CN105219382A - Eu 2+-Eu 3+codoped fluoaluminate substrate fluorescent powder and synthetic method thereof and application - Google Patents
Eu 2+-Eu 3+codoped fluoaluminate substrate fluorescent powder and synthetic method thereof and application Download PDFInfo
- Publication number
- CN105219382A CN105219382A CN201510650628.0A CN201510650628A CN105219382A CN 105219382 A CN105219382 A CN 105219382A CN 201510650628 A CN201510650628 A CN 201510650628A CN 105219382 A CN105219382 A CN 105219382A
- Authority
- CN
- China
- Prior art keywords
- fluoaluminate
- codoped
- fluorescent powder
- europium
- nitrate
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of Eu
2+-Eu
3+codoped fluoaluminate substrate fluorescent powder, the molecular formula of this fluorescent material is: Ca
12-xal
14o
32f
2: xEu, wherein 0.2 < x < 0.6, the Eu in the molecular structure of this fluorescent material refers to Eu
2+and Eu
3+the mixture coexisted.Reaction times of the present invention is short, and calcining temperature is low, and energy consumption is little, by changing synthesis condition and excitation wavelength, can adjust the intensity of blue emission and red emission, obtaining the light of approximate white light.
Description
Technical field
The present invention relates to fluorescent material field.More particularly, the present invention relates to a kind of Eu
2+-Eu
3+codoped fluoaluminate substrate fluorescent powder and synthetic method thereof and application.
Background technology
Along with global warming and energy dilemma are day by day serious, save energy, emissions reduction, protection of the environment become the much-talked-about topic of current era, wherein find the extensive concern that efficient, energy-conservation lighting source is subject to every profession and trade worker.LED (Lightemittingdiode) is the abbreviation of photodiode, is that 20 th century later are invented and a kind of new type light source grown up.The advantages such as LED has energy consumption low (only having 1/8 of incandescent light energy consumption), the life-span grows (several ten thousand hours), pollution-free (without mercury), radiation spectrum is abundant, luminous efficiency is high, color reducibility good, fast response time (in units of us), be widely used in the multiple fields such as pilot lamp, signal lamp, display screen, backlight, industrial equipments, instrument, landscape light in city, indoor and outdoor general lighting, regarded as the forth generation green illumination light source replacing incandescent light, luminescent lamp and high-voltage gas discharging light by people.
Because white light and daylight are very close, more can reflect the true colors of irradiating object preferably, so white light emitting diode (Whitelightemittingdiode is called for short WLED) has great potentiality as lighting source.At present, the main path obtaining WLED has three kinds: the first utilizes the principle of three primary colours and current fertile red, green, blue three kinds of ultra-high brightness LEDs to mix white in the ratio of light intensity 1: 2: 0.38; The second utilizes super brightness InGaN blue led, its tube core adds a little yttrium aluminum garnet is the fluorescent material of main body, and it can at blue-light excited lower generation yellow green light, and this yellow green light can with the blue light synthesize white light appeared, but due to its luminescence center Ce
3+be transmitted in red light portion critical shortage, cause white light LEDs product color developing poor, be difficult to meet low colour temperature illumination needs, utilize this fluorescent material to be difficult to the white light LEDs of the low colour temperature obtaining below 4000K, particularly below 3000K.This light is as lighting source, undue sombre on visual sense feeling, is difficult to use in interior lighting, therefore must reduces the colour temperature of LED.In addition, when utilizing white light which produces as LCD backlight source, display colour gamut is narrow, color reducibility is poor; The third is development ultraviolet leds, adopt ultraviolet excitation three primary colors fluorescent powder or other fluorescent material, produce the white light that polychrome mixes, its color developing can obtain larger raising, and the main difficulty that this method realizes white light LEDs is to lack suitable red fluorescence powder.Therefore develop efficient red fluorescence powder and become the key realizing white light LEDs.
Eu in rare earth ion
3+there is reasonable luminescent properties, it can be launched monochromaticity is good, quantum yield is high red fluorescence, become one of main raw glowed in red-green-blue.Eu
3+the character such as luminous intensity, fluorescence lifetime and emission peak width very large by the impact of matrix, so select suitable matrix, Eu is mixed in research
3+the luminescent properties of rear fluorescent material is Eu
3+one of emphasis of luminescent material research.Fluoaluminate is the emerging family in phosphor, and compare other fluorescent materials, it has cheap, and matrix containing rare metal Tb, Y, does not have the advantages such as good chemical stability and physical strength.Xia Zhiguo etc. have synthesized the adjustable fluorescent material Ca of a series of new luminescent properties by high temperature solid-state method
2al
3o
6f: Ce
3+, Tb
3+, Ca
2al
3o
6f: 0.08Ce
3+, 0.05Tb
3+be found to have strong green emission, this is based on Ce
3+→ Tb
3+efficient energy trasfer, its energy transfer efficiency is more than 90%.At Ca
2al
3o
6ce in F lattice
3+→ Tb
3+energy transfer mechanism owing to the formation of exchange interaction and Ce-Ce bunch, Ce-Tb bunch should be the reason of high-energy conversion efficiency.The critical range usable concentration cancellation method of transmission ofenergy calculates.Kristin etc., by high temperature solid-state method, have synthesized fluorine oxide fluorescent powder sosoloid Sr under reducing atmosphere
1.975ce
0.025ba (AlO
4f)
1-x(SiO
5)
x, by adjusting component x, maximum emission wavelength can be adjusted to yellow from green, the photoluminescence quantum yield of some samples in synthesized series is confirmed as 70 ± 5%, as x=0.5, sample has good thermal characteristics, only drops to 82% of room temperature strength at the photoluminescence intensities of 160 DEG C.Won-ChulLee etc., by high temperature solid-state method, have synthesized oxyfluoride Sr in reducing atmosphere
3-xm
xal
0.9in
0.1o
4f (M=Ca, Ba, 0.1≤x≤0.7) and Sr
2.5m
0.5al
1-yin
yo
4f (0.05≤y≤0.15) luminescent material, Sr
3-xba
xal
0.9in
0.1o
4f (M=Ca, Ba, 0.1≤x≤0.7) and Sr
2.5m
0.5al
1-yin
yo
4the self-excitation kinetics photoluminescence spectra that F (0.05≤y≤0.15) defect causes can clearly be detected, and is attended by bright orange and yellow utilizing emitted light.What the fluorine oxide fluorescent powder excited near 365nm will be suitable near ultraviolet LED (NUV-LED) excites conversion.
In numerous hydrofluoaluminic acid alkali, Ca
12al
14o
32f
2be a kind of good matrix, it has lot of advantages: (1) from ultraviolet 250nm to the wide transparency range of infrared 800nm; (2) lower specific refractory power, preferably chemical stability and physical strength; (3) fusing point is 1465 DEG C, has good thermostability and lower thermal expansivity; (4) have sensibilized to the luminescence of rare earth ion, matrix can absorb energy and pass to rare earth ion, and in this process, power loss is little, under burst of ultraviolel, have stable luminous efficiency.Due to Ca
12al
14o
32f
2ca in matrix
2+with Eu
3+ionic radius closely (be respectively 99pm and 95pm), according to radius matching principle, Eu
3+easy replacement Ca
2+and enter Ca
2+ion site, forms luminescence center.Huang Kuanwei etc. are once with Ca
12al
14o
32f
2for matrix, adopt the Ca of high temperature solid-state method synthesis
12al
14o
32f
2: Eu
3+fluorescent material, its illumination effect is better, but reactant needs long-time grinding just can mix, and temperature is high, and consume energy higher, size distribution is uneven, and reaction not exclusively, and contains solid material original on a small quantity in product.This seminar once utilized sol-gel method to synthesize Ca
12al
14o
32f
2: Eu
3+nano red fluorescent material.
Owing to restricting by f-f transition choosing rule, Eu
3+spectrum be narrow wire, spectral line intensity is lower, be unfavorable for absorb excitation energy.But by Eu
3+be reduced to Eu
2+after, because of Eu
2+outer electronic structure be 4f
65d
1, 5d track is outside exposed, easily by the impact of environment, 4f can occur
65d
1the transition of → 4f7, this transition is launched in broadband, and intensity is higher, and fluorescence lifetime is short, and emmission spectrum changes with the change of matrix composition, structure, and excitation spectrum is positioned near ultraviolet region, can solve Eu
3+luminous Problems existing, so find a kind of synthetic method by the Eu in fluorescent material
3+be reduced to Eu
2+it is a kind of well approach.
Summary of the invention
An object of the present invention is to solve at least the problems referred to above, and the advantage will illustrated at least is below provided.
A further object of the invention adopts combustion method to synthesize Eu
2+-Eu
3+the Ca coexisted
12-xal
14o
32f
2: xEu fluorescent material, and by changing synthesis condition and excitation wavelength, can Eu be adjusted
2+ion blue emission and Eu
3+the intensity of ion red emission, and then synthesized and level off to the light of white light.
In order to realize, according to these objects of the present invention and other advantage, providing a kind of Eu
2+-Eu
3+codoped fluoaluminate substrate fluorescent powder, the molecular formula of this fluorescent material is: Ca
12-xal
14o
32f
2: xEu, wherein 0.2 < x < 0.6, the Eu in the molecular structure of this fluorescent material refers to Eu
2+and Eu
3+the mixture coexisted.
Preferably, described Eu
2+-Eu
3+codoped fluoaluminate substrate fluorescent powder, described x value is 0.36.
Preferably, described Eu
2+-Eu
3+codoped fluoaluminate substrate fluorescent powder, is characterized in that, the ratio range of trivalent europium ion and divalent europium quantity is 0.73-1.88.
Present invention also offers a kind of technical scheme:
A kind of Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, comprises the following steps:
Step one, take nitrocalcite, Neutral ammonium fluoride, after mixing, adding europium nitrate solution and aluminum nitrate solution, then add urea and boric acid, stirring and evenly mixing, being placed in ultra-sonic oscillation 15min to obtaining clear solution, i.e. presoma;
Step 2, presoma to be placed in preset temp be that the box-type high-temperature furnace of 700-1000 DEG C burns 5-15min, and cooling after taking out, grinding, obtain divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent;
Wherein, described nitrocalcite, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis
12-xal
14o
32f
2: each element chemistry metering in xEu is than taking, and described Neutral ammonium fluoride is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is 4-8: 1 to take with mol ratio, and described urea is 1.5-2.0: 1 to take with mass ratio by the total mass with nitrate, and described nitrate refers to nitrocalcite, europium nitrate and aluminum nitrate, described boric acid by and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is 0.1-0.3: 1 to take with mol ratio.
Preferably, described Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, in described step 2, preset temp is 800-900 DEG C.
Preferably, described Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, burn in described step 2 10min.
Preferably, described Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, described Neutral ammonium fluoride is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 6: 1 with mol ratio.
Preferably, described Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, described urea is by being to take at 1.5: 1 with the total mass of nitrate with mass ratio.
Preferably, described Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, described boric acid is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 0.3: 1 with mol ratio.
Present invention also offers a kind of Eu
2+-Eu
3+the application of codoped fluoaluminate substrate fluorescent powder, the excitation wavelength that this fluorescent material uses is 230-250nm and 320-350nm.
Beneficial effect of the present invention is as follows:
The present invention is with the fluoaluminate Ca of cubic(al)grating framework
12al
14o
32f
2for matrix, take europium ion as activator, Neutral ammonium fluoride is fluorizating agent, and urea is incendiary material, in the reducing atmosphere of burning, obtain Eu
2+and Eu
3+ion coexist, the reaction times is short, and calcining temperature is low, and energy consumption is little, by changing synthesis condition and excitation wavelength, can adjust the intensity of blue emission and red emission, obtaining the light of approximate white light;
Fluorescent material Ca of the present invention
12-xal
14o
32f
2: xEu (Eu
2+and Eu
3+coexisting) desired raw material material is cheap and easy to get, and oxyfluoride has that chemical stability is good, the bombardment that can bear high-energy electron, nonradiative relaxation probability are little and can the advantage such as bandwidth, as the matrix of fluorescent material, effectively can improve luminous efficiency;
The advantage that divalent europium has it incomparable relative to trivalent europium, to be divalent europium and trivalent europium launch advantage in broadband with the coexist advantage that had trivalent europium red-emitting concurrently and divalent europium transition of certain proportion with fluorescent material of the present invention, to make fluorescent phosphor of the present invention good, transition emission band is wider, intensity is good, and excitation spectrum is positioned at ultraviolet region and near ultraviolet region, be easier to absorb energy and release energy, energy discharges also easier in the form of light.
Part is embodied by explanation below by other advantage of the present invention, target and feature, part also will by research and practice of the present invention by those skilled in the art is understood.
Accompanying drawing explanation
Fig. 1 is the fluorescent material Ca that the present invention synthesizes
11.64al
14o
32f
2: the XPS figure of 0.36Eu;
Fig. 2 is the fluorescent material Ca of differing temps of the present invention synthesis
11.64al
14o
32f
2: the XRD figure of 0.36Eu;
The fluorescent material Ca of Fig. 3 (a) for synthesizing under the different Neutral ammonium fluoride addition of the present invention
11.64al
14o
32f
2: the utilizing emitted light spectrogram of 0.36Eu under 239nm excites, Fig. 3 (b) to excite the cie color coordinate diagram of lower correspondence for this fluorescent material at 239nm;
The fluorescent material Ca of Fig. 4 (a) for synthesizing under differing temps of the present invention
11.64al
14o
32f
2: the utilizing emitted light spectrogram of 0.36Eu under 244nm excites; Fig. 4 (b) for excitation wavelength be the cie color coordinate diagram that this light-emitting phosphor is corresponding under 244nm;
The fluorescent material Ca that Fig. 5 (a) synthesizes for different urea addition
11.64al
14o
32f
2: the utilizing emitted light spectrogram of 0.36Eu under 241nm excites, the fluorescent material Ca that Fig. 5 (b) synthesizes for different urea addition
11.64al
14o
32f
2: the utilizing emitted light spectrogram of 0.36Eu under 336nm excites;
The fluorescent material Ca of Fig. 6 (a) different europium nitrate addition synthesis for the present invention records
12-xal
14o
32f
2: the utilizing emitted light spectrogram of xEu under 241nm excites, the fluorescent material Ca that Fig. 6 (b) synthesizes for different europium nitrate addition
12-xal
14o
32f
2: the utilizing emitted light spectrogram of xEu under 336nm excites, the fluorescent material Ca that Fig. 6 (c) synthesizes for different europium nitrate addition
12-xal
14o
32f
2: xEu excites the cie color coordinate diagram of lower correspondence at 241nm;
Fig. 7 (a) is synthetizing phosphor powder Ca under the different boric acid addition of the present invention
11.64al
14o
32f
2: the utilizing emitted light spectrogram of 0.36Eu under 241nm excites; Fig. 7 (b) is synthetizing phosphor powder Ca under different boric acid addition
11.64al
14o
32f
2: the utilizing emitted light spectrogram of 0.36Eu under 332nm excites;
The fluorescent material Ca of Fig. 8 (a) for synthesizing under the different Neutral ammonium fluoride addition of the present invention
11.64al
14o
32f
2: 0.36Eu take 438nm as the exciting light spectrogram of determined wavelength; The fluorescent material Ca of Fig. 8 (b) for synthesizing under different Neutral ammonium fluoride addition
11.64al
14o
32f
2: 0.36Eu take 611nm as the exciting light spectrogram of determined wavelength.
Embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is described in further detail, can implement according to this with reference to specification sheets word to make those skilled in the art.
Should be appreciated that used hereinly such as " to have ", other element one or more do not allotted in " comprising " and " comprising " term or the existence of its combination or interpolation.
The invention provides a kind of Eu
2+-Eu
3+codoped fluoaluminate substrate fluorescent powder, the molecular formula of this fluorescent material is: Ca
12-xal
14o
32f
2: xEu, wherein 0.2 < x < 0.6, the Eu in the molecular structure of this fluorescent material refers to Eu
2+and Eu
3+the mixture coexisted.
Wherein, described Eu
2+-Eu
3+codoped fluoaluminate substrate fluorescent powder, described x value is 0.36.
Wherein, described Eu
2+-Eu
3+codoped fluoaluminate substrate fluorescent powder, is characterized in that, the ratio range of trivalent europium ion and divalent europium quantity is 0.73-1.88.
Present invention also offers a kind of technical scheme:
A kind of Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, comprises the following steps:
Step one, take nitrocalcite, Neutral ammonium fluoride, after mixing, adding europium nitrate solution and aluminum nitrate solution, then add urea and boric acid, stirring and evenly mixing, being placed in ultra-sonic oscillation 15min to obtaining clear solution, i.e. presoma;
Step 2, presoma to be placed in preset temp be that the box-type high-temperature furnace of 700-1000 DEG C burns 5-15min, and cooling after taking out, grinding, obtain divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent;
Wherein, described nitrocalcite, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis
12-xal
14o
32f
2: each element chemistry metering in xEu is than taking, and described Neutral ammonium fluoride is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is 4-8: 1 to take with mol ratio, and described urea is 1.5-2.0: 1 to take with mass ratio by the total mass with nitrate, and described nitrate refers to nitrocalcite, europium nitrate and aluminum nitrate, described boric acid by and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is 0.1-0.3: 1 to take with mol ratio.
Wherein, described Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, in described step 2, preset temp is 800-900 DEG C.
Wherein, described Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, burn in described step 2 10min.
Wherein, described Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, described Neutral ammonium fluoride is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 6: 1 with mol ratio.
Wherein, described Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, described urea is by being to take at 1.5: 1 with the total mass of nitrate with mass ratio.
Wherein, described Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, described boric acid is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 0.3: 1 with mol ratio.
Present invention also offers a kind of Eu
2+-Eu
3+the application of codoped fluoaluminate substrate fluorescent powder, the excitation wavelength that this fluorescent material uses is 230-250nm and 320-350nm.
Embodiment 1:
A kind of Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, comprises the following steps:
Step one, take nitrocalcite, Neutral ammonium fluoride, after mixing, adding europium nitrate solution and aluminum nitrate solution, then add urea and boric acid, stirring and evenly mixing, being placed in ultra-sonic oscillation 15min to obtaining clear solution, i.e. presoma;
Step 2, presoma to be placed in preset temp be that the box-type high-temperature furnace of 700 DEG C burns 5min, and cooling after taking out, grinding, obtain divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent;
Wherein, described nitrocalcite, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis
12-xal
14o
32f
2: each element chemistry metering in xEu is than taking, and described Neutral ammonium fluoride is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 4: 1 with mol ratio, and described urea is by being to take at 1.5: 1 with the total mass of nitrate with mass ratio, and described nitrate refers to nitrocalcite, europium nitrate and aluminum nitrate, described boric acid by and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 0.1: 1 with mol ratio, and wherein x is 0.36.
Embodiment 2:
A kind of Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, comprises the following steps:
Step one, take nitrocalcite, Neutral ammonium fluoride, after mixing, adding europium nitrate solution and aluminum nitrate solution, then add urea and boric acid, stirring and evenly mixing, being placed in ultra-sonic oscillation 15min to obtaining clear solution, i.e. presoma;
Step 2, presoma to be placed in preset temp be that the box-type high-temperature furnace of 800 DEG C burns 10min, and cooling after taking out, grinding, obtain divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent;
Wherein, described nitrocalcite, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis
12-xal
14o
32f
2: each element chemistry metering in xEu is than taking, and described Neutral ammonium fluoride is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 6: 1 with mol ratio, and described urea is by being to take at 1.8: 1 with the total mass of nitrate with mass ratio, and described nitrate refers to nitrocalcite, europium nitrate and aluminum nitrate, described boric acid by and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 0.2: 1 with mol ratio, and wherein x is 0.36.
Embodiment 3:
A kind of Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, comprises the following steps:
Step one, take nitrocalcite, Neutral ammonium fluoride, after mixing, adding europium nitrate solution and aluminum nitrate solution, then add urea and boric acid, stirring and evenly mixing, being placed in ultra-sonic oscillation 15min to obtaining clear solution, i.e. presoma;
Step 2, presoma to be placed in preset temp be that the box-type high-temperature furnace of 1000 DEG C burns 15min, and cooling after taking out, grinding, obtain divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent;
Wherein, described nitrocalcite, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis
12-xal
14o
32f
2: each element chemistry metering in xEu is than taking, and described Neutral ammonium fluoride is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 8: 1 with mol ratio, and described urea is by being to take at 2.0: 1 with the total mass of nitrate with mass ratio, and described nitrate refers to nitrocalcite, europium nitrate and aluminum nitrate, described boric acid by and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 0.3: 1 with mol ratio, and wherein x is 0.36.
Embodiment 4:
A kind of Eu
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, comprises the following steps:
Step one, take nitrocalcite, Neutral ammonium fluoride, after mixing, adding europium nitrate solution and aluminum nitrate solution, then add urea and boric acid, stirring and evenly mixing, being placed in ultra-sonic oscillation 15min to obtaining clear solution, i.e. presoma;
Step 2, presoma to be placed in preset temp be that the box-type high-temperature furnace of 900 DEG C burns 10min, and cooling after taking out, grinding, obtain divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent;
Wherein, described nitrocalcite, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis
12-xal
14o
32f
2: each element chemistry metering in xEu is than taking, and described Neutral ammonium fluoride is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 6: 1 with mol ratio, and described urea is by being to take at 1.5: 1 with the total mass of nitrate with mass ratio, and described nitrate refers to nitrocalcite, europium nitrate and aluminum nitrate, described boric acid by and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 0.3: 1 with mol ratio, and wherein x is 0.36.
Applicant of the present invention has also done following experimental study:
Test 1:
Method according to the present invention has synthesized Ca in embodiment 4
11.64al
14o
32f
2: the fluorescent material of 0.36Eu, records XPS and sees Fig. 1.
Fig. 1 is Ca
11.64al
14o
32f
2: the XPS figure of 0.36Eu, XPS (x-ray photoelectron spectrum) is one of important surface analysis technique, can not only the chemical constitution of searching surface, and can determine the chemical state of each element, and can measure each element track in conjunction with energy.Detecting in Fig. 1 containing Ca, Al, O, F and Eu five kinds of elements in fluorescent material, is comparatively ideal fluorescent material sample, and sample does not cause the loss of principal element because of factors such as calcinings.Wherein Eu3d5/2 and Eu3d3/2 show weak intensity in conjunction with energy.
Test 2:
According to method of the present invention, on the basis of embodiment 4, change temperature of combustion, other synthesis conditions are constant, synthesized fluorescent material Ca by studying different temperature of combustion
11.64al
14o
32f
2: 0.36Eu, and record XRD figure and see Fig. 2.
Fig. 2 is the XRD figure of synthetic sample under differing temps, contrasts with Fig. 2 Plays card, can find out that the lower synthesized fluorescent material sample of differing temps burning is pure phase substantially, illustrate that the fluorescent material purity of combustion synthesis is higher.
Test 3:
According to method of the present invention, on the basis of embodiment 3, change the fluorescent material Ca of Neutral ammonium fluoride and synthesis
11.64al
14o
32f
2: the mol ratio of 0.36Eu, other synthesis conditions are constant, by studying different Neutral ammonium fluoride addition to the impact of synthetizing phosphor powder, and record Ca in fluorescent material sample
11.64al
14o
32f
2: the utilizing emitted light spectrogram of 0.36Eu under 239nm excites is as Fig. 3 (a); Fluorescent material sample excites the cie color coordinate of lower correspondence as Fig. 3 (b) at 239nm.This test 3 is to synthesize the Ca of 0.5mmol
11.64al
14o
32f
2x: 0.36Eu is target, the amount choosing Neutral ammonium fluoride is followed successively by 1.0,2.0,3.0,4.0,5.0mmol, the mol ratio corresponding to the fluorescent material of synthesis is followed successively by 2,4,6,8,10.
From Fig. 3 (a), under 391nm excites, the blue light of phosphor emission 400-500nm and the ruddiness of 580-620nm.Along with NH
4the increase of F amount, the luminous intensity of fluorescent material strengthens gradually, at n (NH
4f)=3.0mmol time, fluorescent material reaches the strongest in the luminous intensity of climax 437nm and 611nm, then along with NH
4the increase of F amount, the luminous intensity of fluorescent material reduces gradually.From Fig. 3 (b), by changing NH
4the addition of F, Ca
11.64al
14o
32f
2: the tristimulus coordinates of 0.36Eu is by (0.3717,0.3381) (0.4177 is changed to, 0.3221), then (0.3823 is arrived, 0.2731), glow color changes to pearl opal by blue-greenish colour, then to mazarine, therefore the point of blue white light field is dropped on comparatively close to white light, light-emitting phosphor better performances.
Test 4:
On the basis of embodiment 4, change temperature of combustion, other synthesis condition is identical, the impact of (700,800,900,1000 DEG C) synthetizing phosphor powder under research differing temps, the fluorescent material Ca synthesized under recording differing temps
11.64al
14o
32f
2: 0.36Eu utilizing emitted light spectrogram is shown in Fig. 4 (a); Excitation wavelength is that the cie color coordinate diagram that under 244nm, this light-emitting phosphor is corresponding is shown in Fig. 4 (b).
From Fig. 4 (a), the blue light strength of fluorescent material at 440nm place reduces gradually along with the rising 700 DEG C-900 DEG C of temperature, 1000 DEG C time blue light strength and 900 DEG C basically identical, collection of illustrative plates almost overlaps, and illustrates that divalent europium change in concentration is less.The red light intensity at 580-620nm place is more weak 700 DEG C time, comparatively strong 1000 DEG C time, changes not quite at 800 DEG C and red light intensity when 900 DEG C, the approximate trend of collection of illustrative plates along with the rising of temperature, Eu in sample
2+amount reduce, Eu
3+amount increase.From Fig. 4 (b), along with the rising of temperature, the glow color of fluorescent material under 244nm excites is adjusted to greenish orange redness from lavender, when temperature be 800 DEG C with 900 DEG C time, light-emitting phosphor color is between lavender and greenish orange redness, color, comparatively close to shallow white, provides a good reference can to synthesis target white light.
Test 5:
On the basis of embodiment 4, change the ratio of urea and nitrate total mass, other synthesis condition is identical, study the impact of synthetizing phosphor powder under different urea addition, wherein, the ratio of urea and nitrate total mass is taken as 0.5,1.0,1.5,2.0,2.5,3.0 successively, records the fluorescent material Ca of different urea addition synthesis
11.64al
14o
32f
2: the utilizing emitted light spectrogram of 0.36Eu under 241nm excites is shown in Fig. 5 (a), records the fluorescent material Ca of different urea addition synthesis
11.64al
14o
32f
2: the utilizing emitted light spectrogram of 0.36Eu under 336nm excites is shown in Fig. 5 (b);
From Fig. 5 (a), under 241nm excites, fluorescent material sends out the blue light of 436nm and the ruddiness of 587nm, 617nm.Along with the increase of urea amount, luminous intensity strengthens gradually and then reduces, at m
urine: m
nitre(m when=1.5
nitre isthe quality of nitrate), ruddiness (612nm) and blue light (441nm) reach the strongest.From Fig. 5 (b), under 336nm excites, the blue light of 400-500nm only launched by fluorescent material.Along with the increase of urea amount, the luminous intensity of fluorescent material strengthens gradually and then lowers.
Test 6:
On the basis of embodiment 4, change the addition of europium nitrate, other synthesis condition is identical, studies different europium nitrate addition to the impact of synthetizing phosphor powder, records the fluorescent material Ca of different europium nitrate addition synthesis
12-xal
14o
32f
2: the utilizing emitted light spectrogram of xEu under 241nm excites is shown in Fig. 6 (a), the fluorescent material Ca of different europium nitrate addition synthesis
12-xal
14o
32f
2: the utilizing emitted light spectrogram of xEu under 336nm excites is shown in Fig. 6 (b), the fluorescent material Ca of different europium nitrate addition synthesis
12-xal
14o
32f
2: xEu excites the cie color coordinate diagram of lower correspondence to see Fig. 6 (c) at 241nm.This test 6 is to synthesize the Ca of 0.5mmol
12-xal
14o
32f
2: xEu is target, synthesis x value is the fluorescent material of 0.12,0.24,0.36,0.48,0.60,0.72, then the amount of europium nitrate be followed successively by 0.06,0.12,0.18,0.24,0.30,0.36mmol, be correspondingly followed successively by 0.12,0.24,0.36,0.48,0.60,0.72 with the mol ratio of the fluorescent material of synthesis.
From Fig. 6 (a), under 241nm excites, the blue light of phosphor emission 437nm and the ruddiness of 586nm, 612nm, ruddiness is obviously better than blue light, this is because the NH in raw material
4 +constant with urea amount, the Eu be reduced into
2+amount also just certain, and Eu
3+amount increase gradually.Along with the increase of europium ion amount, the luminous intensity of 586nm and 612nm strengthens gradually and then reduces.From Fig. 6 (b), under 336nm excites, the blue light of fluorescent material dominant emission 400-500nm, along with the increase of europium concentration, luminous intensity reduces gradually, this is because the NH of six samples
4f is identical with the amount of urea, along with europium concentration increases, is not reduced into Eu
2+eu
3+shared ratio increases gradually, and luminous intensity reduces gradually.Fig. 6 (c) for a change europium addition synthesis Ca
12-xal
14o
32f
2: xEu excites the cie color coordinate diagram of lower correspondence at 241nm, as can be seen from Fig. 6 (c), synthesized by the addition of different europium element, the cie color coordinate of fluorescent material is different, color drops in lavender and orange red region, as x=0.361, light-emitting phosphor color is positioned at lilac region the most, and comparatively other point is the most close to white light, and moderate concentration, be the addition of comparatively ideal europium.
Test 7:
On the basis of embodiment 4, change the addition of boric acid and the fluorescent material Ca of synthesis
11.64al
14o
32f
2: the mol ratio of 0.36Eu, other synthesis condition is identical, studies different boric acid addition to the impact of synthetizing phosphor powder, records synthetizing phosphor powder Ca under different boric acid addition
11.64al
14o
32f
2: the utilizing emitted light spectrogram of 0.36Eu under 241nm excites is shown in Fig. 7 (a); Synthetizing phosphor powder Ca under different boric acid addition
11.64al
14o
32f
2: the utilizing emitted light spectrogram of 0.36Eu under 332nm excites is shown in Fig. 7 (b).This test 7 is to synthesize the Ca of 0.5mmol
11.64al
14o
32f
2: 0.36Eu is target, chooses the mol ratio C of the amount of boric acid and the fluorescent material of synthesis
bbe followed successively by 0,0.1,0.2,0.3,0.4,0.5,0.6.
From Fig. 7 (a), under 241nm excites, the blue light of phosphor emission 400-500nm and the ruddiness of 580-620nm, along with the increase of boric acid addition, luminous intensity increases gradually and then reduces, and works as C
b=0.3 (C
bratio for the amount of substance of boric acid and the amount of substance of product) time, luminous intensity reaches maximum.During combustion synthesis fluorescent material, boric acid can as solubility promoter, and it is favourable to fluorescent material to add a certain amount of boric acid, and it can promote the crystal growth of product, strengthens the luminous intensity of fluorescent material.From Fig. 7 (b), under 332nm excites, the blue light of phosphor emission 400-500nm, along with the increase of boric acid addition, the luminous intensity of fluorescent material shows as at c
b=0,0.1, when 0.2, luminous intensity maximum value is greatly within the scope of 100 ~ 150a.u., works as C
bwhen=0.3, it is the strongest that luminous intensity maximum value is about 260a.u. luminous intensity, and work as c
b=0.4,0.5, when 0.6, luminous intensity maximum value drops on again within the scope of about 100 ~ 150a.u., is similar to reducing tendency after first increasing.Therefore, to C
bthe research of seven variablees in C
bwhen=0.3, phosphor emission peak height is the highest, and peak area is the widest, and luminous intensity is the strongest, so, optimum when the usage quantity of boric acid should be 0.3 with the mol ratio of the fluorescent material of synthesis, luminous intensity can be obtained large, close to the light of white light.
Test 8:
Fig. 8 (a) is different N H
4the addition synthetizing phosphor powder Ca of F
11.64al
14o
32f
2: 0.36Eu take 438nm as the exciting light spectrogram of determined wavelength; Fig. 8 (b) different N H
4the addition synthetizing phosphor powder Ca of F
11.64al
14o
32f
2: 0.36Eu take 611nm as the exciting light spectrogram of determined wavelength.
From Fig. 8 (a), fluorescent material take 438nm as the excitation peak of determined wavelength is the weak band of a 220-280nm and the strong band of a 300-400nm; From Fig. 8 (b), fluorescent material is that the excitation peak of determined wavelength is positioned at 220-280nm with 611nm, excites main peak to be positioned near 240nm, and near 380nm and 390nm, has very weak excitation peak.Work as NH
4the amount of F is less, i.e. Eu
3+when being reduced few, the main peak that excites of fluorescent material is positioned near 240nm, and it belongs to O
2--Eu
3+charge migration absorb; Work as NH
4the amount of F is more, i.e. Eu
3+when being reduced many, the main peak that excites of fluorescent material is positioned near 340nm, belongs to Eu
2+4f-5d energy level transition absorb; Very weak excitation peak is had to belong to Eu near 380nm and 390nm
3+4f-4f transition.
Inventive samples does when fluorescence detects and first sample is done ultraviolet-visible absorption, generally using the wavelength at maximum absorption wavelength or isobestic point place as excitation wavelength, in general this (or these) peak is exactly fluorescence peak, because the position of fluorescence peak does not change with the change of excitation wavelength, only that peak height (or peak area) changes, with reference to the characteristic of fluorescence spectrum----excite and the feature of launching in mirror image to determine excitation wavelength.Be 220-280nm and 300-400nm excitated fluorescent powder by excitation wavelength in this experiment, absorption is had at 400nm-700nm place, wherein so that about 450nm, 616nm are absorbed as stronger, then with 438nm, 616nm for determined wavelength excitated fluorescent powder, then there is absorption at 220-280nm and 300-400nm place, neighbouring with 241nm, 336nm is the strongest.
Comprehensive observing Fig. 8 (a) is known with Fig. 8 (b) two collection of illustrative plates, works as NH
4during F=3mmol, absorb comparatively strong, moderate concentration is comparatively ideal concentration.
Test 9:
The single factor experiment drawn in 7 is tested by test 3-, by the fluorescent material synthesized under differential responses synthesis condition one to one in Fig. 3 (a), Fig. 4 (a), Fig. 5 (a), Fig. 6 (a), Fig. 7 (a), get the luminous intensity of spectrum area as divalent europium of wavelength 400-550nm, get the luminous intensity of spectrum area as trivalent europium of wavelength 550-700nm, then trivalent europium and divalent europium and red blue light ratio (i.e. red/blue light area ratio) are in table 1, show that the ratio range of the amount of trivalent europium and divalent europium in fluorescent material is 0.73-1.88.
Red blue light area ratio under table 1 different tests condition
Although embodiment of the present invention are open as above, but it is not restricted to listed in specification sheets and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend described.
Claims (10)
1. an Eu
2+-Eu
3+codoped fluoaluminate substrate fluorescent powder, is characterized in that, the molecular formula of this fluorescent material is: Ca
12-xal
14o
32f
2: xEu, wherein 0.2 < x < 0.6, the Eu in the molecular structure of this fluorescent material refers to Eu
2+and Eu
3+the mixture coexisted.
2. Eu as claimed in claim 1
2+-Eu
3+codoped fluoaluminate substrate fluorescent powder, is characterized in that, described x value is 0.36.
3. Eu as claimed in claim 2
2+-Eu
3+codoped fluoaluminate substrate fluorescent powder, is characterized in that, the ratio range of trivalent europium ion and divalent europium quantity is 0.73-1.88.
4. one kind as the Eu as described in arbitrary in claim 1-3
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, is characterized in that, comprise the following steps:
Step one, take nitrocalcite, Neutral ammonium fluoride, after mixing, adding europium nitrate solution and aluminum nitrate solution, then add urea and boric acid, stirring and evenly mixing, being placed in ultra-sonic oscillation 15min to obtaining clear solution, i.e. presoma;
Step 2, presoma to be placed in preset temp be that the box-type high-temperature furnace of 700-1000 DEG C burns 5-15min, and cooling after taking out, grinding, obtain divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent;
Wherein, described nitrocalcite, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis
12-xal
14o
32f
2: each element chemistry metering in xEu is than taking, and described Neutral ammonium fluoride is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is 4-8: 1 to take with mol ratio, and described urea is 1.5-2.0: 1 to take with mass ratio by the total mass with nitrate, and described nitrate refers to nitrocalcite, europium nitrate and aluminum nitrate, described boric acid by and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is 0.1-0.3: 1 to take with mol ratio.
5. Eu as claimed in claim 4
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, is characterized in that, in described step 2, preset temp is 800-900 DEG C.
6. Eu as claimed in claim 4
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, is characterized in that, burn in described step 2 10min.
7. Eu as claimed in claim 4
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, is characterized in that, described Neutral ammonium fluoride is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 6: 1 with mol ratio.
8. Eu as claimed in claim 4
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, is characterized in that, described urea is by being to take at 1.5: 1 with the total mass of nitrate with mass ratio.
9. Eu as claimed in claim 4
2+-Eu
3+the synthetic method of codoped fluoaluminate substrate fluorescent powder, is characterized in that, described boric acid is pressed and synthesis Ca
12-xal
14o
32f
2: the amount of xEu is to take at 0.3: 1 with mol ratio.
10. one kind as the Eu as described in arbitrary in claim 1-3
2+-Eu
3+the application of codoped fluoaluminate substrate fluorescent powder, is characterized in that, the excitation wavelength that this fluorescent material uses is 230-250nm and 320-350nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510650628.0A CN105219382B (en) | 2015-10-10 | 2015-10-10 | Eu2+ Eu3+ codope fluoaluminate substrate fluorescent powders and its synthetic method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510650628.0A CN105219382B (en) | 2015-10-10 | 2015-10-10 | Eu2+ Eu3+ codope fluoaluminate substrate fluorescent powders and its synthetic method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105219382A true CN105219382A (en) | 2016-01-06 |
| CN105219382B CN105219382B (en) | 2017-05-31 |
Family
ID=54988667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510650628.0A Expired - Fee Related CN105219382B (en) | 2015-10-10 | 2015-10-10 | Eu2+ Eu3+ codope fluoaluminate substrate fluorescent powders and its synthetic method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105219382B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987828A (en) * | 2017-12-29 | 2018-05-04 | 河北工业大学 | A kind of mayenite structure fluorescent powder of LED white light emissions |
| CN108384536A (en) * | 2018-05-16 | 2018-08-10 | 长春理工大学 | Er3+/Yb3+Codope calcium aluminum fluoride green up conversion luminescent material and preparation method thereof |
| CN108410453A (en) * | 2018-03-12 | 2018-08-17 | 盐城工学院 | Europium adulterates single-matrix white fluorescent material and its preparation method and application |
| CN108949172A (en) * | 2018-07-25 | 2018-12-07 | 河南大学 | A kind of fluorescent powder and preparation method thereof of tunable radiation emitting color |
| CN110872512A (en) * | 2018-08-30 | 2020-03-10 | 长春理工大学 | Bismuth ion activated calcium fluoroaluminate blue fluorescent powder and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484112A (en) * | 2013-09-05 | 2014-01-01 | 青岛大学 | Rare-earth europium-activated single-component white-light fluorescent powder and preparation method thereof |
| CN104119888A (en) * | 2014-08-06 | 2014-10-29 | 广西师范学院 | Europium-doped fluoroaluminate matrix fluorescent powder and preparation method thereof |
-
2015
- 2015-10-10 CN CN201510650628.0A patent/CN105219382B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484112A (en) * | 2013-09-05 | 2014-01-01 | 青岛大学 | Rare-earth europium-activated single-component white-light fluorescent powder and preparation method thereof |
| CN104119888A (en) * | 2014-08-06 | 2014-10-29 | 广西师范学院 | Europium-doped fluoroaluminate matrix fluorescent powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZIQIANG JIANG等: "Crystal structure and luminescence properties of Eu2+ activated Sr12Al14O32Cl2: A potential green-emitting phosphor for near UV light-emitting diodes", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987828A (en) * | 2017-12-29 | 2018-05-04 | 河北工业大学 | A kind of mayenite structure fluorescent powder of LED white light emissions |
| CN108410453A (en) * | 2018-03-12 | 2018-08-17 | 盐城工学院 | Europium adulterates single-matrix white fluorescent material and its preparation method and application |
| CN108410453B (en) * | 2018-03-12 | 2021-04-13 | 盐城工学院 | Europium-doped single-matrix white-light fluorescent material and preparation method and application thereof |
| CN108384536A (en) * | 2018-05-16 | 2018-08-10 | 长春理工大学 | Er3+/Yb3+Codope calcium aluminum fluoride green up conversion luminescent material and preparation method thereof |
| CN108949172A (en) * | 2018-07-25 | 2018-12-07 | 河南大学 | A kind of fluorescent powder and preparation method thereof of tunable radiation emitting color |
| CN108949172B (en) * | 2018-07-25 | 2021-04-06 | 河南大学 | Fluorescent powder with adjustable luminous color and preparation method thereof |
| CN110872512A (en) * | 2018-08-30 | 2020-03-10 | 长春理工大学 | Bismuth ion activated calcium fluoroaluminate blue fluorescent powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105219382B (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kuo et al. | Synthesis and luminescence properties of Eu3+, Ce3+ and Tb3+-activated Sr3La2 (BO3) 4 under UV excitation | |
| CN105219382B (en) | Eu2+ Eu3+ codope fluoaluminate substrate fluorescent powders and its synthetic method and application | |
| CN105331364A (en) | YAG:Mn red phosphor, preparation method and applications thereof | |
| Guo et al. | Blue-white-yellow tunable emission from Ce3+ and Eu2+ Co-doped BaSiO3 phosphors | |
| CN102559179B (en) | Single-matrix white light fluorescent powder for white light light-emitting diode (LED) and preparation method thereof | |
| CN105778913A (en) | Single-matrix triple-doped white fluorescent material and preparation method and application thereof | |
| Hong et al. | Photoluminescence properties of Tb3+ and Ce3+ co-doped Sr2MgSi2O7 phosphors for solid-state lighting | |
| Yan et al. | Color-tunable Al 6 Si 2 O 13: Eu 2+, Mn 2+ phosphor with high color rendering index based on energy transfer for warm white LEDs | |
| Zhong et al. | The self-reduction synthesis and luminescent properties of color-tunable BaSnxSi3O7+ 2x: Eu2+-Eu3+ phosphors with high quantum efficiency for white light-emitting diodes | |
| CN101402857A (en) | Red luminous material for LED and producing process thereof | |
| CN102994086B (en) | Red phosphor suitable for ultraviolet light excitation, and preparation method thereof | |
| Qu et al. | Wide-band blue-emitting in Ce3+ doped Ca2YZr2Al3O12 garnet-type phosphor designed via local structural lattice distortion and synthesized in nonreducing atmosphere | |
| CN109957403A (en) | A kind of Eu3+Activate fluoboric acid strontium barium red fluorescence powder and its preparation and application | |
| CN110003908A (en) | White light LEDs silicate red fluorescent powder and preparation method and White LED light-emitting device | |
| CN106634997A (en) | Composite phosphate fluorophor and application thereof | |
| Zhao et al. | Novel color tunable phosphors NaYGeO 4: Tm 3+, Tb 3+, Eu 3+ for ultraviolet excited white LEDs with good thermal stability | |
| CN101760191B (en) | High-brightness barium-silicate-based blue-green fluorescent powder for LED and high-temperature reducing preparation method thereof | |
| CN107353900A (en) | A kind of niobates fluorescent material, its preparation method and light emitting diode | |
| Rajagopal et al. | Rare earth free BaZnBO3F: Bi2+ phosphor with a narrow-band red emission | |
| CN106634996A (en) | Fluorophor and application method thereof | |
| CN103275705A (en) | Fluorescent powder, preparation method thereof and light-emitting device comprising same | |
| CN102936497B (en) | Main emission peak changeable and adjustable fluorescent material and preparation method thereof | |
| CN102181284A (en) | Ultraviolet excited or near ultraviolet excited borate fluorescent powder and preparation method thereof | |
| CN102399554B (en) | Nitride red luminescence material, and luminescent part and luminescent device containing the same | |
| Wu et al. | Triple luminescent center energy transfer enables color tuning in Na3Y (PO4) 2: RE3+ (RE= Tb/Eu/Tm) for w-LEDs |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170531 Termination date: 20181010 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |