucible, inserts the high temperature kiln roasting together.The stove that uses when burning till is because of firing temperature is a high temperature, so be preferably metallic resistance type of heating or graphite resistance type of heating.As process for calcining, preferably normal pressure sintering method or air pressure (with gas pressurization) sintering method etc. is from the outside process for calcining that does not apply the mechanicalness pressurization.Crucible is preferably the high purity material that does not contain impurity, like Al
2O
3Crucible, Si
3N
4The crucible that crucible, AlN crucible, the grand crucible of match, BN (SP 1) crucible etc. can use in inert environment, but the BN crucible preferably used, because the impurity that can avoid being derived from crucible is sneaked into.Firing atmosphere is a non-oxidizing gas, for example, can be the arbitrary combination of nitrogen, hydrogen, ammonia, argon etc. or aforementioned gas.The firing temperature of fluor is more than 1200 ℃ below 2200 ℃, is more preferred from more than 1400 ℃ below 2000 ℃, and heat-up rate is 3～15 ℃/min.Burn till under the lower temperature and can get the trickleer fluor of particle diameter, burn till under the higher temperatures and can get the bigger fluor of particle diameter.Firing time is different and difference to some extent according to raw material type, the general reaction times be 1～10 hour preferable.Pressure when burning till under inert environment is preferably in below the 0.5MPa (especially with below the 0.1MPa for good) and burns till.After burning till completion, be cooled to room temperature, can use modes such as ball milling or industrial size reduction machinery to pulverize, through steps such as filtration, drying, classifications, can obtain fluor of the present invention afterwards.
In order to obtain high briliancy fluor, fluor is when burning till, and because of the influence of factors such as the interpolation of fusing assistant, impurities in raw materials, treating processes pollution, being included in the foreign matter content of said fluor in forming should be as much as possible little.When particularly elements such as fluorine element, boron, chlorine element, carbon exist in a large number, will suppress luminous.Therefore can select the raw material and the control synthesis step of higher degree to avoid polluting, make the content of aforementioned elements respectively less than 1000ppm.
When fluor of the present invention used with the form of powder, the median size of this fluor powder was preferably in below the 20 μ m.Reason is because the luminous of fluor powder mainly betides on the particle surface; If median size (so-called among the present invention " median size " is meant number particle diameter (D50) in the volume) is below 20 μ m; Can guarantee the surface-area of fluor powder per unit weight, and avoid briliancy to reduce.In addition, coat the situation on the luminescence component, can improve the density of this fluor powder, with regard to this viewpoint, also can avoid briliancy to reduce when this fluor powder.In addition, according to contriver's discussion,, learn that median size is being preferable greater than 1 μ m from the luminous efficiency viewpoint of fluorophor powder.According to above-mentioned, it is above and below the 20 μ m that the median size of fluor powder of the present invention is preferably in 1 μ m, especially with more than the 3.0 μ m and the particle diameter below the 15 μ m be good.So-called here " median size (D50) " is to utilize BeckmanCoulter corporate system Multisizer-3, measures the value of gained with Ku Ertefa.
Fluor of the present invention is applicable to fluorescent display tube (VFD), Field Emission Display (FED), plasma display panel (PDP), cathode ray tube (CRT), photodiode (LED) etc.Especially, when using 455nm light source irradiation fluor of the present invention, the luminous predominant wavelength of fluor is 600～680nm; The CIE 1931 tristimulus coordinates (x of luminous tone; Y) be 0.45≤x≤0.72,0.2≤y≤0.5; And glorious degrees is high, and 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 preferable with the material that sends 300～550nm wavelength, and is especially preferable with the blue semiconductor luminescence component of the ultraviolet of sending 330～420nm (or purple) semiconductor luminous assembly or 420～500nm.As these luminescence components, semiconductor luminous assembly can be various semi-conductors such as zinc sulphide or gan, and with luminous efficiency, uses gallium nitride semiconductor preferable.The gallium nitride light-emitting assembly can form nitride-based semiconductor by Metalorganic chemical vapor deposition method (MOCVD) or hydrogenate gas phase brilliant method methods such as (HVPE) of heap of stone on substrate, with In
αAl
βGa
The 1-alpha-betaThe formed semiconductor luminous assembly of N (0≤α, 0≤β, (alpha+beta)＜1) is best.Semiconductor construction can be homophaneous structures such as MIS joint, PIN joint, PN joint, heterojunction structure or two heterojunction structure.In addition, can control its emission wavelength by material or its mixed crystal degree of semiconductor layer.
In the light-emitting device of the present invention, except fluor of the present invention is used separately, also can use with fluor with other characteristics of luminescences, with constitute can send wanted the light-emitting device of color.For example, use 330～420nm the UV-light semiconductor luminous assembly, be excited and send more than the 420nm and the blue emitting phophor of the following wavelength of 500nm, send more than the 500nm and the green-emitting phosphor of the following wavelength of 570nm and the combination of fluor of the present invention at this wavelength.Aforementioned blue emitting phophor can be BaMgAl for example
10O
17: Eu, green-emitting phosphor can be β-Sialon phosphor.Constitute according to this,, can send red, green, blue three coloured light, mix via it and be white luminous device when uviolizing that semiconductor luminous assembly sent during in fluor.
In addition, still can use 420～500nm the blue semiconductor luminescence component, be excited and the combination of sending the yellow fluorophor and the fluor of the present invention of the wavelength more than the 550nm and below the 600nm at this wavelength.Aforementioned yellow fluorophor for example can be (Y, Gd)
3(Al, Ga)
5O
12: Ce.Constitute according to this, when blue light that semiconductor luminous assembly sends shines in fluor, can send red, yellow dichroscope, these and the blue light of semiconductor luminous assembly own are mixed the lighting fixtures into white or band bulb look.
In addition, still can use 420～500nm the blue semiconductor luminescence component, be excited at this wavelength and send more than the 500nm and the green-emitting phosphor of wavelength below the 570nm and the combination of fluor of the present invention.This kind green-emitting phosphor can be β-Sialon phosphor for example.Constitute according to this, when blue light that semiconductor luminous assembly sends shines in fluor, can send red, green dichroscope, the blue light of these and semiconductor luminous assembly itself is mixed be the white illumination utensil.
[embodiment and comparative example]
Below, explain with regard to the embodiment of the invention, but the present invention is only for scheduling this.
The measuring method explanation:
(1) fluor briliancy and tristimulus coordinates:, and use TOPCON brightness photometer SR-3A to measure light-emitting phosphor briliancy and tristimulus coordinates with 455nm irradiate light fluor.It is in ± 0.3% that brightness value is measured difference.
(2) light-emitting phosphor predominant wavelength: the Fluoro Max-3 with Jobin YVON measures.When luminous predominant wavelength is to use the 455nm optical excitation, the wavelength that light-emitting phosphor intensity is maximum.
(3) the fluor component is analyzed:
(3-1a) instrument: the ULTIMA-2 type induction coupled plasma atomic radiations spectrograph (ICP) with Jobin YVON is measured.
(3-1b) sample pre-treatments: accurately take by weighing the sample of 0.1g, in platinum crucible, add Na
2CO
3After 1g mixes; With 1200 ℃ of High Temperature Furnaces Heating Apparatus fusions (temperature condition: being heated up by room temperature arrived 1200 ℃ in 2 hours, in 1200 ℃ of constant temperature 5 hours), treat that melts cooling back adds acid solution; 25ml HCl (36%) for example; And heating for dissolving to the clarification, insert after the cooling in the 100ml PFA volumetric bottle, with pure water quantitatively to graticule.
The nitrogen oxygen analyzer of (3-2a) instrument: Horiba.Model EMGA-620W.
(3-2b) measure: fluor 20mg is inserted in the tin capsule, be positioned in the crucible, measure.
(4) regular calcium, regular strontium stripping assay:
(4a) instrument: the ULTIMA-2 type induction coupled plasma atomic radiations spectrograph (ICP) with Jobin YVON is measured.
(4b) pre-treatment: get the fluor below the conductance 200 μ s/cm; Is that 1: 100 weight ratio is added pure water according to fluor than pure water; Form the mixing solutions of fluor and water, after heating in 80 ℃, 40 hours, cool off this mixing solutions to room temperature; Via the membrane filtration in 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 D with Beckman Coulter Multisizer-3
50The expression particle diameter less than the particle cumulative volume of this value account for overall particle long-pending 50%.
Embodiment 1
Preparing required calcium metal (2N) places under the pure nitrogen gas atmosphere and burns till; Reaction conditions is that nitrogen flow rate is 50 liters/minute, begins to be warming up to medium temperature from room temperature, and heat-up rate is 5 ℃/minute; The change heat-up rate is 5 ℃/minute when 650 ℃ of medium temperatures, up to 750 ℃.Burnt till 12 hours in 750 ℃ of following constant temperature, reduce to room temperature with 10 ℃/minute afterwards, can obtain CaCl2 (Ca
3N
2) compound.
Preparing required strontium metal (2N) places under the pure nitrogen gas atmosphere and burns till; Reaction conditions is that nitrogen flow rate is 85 liters/minute, begins to be warming up to medium temperature from room temperature, and heat-up rate is 10 ℃/minute; The change heat-up rate is 1 ℃/minute when 620 ℃ of medium temperatures, up to 900 ℃.Burnt till 24 hours in 900 ℃ of following constant temperature, reduce to room temperature with 10 ℃/minute afterwards, can obtain strontium nitride (Sr
3N
2) compound.
Above-mentioned synthetic Ca
3N
2, Sr
3N
2With commercially available 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 and get 1 mole, Si
3N
4Get 1/3 mole, Eu
2O
3The ratio of getting 0.008/2 mole takes by weighing each raw material powder, and in the glove box under the nitrogen environment, uses mortar to mix.The molar ratio of each element is seen table 2 in the raw materials mix powder.The aforementioned base materials mixed powder is inserted in the boron nitride crucible, and this crucible is inserted High Temperature Furnaces Heating Apparatus, furnace atmosphere is the environment of high-purity nitrogen; 80 liters/minute of gas flows; Heat-up rate according to 10 ℃/min is warming up to 1800 ℃, and burns till in 1800 ℃ of following maintenances 12 hours, reduces to room temperature according to the speed of 10 ℃/min afterwards; And, can obtain fluor of the present invention via steps such as pulverizing, ball milling, filtration, drying, classifications.Median size (D50) analytical results is 8.5 μ m.Nitrogen oxygen is analyzed and the icp analysis result is Ca:4.71 weight %, Sr:34.33 weight %, Al:16.13 weight %, Si:16.70 weight %, N:23.96 weight %, O:1.59 weight %, Eu:0.67 weight %, and an actual sets accepted way of doing sth is Ca
0.197Sr
0.655Al
1Si
0.995N
2.861O
0.166: Eu
0.007, that is Ca
pSr
qM
m-A
a-B
b-O
t-N
n: Z
r, p=0.197 in the formula, q=0.655, m=0, t=0.166, r=0.007, a=1, b=0.995, n=2.861.Get conductance less than 0.1 gram of the fluor below the 200 μ s/cm; Is that 1: 100 weight ratio is added pure water according to fluor than pure water; In container, mix the back sealing, after heating in 80 ℃, 40 hours, be cooled to room temperature; Detect that calcium contents is 0.47ppm in this solution, regular calcium stripping quantity is (0.47/0.197)=2.4ppm; Content of strontium is 0.45ppm in this solution, and regular strontium stripping quantity is (0.45/0.655)=0.7ppm.Again, after this fluor excited with 455nm light, recording its luminous predominant wavelength was 616nm, and CIE 1931 chromaticity coordinates x=0.634, y=0.364, glorious degrees are 167% (asking for an interview table 3).The embodiment among the present invention and the glorious degrees of comparative example are meant for the glorious degrees (100%) of following embodiment 8 fluor.
Embodiment 2～4 and comparative example 1～3
The CaCl2 synthesis condition carries out according to table 1 condition, and the molar ratio of each element is seen table 2 in the raw materials mix powder, and all the other programs and strontium nitride are synthetic with embodiment 1.The test result of fluor rerum natura is with reference to table 3.Experimental result by table 3 can find, by the firing condition of adjustment CaCl2, regular calcium stripping quantity has preferable brightness value in 1～25ppm scope the time.
Embodiment 5～7 and comparative example 4～5
The CaCl2 synthesis condition carries out according to table 1 condition, and the molar ratio of each element is seen table 2 in the raw materials mix powder, and all the other programs and strontium nitride are synthetic with embodiment 1.Fluor physical property measurement result is with reference to table 3.Regular calcium stripping quantity is 16.1ppm among the embodiment 5, and regular strontium stripping quantity is 0.6ppm.Can be obtained and above-mentioned identical conclusion by experimental result, regular calcium stripping quantity has preferable brightness value in 1～25ppm scope the time.
Embodiment 8～10 and comparative example 6～7
The CaCl2 synthesis condition carries out according to table 1 condition, and the molar ratio of each element is seen table 2 in the raw materials mix powder, and Y uses Y
2O
3(3N), Ge uses GeO
2(3N), Zn uses ZnO (3N), and all the other programs and strontium nitride are synthetic 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, regular calcium stripping quantity has preferable brightness value in 1～25ppm scope the time.
The CaCl2 synthesis condition carries out according to table 1 condition, and the molar ratio of each element is seen table 2 in the raw materials mix powder, and all the other programs are with embodiment 1.Fluor physical property measurement result is with reference to table 4.Can know by experimental result; Normalization calcium stripping content be 1～25ppm and regular strontium stripping content be in 1～20ppm scope embodiment 11 with only meet embodiment 1, two that regular calcium stripping content is positioned at 1～25ppm scope and compare and can find that embodiment 11 glorious degrees can obviously promote 5% under identical tristimulus coordinates.Embodiment 12 and embodiment 5 also have same phenomenon, and briliancy differs 3%.Show that regular calcium stripping content is 1～25ppm and regular strontium stripping content when being 1～20ppm scope, has better briliancy and promotes effect.
The CaCl2 synthesis condition carries out according to table 1 condition, and the molar ratio of each element is seen table 2 in the raw materials mix powder, 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, regular calcium stripping quantity has preferable brightness value in 1～25ppm scope the time.
Table 1
Annotate: "-" expression medium temperature equals holding temperature in the table 1.
Table 2
Table 3
Table 4
The briliancy of fluor of the present invention is to measure and get via a briliancy measuring apparatus; As shown in Figure 1, this briliancy measuring apparatus comprises casing 11, sample groove 12, a light source 13, a photoconduction skirt 14, a speculum 15 and a brightness photometer 16 of a black, wherein; This sample cell 12 is seated in this casing 11; This light source 13 is vertical these sample cell 12 about 5 centimeters highly settings, these photoconduction skirt 14 diameters be about 2 centimeters and with 13 one-tenth 45 settings of this light source, this speculum 15 is arranged in this photoconduction skirt 14; And with about 8 centimeters of this sample cell 12 distances; And this brightness photometer 16 is about 40 centimeters with the distance of this speculum 15, and after the fluor that places this sample cell 12 was via these light source 13 irradiations, 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 the briliancy measurement.
At length say; In aforementioned each embodiment of the present invention and the comparative example, the briliancy measurement of fluor is to get testing sample 1.3 grams to insert in the sample cell 12, and makes sample be uniformly distributed in this sample cell 12 through flattening; Then this sample cell 12 is placed in this casing 11; Use the light source 13 vertical irradiation samples of emission wavelength, and this brightness photometer 16 (TOPCON system, model are SR-3A) is to use 1 ° of sense mode of field to detect the fluorescent intensity that this fluor is sent after light source irradiation as 455nm.
Be noted that this light-emitting phosphor spectrographic predominant wavelength is meant the wavelength that luminous intensity is maximum.
Then, after being encapsulated, the fluor sample of aforementioned various embodiments of the present invention and semiconductor luminous assembly make light-emitting device of the present invention.
Consult Fig. 2, light-emitting device embodiment of the present invention comprises semiconductor luminescence component 21, a fluorescent layer 22 and an encapsulated layer 23.
Wherein, this semiconductor luminous assembly 21 comprise one can conduct electricity and have the loading end 212 that without exception is matrix pedestal 211, be arranged at this matrix loading end 212 and the LED crystal particle 213, the wire 214 that are electrically connected with this pedestal 211 are electrically connected with this LED crystal particle 213, a lead 215 is electrically connected with this wire 214; Wherein, this pedestal 211 can cooperate from the external world with this lead 215 provides electric energy to this LED crystal particle 213, and this LED crystal particle 213 can convert the electric energy of accepting to luminous energy and outwards send.Present embodiment is with a commercially available emission wavelength 455nm; The blue LED crystal grain 213 of InGaN (manufacturers: strange power photoelectricity) with conductive silver glue (model: BQ6886; Manufacturers: UNINWELL) bind on the loading end 212 of this pedestal 211, then extend this wire 214 and this lead 215 that is electrically connected with this LED crystal particle 213 from these LED crystal particle 213 end faces.
This encapsulated layer 23 coats pedestal 211, wire 214, partly lead 215 and this fluorescent layer 22 of these semiconductor luminous assembly 21 parts.
In sum, the present invention is by the ratio of each element in the phosphor structures, and regular calcium stripping content is between 1～25ppm in the cooperation control fluor, and can obtain a luminous predominant wavelength is the high briliancy fluor of 600～680nm.And this fluor collocation semiconductor luminous assembly can obtain the light-emitting device of high briliancy simultaneously.
The above is merely preferred embodiment of the present invention, when not limiting practical range of the present invention with this, promptly changes and modification according to claim of the present invention and invention simple equivalent that description is done generally, all still belongs to patent covering scope of the present invention.
Claims (12)
1. fluor, comprising composition formula is Ca
pSr
qM
m-A
a-B
b-O
t-N
n: Z
rConstituent, wherein, M is selected from the group that magnesium, barium, beryllium and zinc are formed, A is selected from the group that aluminium, gallium, indium, scandium, yttrium, lanthanum, gadolinium and gold-plating are formed; B is selected from the group that silicon, germanium, tin, titanium, zirconium and hafnium are formed, and the Z element is to be selected from the group that europium and cerium are formed, 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 stripping content of regular calcium is 1～25ppm in the said fluor; The stripping content of said regular calcium adopts with following method and measures: get the fluor below the conductance 200 μ s/cm; Is to add pure water at 1: 100 according to fluor than the weight ratio of pure water; Form the mixing solutions of fluor and water; After heating in 80 ℃, 40 hours, cool off said mixing solutions to room temperature, the water of getting said mixing solutions is measured the stripping content of its regular calcium.
2. fluor according to claim 1 is characterized in that, the stripping content of said regular calcium is 5～20ppm.
3. fluor according to claim 1 and 2 is characterized in that, wherein q=0.
4. fluor according to claim 1 is characterized in that, wherein 0＜p＜1,0＜q＜1.
5. fluor according to claim 4 is characterized in that, the stripping content of regular strontium is 1～20ppm; The stripping content of said regular strontium adopts with following method and measures: get the fluor below the conductance 200 μ s/cm; Is to add pure water at 1: 100 according to fluor than the weight ratio of pure water; Form the mixing solutions of fluor and water; After heating in 80 ℃, 40 hours, cool off said mixing solutions to room temperature, the water of getting said mixing solutions is measured the stripping content of its regular strontium.
6. fluor according to claim 5 is characterized in that, the stripping content of said regular calcium is that the stripping content of 5～20ppm and said regular strontium is 3～17ppm.
7. fluor according to claim 5 is characterized in that, wherein 0.05≤p≤0.9,0.1≤q≤0.95.
8. according to claim 1 or 5 described fluor, it is characterized in that M is selected from the group that magnesium and zinc are formed; A is selected from the group that aluminium and gallium are formed; B is selected from the group that silicon and germanium are formed.
9. according to claim 1 or 5 described fluor; It is characterized in that, use the said fluor of 455nm light source irradiation, said fluor is stimulated and luminous luminous predominant wavelength is 600～680nm; The CIE 1931 tristimulus coordinates (x of its luminous tone; Y) be 0.45≤x≤0.72,0.2≤y≤0.5.
10. fluor according to claim 9 is characterized in that, uses this said smooth body of 455nm light source irradiation, and (x y) is 0.6≤x≤0.7,0.3≤y≤0.4 to the cie color coordinate of the luminous tone of said fluor.
11. a light-emitting device is characterized in that, comprises:
The semiconductor luminescence component; And
One fluor, the optical excitation that said fluor is sent by said semiconductor luminous assembly, and change and send the light that is different from exciting light, wherein, said fluor is the described fluor of each claim in the claim 1 to 10.
12. light-emitting device according to claim 11 is characterized in that, said semiconductor luminous assembly sends the light of 300～550nm wavelength.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105491552A CN102464979A (en) | 2010-11-09 | 2010-11-09 | Fluorophor and light emitting device |
| CN201810448355.5A CN108456516A (en) | 2010-11-09 | 2010-11-09 | The manufacturing method of fluorophor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105491552A CN102464979A (en) | 2010-11-09 | 2010-11-09 | Fluorophor and light emitting device |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810448355.5A Division CN108456516A (en) | 2010-11-09 | 2010-11-09 | The manufacturing method of fluorophor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102464979A true CN102464979A (en) | 2012-05-23 |
Family
ID=46069111
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810448355.5A Pending CN108456516A (en) | 2010-11-09 | 2010-11-09 | The manufacturing method of fluorophor |
| CN2010105491552A Pending CN102464979A (en) | 2010-11-09 | 2010-11-09 | Fluorophor and light emitting device |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810448355.5A Pending CN108456516A (en) | 2010-11-09 | 2010-11-09 | The manufacturing method of fluorophor |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN108456516A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994079A (en) * | 2012-12-21 | 2013-03-27 | 北京有色金属研究总院 | Nitrogen-oxide orange-red fluorescent material comprising light-emitting film or light-emitting piece and light-emitting device |
| CN103555325A (en) * | 2013-11-01 | 2014-02-05 | 江苏罗化新材料有限公司 | Red nitride fluorescent powder and preparation method thereof |
| CN103881718A (en) * | 2012-12-21 | 2014-06-25 | 有研稀土新材料股份有限公司 | Nitrogen oxide orange-yellow fluorescent powder, and luminescent film containing the fluorescent powder or luminescent sheet containing the fluorescent powder and luminescent device containing the fluorescent powder |
| CN103881706A (en) * | 2012-12-21 | 2014-06-25 | 有研稀土新材料股份有限公司 | Nitrogen oxide fluorescent powder, preparation method thereof and luminescent device containing the fluorescent powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1918262A (en) * | 2003-11-26 | 2007-02-21 | 独立行政法人物质·材料研究机构 | Phosphor and light emission appliance using phosphor |
| US20070259206A1 (en) * | 2004-04-27 | 2007-11-08 | Matsushita Electric Industrial Co., Ltd. | Phosphor Composition and Method for Producing the Same, and Light-Emitting Device Using the Same |
| CN102453485A (en) * | 2010-10-27 | 2012-05-16 | 奇美实业股份有限公司 | Fluorophor and light-emitting device |
| CN102453484A (en) * | 2010-10-15 | 2012-05-16 | 奇美实业股份有限公司 | Phosphor and luminescence device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1845146B1 (en) * | 2005-01-31 | 2015-03-04 | Ube Industries, Ltd. | Red emitting nitride phosphor and process for producing the same |
-
2010
- 2010-11-09 CN CN201810448355.5A patent/CN108456516A/en active Pending
- 2010-11-09 CN CN2010105491552A patent/CN102464979A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1918262A (en) * | 2003-11-26 | 2007-02-21 | 独立行政法人物质·材料研究机构 | Phosphor and light emission appliance using phosphor |
| US20070259206A1 (en) * | 2004-04-27 | 2007-11-08 | Matsushita Electric Industrial Co., Ltd. | Phosphor Composition and Method for Producing the Same, and Light-Emitting Device Using the Same |
| CN102453484A (en) * | 2010-10-15 | 2012-05-16 | 奇美实业股份有限公司 | Phosphor and luminescence device |
| CN102453485A (en) * | 2010-10-27 | 2012-05-16 | 奇美实业股份有限公司 | Fluorophor and light-emitting device |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994079A (en) * | 2012-12-21 | 2013-03-27 | 北京有色金属研究总院 | Nitrogen-oxide orange-red fluorescent material comprising light-emitting film or light-emitting piece and light-emitting device |
| CN103756674A (en) * | 2012-12-21 | 2014-04-30 | 有研稀土新材料股份有限公司 | Oxynitride orange-red fluorescent material as well as light-emitting film or light-emitting sheet and light-emitting element comprising same |
| CN103881718A (en) * | 2012-12-21 | 2014-06-25 | 有研稀土新材料股份有限公司 | Nitrogen oxide orange-yellow fluorescent powder, and luminescent film containing the fluorescent powder or luminescent sheet containing the fluorescent powder and luminescent device containing the fluorescent powder |
| CN103881706A (en) * | 2012-12-21 | 2014-06-25 | 有研稀土新材料股份有限公司 | Nitrogen oxide fluorescent powder, preparation method thereof and luminescent device containing the fluorescent powder |
| WO2014094657A1 (en) * | 2012-12-21 | 2014-06-26 | 有研稀土新材料股份有限公司 | Oxynitride orange-red fluorescent substance and light-emitting film or light-emitting sheet and light-emitting device comprising same |
| KR20150065802A (en) * | 2012-12-21 | 2015-06-15 | 그리렘 어드밴스드 머티리얼스 캄파니 리미티드 | Oxynitride orange-red fluorescent substance and light-emitting film or light-emitting sheet and light-emitting device comprising same |
| CN103881718B (en) * | 2012-12-21 | 2015-10-28 | 有研稀土新材料股份有限公司 | A kind of oxynitride orange-yellow fluorescent powder and containing the luminescent film of this fluorescent material or light tiles, luminescent device |
| CN103881706B (en) * | 2012-12-21 | 2016-01-20 | 有研稀土新材料股份有限公司 | A kind of nitric oxide fluorescent powder, its preparation method and the light-emitting device containing this fluorescent material |
| CN103756674B (en) * | 2012-12-21 | 2016-05-04 | 有研稀土新材料股份有限公司 | Nitrogen oxide orange-red fluorescent material, comprises its luminescent film or light tiles and luminescent device |
| KR101726246B1 (en) * | 2012-12-21 | 2017-04-12 | 그리렘 어드밴스드 머티리얼스 캄파니 리미티드 | Oxynitride orange-red fluorescent substance and light-emitting film or light-emitting sheet and light-emitting device comprising same |
| US9671086B2 (en) | 2012-12-21 | 2017-06-06 | Grirem Advanced Materials Co., Ltd. | Oxynitride orange-red fluorescent substance and light-emitting film or sheet and light-emitting device comprising the same |
| CN103555325A (en) * | 2013-11-01 | 2014-02-05 | 江苏罗化新材料有限公司 | Red nitride fluorescent powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108456516A (en) | 2018-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102443391B (en) | Method for controlling ratio of structural components of fired phosphor, and light-emitting device | |
| JP5442677B2 (en) | Phosphor and light emitting device | |
| CN102433122B (en) | Nitride phosphor, method for producing same, and light-emitting device | |
| JP5129375B2 (en) | Phosphor and light emitting device | |
| JP5770192B2 (en) | Blue light emitting phosphor and light emitting device using the blue light emitting phosphor | |
| CN102753650B (en) | Li-containing alpha-sialon fluorescent particles, method for producing same, illumination device, and image display device | |
| CN103131416A (en) | Phosphor and light emitting device using the same | |
| CN102464979A (en) | Fluorophor and light emitting device | |
| CN102453485A (en) | Fluorophor and light-emitting device | |
| CN102453484B (en) | Phosphor and luminescence device | |
| CN104745190B (en) | fluorescent powder and light-emitting device | |
| JP5756540B2 (en) | Phosphor and light emitting device | |
| JP5129374B2 (en) | Phosphor and light emitting device | |
| CN103881710B (en) | Phosphor and light emitting device | |
| JP5736272B2 (en) | Blue light emitting phosphor and light emitting device using the blue light emitting phosphor | |
| CN103881719B (en) | Phosphor and light emitting device | |
| CN104745189B (en) | Phosphor and light emitting device | |
| TWI374179B (en) | Fluorescent substance and light-emitting device | |
| JP5676729B6 (en) | Phosphor and light emitting device | |
| TWI464236B (en) | Phosphor particle and light emitting device | |
| TW201437329A (en) | Phosphor particle and light emitting device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120523 |
|
| RJ01 | Rejection of invention patent application after publication |