CN105219382B - Eu2+ Eu3+ codope fluoaluminate substrate fluorescent powders and its synthetic method and application - Google Patents
Eu2+ Eu3+ codope fluoaluminate substrate fluorescent powders and its synthetic method and application Download PDFInfo
- Publication number
- CN105219382B CN105219382B CN201510650628.0A CN201510650628A CN105219382B CN 105219382 B CN105219382 B CN 105219382B CN 201510650628 A CN201510650628 A CN 201510650628A CN 105219382 B CN105219382 B CN 105219382B
- Authority
- CN
- China
- Prior art keywords
- nitrate
- fluoaluminate
- europium
- synthesis
- codope
- 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.)
- Expired - Fee Related
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
Abstract
The invention discloses a kind of Eu2+‑Eu3+Codope fluoaluminate substrate fluorescent powder, the molecular formula of the fluorescent material is：Ca12‑ xAl14O32F2：XEu, wherein 0.2 ＜ x ＜ 0.6, the Eu in the molecular structure of the fluorescent material refers to Eu2+And Eu3+The mixture for coexisting.Reaction time of the invention is short, and calcining heat is low, and energy consumption is small, by changing synthesis condition and excitation wavelength, can adjust the intensity of blue emission and red emission, obtains the light of approximate white light.
Description
Technical field
The present invention relates to fluorescent material field.It is more particularly related to a kind of Eu2+-Eu3+Codope fluoaluminate
Substrate fluorescent powder and its synthetic method and application.
Background technology
As global warming and energy crisis are increasingly serious, energy saving, reduction discharge, environmental protection turn into current
The much-talked-about topic in epoch, wherein the lighting source for finding efficient, energy-conservation is subject to the extensive concern of every profession and trade worker.LED
(Light emitting diode) is the abbreviation of light emitting diode, and be that 20 th century laters are invented and grown up is a kind of new
Light source.LED has energy consumption low (only the 1/8 of incandescent lamp energy consumption), long lifespan (tens of thousands of hours), pollution-free (mercury-free), radiant light
Spectrum is abundant, luminous efficiency is high, color reducibility is good, fast response time (in units of us) the advantages of, be widely used in referring to
Show that lamp, signal lamp, display screen, backlight, industrial equipment, instrument and meter, landscape light in city, indoor and outdoor general lighting etc. are various
Field, is regarded as the forth generation green illumination light source of substitution incandescent lamp, fluorescent lamp and high-voltage gas discharging light by people.
Because white light is very close to daylight, more can preferably reflect the true colors of irradiation object, so white-light emitting
Diode (White light emitting diode, abbreviation WLED) has great potentiality as lighting source.At present, obtain
Taking the main path of WLED has three kinds：The first is using the principle of three primary colours and current three kinds of superelevation of fertile red, green, blue
Brightness LED mixes white in the ratio of light intensity 1: 2: 0.38；Second is its pipe using super brightness InGaN blue leds
Plus fraction of yttrium-aluminium-garnet it is the fluorescent material of main body on core, it can excite lower generation green-yellow light in blue light, and this green-yellow light
White light can be synthesized with the blue light for appearing again, but due to its centre of luminescence Ce3+Be transmitted in red light portion critical shortage, cause white light
LED product colour rendering is poor, it is difficult to meet low colour temperature illumination needs, is difficult to obtain below 4000K using the fluorescent material, is particularly
The white light LEDs of the low colour temperature of below 3000K.This light is undue sombre on visual sense feeling, it is difficult to for room as lighting source
Intraoral illumination, it is therefore necessary to reduce the colour temperature of LED.Additionally, when white light is as LCD backlight source produced by which,
Display colour gamut is narrow, color reducibility is poor；The third be develop ultraviolet leds, using ultraviolet excitation three primary colors fluorescent powder or its
His fluorescent material, the white light for producing polychrome to mix, its colour rendering can obtain larger raising, and this method realizes white light LEDs
Main difficulty be to lack suitable red fluorescence powder.Therefore develop efficient red fluorescence powder turn into realize white light LEDs
It is crucial.
Eu in rare earth ion3+With relatively good luminescent properties, it is red glimmering that it can launch, and monochromaticjty is good, quantum efficiency is high
Light, it has also become one of main material glowed in red-green-blue.Eu3+Luminous intensity, fluorescence lifetime and transmitting peak width
The property such as narrow is influenceed very big by matrix, so selecting suitable matrix, research mixes Eu3+Luminescent properties of fluorescent material afterwards, be
Eu3+One of emphasis of luminescent material research.Fluoaluminate is the emerging family in phosphor, compared to other phosphors
Material, its have it is cheap, matrix be free of rare metal Tb, Y, have the advantages that preferable chemical stability and mechanical strength.Summer
Will state etc. has synthesized a series of adjustable fluorescent material Ca of new luminescent properties by high temperature solid-state method2Al3O6F∶Ce3+, Tb3+,
Ca2Al3O6F∶0.08Ce3+, 0.05Tb3+Strong green emission is found to have, this is based on Ce3+→Tb3+Efficient energy
Transfer, its energy transfer efficiency is more than 90%.In Ca2Al3O6Ce in F lattices3+→Tb3+Energy transfer mechanism be attributed to exchange
Interact and Ce-Ce clusters formation, the reason for Ce-Tb clusters should be high-energy conversion efficiency.The critical distance of energy transmission
Usable concentration is quenched method calculating.Kristin etc. has been synthesized fluorine oxide fluorescent powder and has been consolidated under reducing atmosphere by high temperature solid-state method
Solution Sr1.975Ce0.025Ba(AlO4F)1-x(SiO5)x, by adjusting component x, maximum emission wavelength can be from green regulation to Huang
Color, the photoluminescence quantum yield of some samples in synthesized series is confirmed as 70 ± 5%, and as x=0.5, sample has
Good hot property, the 82% of room temperature strength is only dropped in 160 DEG C of photoluminescence intensities.Won-Chul Lee etc. are by height
Warm solid phase method, has synthesized oxyfluoride Sr in reducing atmosphere3-xMxAl0.9In0.1O4F (M=Ca, Ba, 0.1≤x≤0.7) and
Sr2.5M0.5Al1-yInyO4F (0.05≤y≤0.15) luminescent material, Sr3-xBaxAl0.9In0.1O4F (M=Ca, Ba, 0.1≤x≤
And Sr 0.7)2.5M0.5Al1-yInyO4The self-excitation dynamics photoluminescence spectra that F (0.05≤y≤0.15) defect causes can be clear
Be detected, and with bright orange and yellow emission light.The fluorine oxide fluorescent powder excited near 365nm will be adapted to
Conversion is excited near ultraviolet LED (NUV-LED).
In numerous fluoaluminic acid alkali, Ca12Al14O32F2It is a kind of good matrix, it has lot of advantages：(1) from purple
The transparency range wide of outer 250nm infrared 800nm in；(2) lower refractive index, preferable chemical stability and mechanical strength；
(3) fusing point is 1465 DEG C, there is good heat endurance and relatively low thermal coefficient of expansion；(4) to the luminous with quick of rare earth ion
Change is acted on, and matrix with energy absorption and can pass to rare earth ion, and during this energy loss seldom, under burst of ultraviolel
There is the luminous efficiency of stabilization.Due to Ca12Al14O32F2Ca in matrix2+With Eu3+Ionic radius closely (respectively 99pm
And 95pm), according to radius matching principle, Eu3+Easily replace Ca2+And enter Ca2+Ion site, forms the centre of luminescence.Huang Kuanwei
Deng once with Ca12Al14O32F2It is matrix, the Ca synthesized using high temperature solid-state method12Al14O32F2∶Eu3+Fluorescent material, its illumination effect
Preferably, but reactant needs the grinding for a long time could be well mixed, and temperature is high, and power consumption is higher, and particle diameter distribution is uneven, reacts
Not exclusively, and in product a small amount of original solid material is contained.This seminar is once synthesized using sol-gel process
Ca12Al14O32F2∶Eu3+Nano red fluorescent material.
Due to by f-f transition choosing rule restriction, Eu3+Spectrum be in narrow wire, the intensity of spectral line is relatively low, is unfavorable for that absorption is excited
Energy.But by Eu3+It is reduced to Eu2+Afterwards, because of Eu2+Outer electronic structure be 4f65d1, 5d tracks are exposed outside, easily by environment
Influence, 4f can occur65d1The transition of → 4f7, this transition transmitting is in broadband, and intensity is higher, and fluorescence lifetime is short, emission spectrum
Changed with matrix composition, the change of structure, and excitation spectrum is located near ultraviolet band, can solve Eu3+It is luminous to deposit
Problem, so finding a kind of synthetic method by the Eu in fluorescent material3+It is reduced to Eu2+It is a kind of good approach.
The content of the invention
It is an object of the invention to solve at least the above, and provide the advantage that at least will be described later.
A further object of the invention is can to synthesize Eu using combustion method2+-Eu3+The Ca for coexisting12-xAl14O32F2∶xEu
Fluorescent material, and by changing synthesis condition and excitation wavelength, Eu can be adjusted2+Ion blue emission and Eu3+Ion red emission
Intensity, and then synthesized and leveled off to the light of white light.
In order to realize these purposes of the invention and further advantage, there is provided a kind of Eu2+-Eu3+Codope fluoaluminic acid
Base status fluorescent material, the molecular formula of the fluorescent material is：Ca12-xAl14O32F2: xEu, wherein 0.2 ＜ x ＜ 0.6, the fluorescent material point
Eu in minor structure refers to Eu2+And Eu3+The mixture for coexisting.
Preferably, described Eu2+-Eu3+Codope fluoaluminate substrate fluorescent powder, the x values are 0.36.
Preferably, described Eu2+-Eu3+Codope fluoaluminate substrate fluorescent powder, it is characterised in that trivalent europium ion
It is 0.73-1.88 with the ratio range of divalent europium quantity.
Present invention also offers a kind of technical scheme：
A kind of Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, comprises the following steps：
Step one, calcium nitrate, ammonium fluoride are weighed, after mixing, add europium nitrate solution and aluminum nitrate solution, add urea
And boric acid, stir and evenly mix, supersonic oscillations 15min is placed in obtaining clear solution, i.e. presoma；
Step 2, presoma is placed in preset temperature is the 5-15min that burns in 700-1000 DEG C of box-type high-temperature furnace, is taken out
Cool down afterwards, grind, obtain divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent；
Wherein, the calcium nitrate, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis12-xAl14O32F2: each unit in xEu
Plain stoichiometric proportion is weighed, and the ammonium fluoride is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is with mol ratio as 4-8: 1 weighs, institute
Urea is stated by the gross mass with nitrate with mass ratio as 1.5-2.0: 1 weighs, the nitrate refer to calcium nitrate, europium nitrate and
Aluminum nitrate, the boric acid is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is with mol ratio as 0.1-0.3: 1 weighs.
Preferably, described Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, the step 2
Middle preset temperature is 800-900 DEG C.
Preferably, described Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, the step 2
Middle burning 10min.
Preferably, described Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, the ammonium fluoride
By with synthesis Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 6: 1.
Preferably, described Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, the urea is pressed
Gross mass with nitrate is weighed with mass ratio as 1.5: 1.
Preferably, described Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, the boric acid is pressed
With synthesis Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 0.3: 1.
Present invention also offers a kind of Eu2+-Eu3+The application of codope fluoaluminate substrate fluorescent powder, the fluorescent material is used
Excitation wavelength be 230-250nm and 320-350nm.
Beneficial effects of the present invention are as follows：
The present invention is with the fluoaluminate Ca of cubic lattice framework12Al14O32F2It is matrix, with europium ion as activator, fluorination
Ammonium is fluorization agent, and urea is incendiary agent, and Eu is obtained in the reducing atmosphere of burning2+And Eu3+Ion coexists, and the reaction time is short, forges
Burning temperature is low, and energy consumption is small, by changing synthesis condition and excitation wavelength, can adjust the strength ratio of blue emission and red emission
Example, obtains the light of approximate white light；
Fluorescent material Ca of the invention12-xAl14O32F2∶xEu(Eu2+And Eu3+Coexist) needed for raw material it is cheap and easy to get, fluorine
Oxide has the advantages that chemical stability is good, can bear high energy electron bombardment, nonradiative relaxation probability it is small and can bandwidth,
As the matrix of fluorescent material, luminous efficiency can be effectively improved；
Divalent europium has the advantages that its is incomparable relative to trivalent europium, fluorescent material of the invention be divalent europium and trivalent europium with
Certain proportion coexist had concurrently trivalent europium transmitting feux rouges advantage and divalent europium transition transmitting in broadband advantage so that this hair
Bright fluorescent phosphor is good, and transition emission band is wider, and intensity is good, and excitation spectrum is located at ultra-violet (UV) band and near ultraviolet band, compared with
Easy energy absorption and releasing energy, energy discharge be also easier in the form of light.
Further advantage of the invention, target and feature embody part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Brief description of the drawings
Fig. 1 is the fluorescent material Ca of present invention synthesis11.64Al14O32F2: the XPS figures of 0.36Eu；
Fig. 2 is the fluorescent material Ca of different temperatures synthesis of the present invention11.64Al14O32F2: the XRD of 0.36Eu；
Fig. 3 (a) is the fluorescent material Ca of synthesis under difference ammonium fluoride addition of the invention11.64Al14O32F2: 0.36Eu exists
239nm excite under launching light spectrogram, Fig. 3 (b) be the fluorescent material corresponding cie color coordinate diagram in the case where 239nm is excited；
Fig. 4 (a) is the fluorescent material Ca of synthesis under different temperatures of the present invention11.64Al14O32F2: 0.36Eu is in the case where 244nm is excited
Launching light spectrogram；Fig. 4 (b) is that excitation wavelength is the corresponding cie color coordinate diagram of the light-emitting phosphor under 244nm；
Fig. 5 (a) is the fluorescent material Ca of different urea addition synthesis11.64Al14O32F2: 0.36Eu is in the case where 241nm is excited
Launching light spectrogram, Fig. 5 (b) is the fluorescent material Ca of different urea addition synthesis11.64Al14O32F2: 0.36Eu is excited in 336nm
Under launching light spectrogram；
Fig. 6 (a) is the fluorescent material Ca that the present invention measures different europium nitrate addition synthesis12-xAl14O32F2: xEu is in 241nm
Launching light spectrogram under exciting, Fig. 6 (b) is the fluorescent material Ca of different europium nitrate addition synthesis12-xAl14O32F2: xEu exists
336nm excite under launching light spectrogram, Fig. 6 (c) is the fluorescent material Ca of different europium nitrate additions synthesis12-xAl14O32F2∶xEu
The corresponding cie color coordinate diagram in the case where 241nm is excited；
Fig. 7 (a) is synthetizing phosphor powder Ca under present invention difference boric acid addition11.64Al14O32F2: 0.36Eu swashs in 241nm
The launching light spectrogram given；Fig. 7 (b) is synthetizing phosphor powder Ca under different boric acid additions11.64Al14O32F2: 0.36Eu exists
332nm excite under launching light spectrogram；
Fig. 8 (a) is the fluorescent material Ca of synthesis under difference ammonium fluoride addition of the invention11.64Al14O32F2: 0.36Eu with
438nm is the exciting light spectrogram of Detection wavelength；Fig. 8 (b) is the fluorescent material of synthesis under different ammonium fluoride additions
Ca11.64Al14O32F2: exciting light spectrograms of the 0.36Eu with 611nm as Detection wavelength.
Specific embodiment
With reference to specific embodiments and the drawings, the present invention is described in further detail, to make those skilled in the art
Can implement according to this with reference to specification word.
It should be appreciated that it is used herein such as " have ", "comprising" and " including " term do not allot one or many
The presence or addition of individual other elements or its combination.
The present invention provides a kind of Eu2+-Eu3+Codope fluoaluminate substrate fluorescent powder, the molecular formula of the fluorescent material is：
Ca12-xAl14O32F2: xEu, wherein 0.2 ＜ x ＜ 0.6, the Eu in the molecular structure of the fluorescent material refers to Eu2+And Eu3+Coexist
Mixture.
Wherein, described Eu2+-Eu3+Codope fluoaluminate substrate fluorescent powder, the x values are 0.36.
Wherein, described Eu2+-Eu3+Codope fluoaluminate substrate fluorescent powder, it is characterised in that trivalent europium ion and two
The ratio range of valency europium ion quantity is 0.73-1.88.
Present invention also offers a kind of technical scheme：
A kind of Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, comprises the following steps：
Step one, calcium nitrate, ammonium fluoride are weighed, after mixing, add europium nitrate solution and aluminum nitrate solution, add urea
And boric acid, stir and evenly mix, supersonic oscillations 15min is placed in obtaining clear solution, i.e. presoma；
Step 2, presoma is placed in preset temperature is the 5-15min that burns in 700-1000 DEG C of box-type high-temperature furnace, is taken out
Cool down afterwards, grind, obtain divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent；
Wherein, the calcium nitrate, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis12-xAl14O32F2: each unit in xEu
Plain stoichiometric proportion is weighed, and the ammonium fluoride is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is with mol ratio as 4-8: 1 weighs, institute
Urea is stated by the gross mass with nitrate with mass ratio as 1.5-2.0: 1 weighs, the nitrate refer to calcium nitrate, europium nitrate and
Aluminum nitrate, the boric acid is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is with mol ratio as 0.1-0.3: 1 weighs.
Wherein, described Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, it is pre- in the step 2
If temperature is 800-900 DEG C.
Wherein, described Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, fires in the step 2
Burn 10min.
Wherein, described Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, the ammonium fluoride press with
Synthesis Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 6: 1.
Wherein, described Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, the urea is pressed and nitre
The gross mass of hydrochlorate is weighed with mass ratio as 1.5: 1.
Wherein, described Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, the boric acid is pressed and conjunction
Into Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 0.3: 1.
Present invention also offers a kind of Eu2+-Eu3+The application of codope fluoaluminate substrate fluorescent powder, the fluorescent material is used
Excitation wavelength be 230-250nm and 320-350nm.
Embodiment 1：
A kind of Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, comprises the following steps：
Step one, calcium nitrate, ammonium fluoride are weighed, after mixing, add europium nitrate solution and aluminum nitrate solution, add urea
And boric acid, stir and evenly mix, supersonic oscillations 15min is placed in obtaining clear solution, i.e. presoma；
Step 2, presoma is placed in the 5min that burnt in the box-type high-temperature furnace that preset temperature is 700 DEG C, cooling after taking-up,
Grinding, obtains divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent；
Wherein, the calcium nitrate, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis12-xAl14O32F2: each unit in xEu
Plain stoichiometric proportion is weighed, and the ammonium fluoride is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 4: 1, described
By being weighed with mass ratio as 1.5: 1 with the gross mass of nitrate, the nitrate refers to calcium nitrate, europium nitrate and nitric acid to urea
Aluminium, the boric acid is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 0.1: 1, and wherein x is 0.36.
Embodiment 2：
A kind of Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, comprises the following steps：
Step one, calcium nitrate, ammonium fluoride are weighed, after mixing, add europium nitrate solution and aluminum nitrate solution, add urea
And boric acid, stir and evenly mix, supersonic oscillations 15min is placed in obtaining clear solution, i.e. presoma；
Step 2, presoma is placed in the 10min that burnt in the box-type high-temperature furnace that preset temperature is 800 DEG C, cooling after taking-up,
Grinding, obtains divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent；
Wherein, the calcium nitrate, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis12-xAl14O32F2: each unit in xEu
Plain stoichiometric proportion is weighed, and the ammonium fluoride is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 6: 1, described
By being weighed with mass ratio as 1.8: 1 with the gross mass of nitrate, the nitrate refers to calcium nitrate, europium nitrate and nitric acid to urea
Aluminium, the boric acid is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 0.2: 1, and wherein x is 0.36.
Embodiment 3：
A kind of Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, comprises the following steps：
Step one, calcium nitrate, ammonium fluoride are weighed, after mixing, add europium nitrate solution and aluminum nitrate solution, add urea
And boric acid, stir and evenly mix, supersonic oscillations 15min is placed in obtaining clear solution, i.e. presoma；
Step 2, presoma is placed in the 15min that burnt in the box-type high-temperature furnace that preset temperature is 1000 DEG C, it is cold after taking-up
But, grind, obtain divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent；
Wherein, the calcium nitrate, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis12-xAl14O32F2: each unit in xEu
Plain stoichiometric proportion is weighed, and the ammonium fluoride is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 8: 1, described
By being weighed with mass ratio as 2.0: 1 with the gross mass of nitrate, the nitrate refers to calcium nitrate, europium nitrate and nitric acid to urea
Aluminium, the boric acid is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 0.3: 1, and wherein x is 0.36.
Embodiment 4：
A kind of Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, comprises the following steps：
Step one, calcium nitrate, ammonium fluoride are weighed, after mixing, add europium nitrate solution and aluminum nitrate solution, add urea
And boric acid, stir and evenly mix, supersonic oscillations 15min is placed in obtaining clear solution, i.e. presoma；
Step 2, presoma is placed in the 10min that burnt in the box-type high-temperature furnace that preset temperature is 900 DEG C, cooling after taking-up,
Grinding, obtains divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent；
Wherein, the calcium nitrate, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis12-xAl14O32F2: each unit in xEu
Plain stoichiometric proportion is weighed, and the ammonium fluoride is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 6: 1, described
By being weighed with mass ratio as 1.5: 1 with the gross mass of nitrate, the nitrate refers to calcium nitrate, europium nitrate and nitric acid to urea
Aluminium, the boric acid is pressed and synthesis Ca12-xAl14O32F2: the amount of xEu is weighed with mol ratio as 0.3: 1, and wherein x is 0.36.
Applicant of the present invention has also done tests below research：
Experiment 1：
The method according to the invention has synthesized Ca in embodiment 411.64Al14O32F2: the fluorescent material of 0.36Eu, measure XPS and see
Fig. 1.
Fig. 1 is Ca11.64Al14O32F2: the XPS figures of 0.36Eu, XPS (x-ray photoelectron spectroscopy) is important surface analysis
One of technology, can not only searching surface chemical composition, and the chemical state of each element can be determined, and each element can be determined
Track combination energy.Detected in Fig. 1 containing five kinds of elements of Ca, Al, O, F and Eu in fluorescent material, be comparatively ideal fluorescent material sample,
Sample does not cause the loss of essential element because of the factor such as calcining.Wherein Eu3d5/2 and Eu3d3/2 shows the combination of weak intensity
Energy.
Experiment 2：
The method according to the invention, on the basis of embodiment 4, change burning temperature, other synthesis conditions are constant, pass through
The different ignition temperature of research has synthesized fluorescent material Ca11.64Al14O32F2: 0.36Eu, and measure XRD and see Fig. 2.
Fig. 2 is the XRD of synthetic sample under different temperatures, is contrasted with Fig. 2 Plays card, it can be seen that different temperatures is fired
Burn lower synthesized fluorescent material sample and be essentially pure phase, illustrate that the fluorescence powder purity of combustion synthesis is higher.
Experiment 3：
The method according to the invention, on the basis of embodiment 3, changes the fluorescent material of ammonium fluoride and synthesis
Ca11.64Al14O32F2: the mol ratio of 0.36Eu, other synthesis conditions are constant, by studying different ammonium fluoride additions to synthesis
The influence of fluorescent material, and measure Ca in fluorescent material sample11.64Al14O32F2: launching light spectrograms of the 0.36Eu in the case where 239nm is excited
Such as Fig. 3 (a)；Fluorescent material sample corresponding cie color coordinate such as Fig. 3 (b) in the case where 239nm is excited.This experiment 3 is with synthesis
The Ca of 0.5mmol11.64Al14O32F2x: 0.36Eu is target, the amount for choosing 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), in the case where 391nm is excited, the blue light of phosphor emission 400-500nm and 580-620nm's is red
Light.With NH4The increase of F amounts, the luminous intensity of fluorescent material gradually strengthens, in n (NH4F)=3.0mmol when, fluorescent material is in highest
The luminous intensity of peak 437nm and 611nm is reached most by force, then as NH4The increase of F amounts, the luminous intensity of fluorescent material gradually drops
It is low.From Fig. 3 (b), by changing NH4The addition of F, Ca11.64Al14O32F2: the chromaticity coordinate of 0.36Eu by (0.3717,
0.3381) (0.4177,0.3221) is changed to, then to (0.3823,0.2731), glow color is changed to blue white by blue-green
Color, then to navy blue, therefore the point fallen in blue white light field is closer to white light, light-emitting phosphor better performances.
Experiment 4：
On the basis of embodiment 4, change burning temperature, other synthesis conditions are identical, under research different temperatures (700,
800th, 900,1000 DEG C) influence of synthetizing phosphor powder, measure the fluorescent material Ca synthesized under different temperatures11.64Al14O32F2∶
0.36Eu launching light spectrograms are shown in Fig. 4 (a)；Excitation wavelength be 244nm under the corresponding cie color coordinate diagram of the light-emitting phosphor see figure
4(b)。
From Fig. 4 (a), blue light strength of the fluorescent material at 440nm with 700 DEG C -900 DEG C of the rising of temperature gradually
Reduce, at 1000 DEG C, blue light strength is basically identical with 900 DEG C, and collection of illustrative plates almost overlaps, and illustrates that divalent europium change in concentration is smaller.
Red light intensity at 580-620nm is weaker at 700 DEG C, stronger at 1000 DEG C, and at 800 DEG C and 900 DEG C, red light intensity becomes
Change it is little, the approximate trend of collection of illustrative plates with the rising of temperature, Eu in sample2+Amount reduce, Eu3+Amount increase.Can by Fig. 4 (b)
Know, with the rising of temperature, glow color of the fluorescent material in the case where 244nm is excited is adjusted to greenish orange red from lavender, works as temperature
During for 800 DEG C with 900 DEG C, between lavender and greenish orange red, color is closer to shallow white, energy to light-emitting phosphor color
A reference well is provided to synthesis target white light.
Experiment 5：
On the basis of embodiment 4, change the ratio of urea and nitrate gross mass, other synthesis conditions are identical, research
The influence of synthetizing phosphor powder under different urea additions, wherein, the ratio of urea and nitrate gross mass is taken as 0.5 successively, 1.0,
1.5th, 2.0,2.5,3.0, measure the fluorescent material Ca of different urea addition synthesis11.64Al14O32F2: 0.36Eu is excited in 241nm
Under launching light spectrogram see Fig. 5 (a), measure the fluorescent material Ca of different urea additions synthesis11.64Al14O32F2: 0.36Eu exists
Launching light spectrogram under 336nm is excited is shown in Fig. 5 (b)；
From Fig. 5 (a), in the case where 241nm is excited, fluorescent material sends out the blue light of 436nm and the feux rouges of 587nm, 617nm.With
The increase of urea amount, luminous intensity gradually strengthens then to be reduced, in mUrine∶mNitre(m when=1.5Nitre isThe quality of nitrate), feux rouges
(612nm) and blue light (441nm) reach most strong.From Fig. 5 (b), in the case where 336nm is excited, fluorescent material only launches 400-500nm
Blue light.With the increase of urea amount, the luminous intensity of fluorescent material gradually strengthens and then lowers.
Experiment 6：
On the basis of embodiment 4, change the addition of europium nitrate, other synthesis conditions are identical, study different nitric acid
Influence of the europium addition to synthetizing phosphor powder, measures the fluorescent material Ca of different europium nitrate addition synthesis12-xAl14O32F2: xEu exists
Launching light spectrogram under 241nm is excited is shown in Fig. 6 (a), the fluorescent material Ca of different europium nitrate addition synthesis12-xAl14O32F2∶xEu
Launching light spectrogram in the case where 336nm is excited is shown in Fig. 6 (b), the fluorescent material Ca of different europium nitrate addition synthesis12-xAl14O32F2∶
XEu corresponding cie color coordinate diagrams in the case where 241nm is excited are shown in Fig. 6 (c).This experiment 6 is synthesizing the Ca of 0.5mmol12- xAl14O32F2: xEu is target, and synthesis x values are 0.12,0.24,0.36,0.48,0.60,0.72 fluorescent material, then europium nitrate
Amount be followed successively by 0.06,0.12,0.18,0.24,0.30,0.36mmol, correspondence is followed successively by with the mol ratio of the fluorescent material for synthesizing
0.12、0.24、0.36、0.48、0.60、0.72。
From Fig. 6 (a), in the case where 241nm is excited, the blue light of phosphor emission 437nm and the feux rouges of 586nm, 612nm,
Feux rouges is significantly stronger than blue light, because the NH in raw material4 +Eu constant with urea amount, being reduced into2+Amount it is also just certain,
And Eu3+Amount gradually increase.With the increase of europium ion amount, the luminous intensity of 586nm and 612nm gradually strengthens then to be reduced.
From Fig. 6 (b), in the case where 336nm is excited, fluorescent material mainly launches the blue light of 400-500nm, with the increase of europium concentration, hair
Luminous intensity is gradually reduced, because six NH of sample4F is identical with the amount of urea, as europium concentration increases, is not reduced into
Eu2+Eu3+Shared ratio gradually increases, and luminous intensity is gradually reduced.Fig. 6 (c) is the addition synthesis Ca for changing europium12- xAl14O32F2: xEu corresponding cie color coordinate diagrams in the case where 241nm is excited, adding for different europium elements can be seen that by Fig. 6 (c)
The cie color coordinate of fluorescent material synthesized by dosage is different, and color falls in lavender with orange red region, works as x=0.361
When, light-emitting phosphor color is located at lilac region the most, is more satisfactory compared with other closest white lights of point, and moderate concentration
Europium addition.
Experiment 7：
On the basis of embodiment 4, change the addition of boric acid and the fluorescent material Ca of synthesis11.64Al14O32F2∶0.36Eu
Mol ratio, other synthesis conditions are identical, study influence of the different boric acid additions to synthetizing phosphor powder, measure different boric acid
Synthetizing phosphor powder Ca under addition11.64Al14O32F2: launching light spectrograms of the 0.36Eu in the case where 241nm is excited is shown in Fig. 7 (a)；It is different
Synthetizing phosphor powder Ca under boric acid addition11.64Al14O32F2: launching light spectrograms of the 0.36Eu in the case where 332nm is excited is shown in Fig. 7 (b).
This experiment 7 is synthesizing the Ca of 0.5mmol11.64Al14O32F2: 0.36Eu is target, chooses the amount and the fluorescent material of synthesis of boric acid
Mol ratio CBIt is followed successively by 0,0.1,0.2,0.3,0.4,0.5,0.6.
From Fig. 7 (a), in the case where 241nm is excited, the blue light of phosphor emission 400-500nm and 580-620nm's is red
Light, with the increase of boric acid addition, luminous intensity gradually increases then to be reduced, and works as CB=0.3 (CBIt is the amount of the material of boric acid
With the ratio of the amount of the material of product) when, luminous intensity reaches maximum.During combustion synthesis fluorescent material, boric acid can be as helping
Solvent, adds a certain amount of boric acid favourable to fluorescent material, and it can promote the crystal growth of product, strengthens the luminous strong of fluorescent material
Degree.From Fig. 7 (b), in the case where 332nm is excited, the blue light of phosphor emission 400-500nm, with the increase of boric acid addition,
The luminous intensity of fluorescent material is shown as in cB=0, luminous intensity maximum is about in 100~150a.u. scopes when 0.1,0.2
It is interior, work as CBWhen=0.3, it is most strong that luminous intensity maximum is about 260a.u. luminous intensities, and works as cB=0.4, lighted when 0.5,0.6
Maximum of intensity falls in the range of about 100~150a.u. again, similar to reducing tendency after first increasing.Therefore, to CBSeven
C in individual change quantity researchBPhosphor emission peak height is highest when=0.3, and peak area is most wide, and luminous intensity is most strong, so, boric acid
Usage amount is optimal when should be 0.3 with the mol ratio of the fluorescent material of synthesis, luminous intensity can be obtained greatly, close to the light of white light.
Experiment 8：
Fig. 8 (a) is different NH4The addition synthetizing phosphor powder Ca of F11.64Al14O32F2: 0.36Eu is to detect ripple with 438nm
Exciting light spectrogram long；Fig. 8 (b) differences NH4The addition synthetizing phosphor powder Ca of F11.64Al14O32F2: 0.36Eu is to examine with 611nm
Survey the exciting light spectrogram of wavelength.
From Fig. 8 (a), excitation peak of the fluorescent material with 438nm as Detection wavelength is a weak band and of 220-280nm
The strong band of individual 300-400nm；From Fig. 8 (b), excitation peak of the fluorescent material with 611nm as Detection wavelength is located at 220-280nm,
Excite main peak to be located near 240nm, and have very weak excitation peak near 380nm and 390nm.Work as NH4The amount of F is less, i.e. Eu3+
When being reduced few, the main peak that excites of fluorescent material is located near 240nm, and it belongs to O2--Eu3+Charge migration absorb；Work as NH4F
Amount it is more, i.e. Eu3+When being reduced many, the main peak that excites of fluorescent material is located near 340nm, belongs to Eu2+4f-5d energy
Order transition absorbs；There is very weak excitation peak to belong to Eu near 380nm and 390nm3+4f-4f transition.
Inventive samples do when fluorescence is detected and sample first are done into ultraviolet-visible absorption, typically with maximum absorption wavelength or
Used as excitation wavelength, in general this (or these) peak is exactly fluorescence peak for wavelength at person's isobestic point, because fluorescence peak
Position is not change with the change of excitation wavelength, is only that peak height (or peak area) changes, with reference to the spy of fluorescence spectrum
Property ----excite and determine excitation wavelength the characteristics of transmitting in mirror image.In this experiment with excitation wavelength be 220-280nm and
300-400nm excitated fluorescent powders, there is absorption at 400nm-700nm, wherein be absorbed as with about 450nm, 616nm it is relatively strong, then with
438nm, 616nm are Detection wavelength excitated fluorescent powder, then have absorption at 220-280nm and 300-400nm, with 241nm,
It is most strong near 336nm.
Knowable to comprehensive observing Fig. 8 (a) and two collection of illustrative plates of Fig. 8 (b), work as NH4During F=3mmol, absorb relatively strong, moderate concentration,
It is comparatively ideal concentration.
Experiment 9：
By testing the single factor experiment for drawing in 3- experiments 7, by Fig. 3 (a), Fig. 4 (a), Fig. 5 (a), Fig. 6 (a), Fig. 7
A the fluorescent material synthesized under one-to-one differential responses synthesis condition in (), takes the light area under spectrum conduct of wavelength 400-550nm
The luminous intensity of divalent europium, takes the light area under spectrum of wavelength 550-700nm as the luminous intensity of trivalent europium, then trivalent europium and divalence
Europium is that red blue light ratio (i.e. red blue area ratio) is shown in Table 1, draws the ratio range of the amount of trivalent europium and divalent europium in fluorescent material
It is 0.73-1.88.
Red blue light area ratio under the conditions of the different tests of table 1
Although embodiment of the present invention is disclosed as above, it is not restricted to listed in specification and implementation method
With, it can be applied to various suitable the field of the invention completely, for those skilled in the art, can be easily
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited
In specific details and shown here as the legend with description.
Claims (6)
1. a kind of Eu2+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, it is characterised in that the molecule of the fluorescent material
Formula is：Ca12-xAl14O32F2:XEu, wherein 0.2 ＜ x ＜ 0.6, the Eu in the molecular structure of the fluorescent material refers to Eu2+And Eu3+Altogether
The mixture deposited, the x values are 0.36, and trivalent europium ion is 0.73-1.88 with the ratio range of divalent europium quantity；
The synthetic method is comprised the following steps：
Step one, calcium nitrate, ammonium fluoride are weighed, after mixing, add europium nitrate solution and aluminum nitrate solution, add urea and boron
Acid, stirs and evenly mixs, and is placed in supersonic oscillations 15min to obtaining clear solution, i.e. presoma；
Step 2, presoma is placed in preset temperature is the 5-15min that burns in 700-1000 DEG C of box-type high-temperature furnace, cold after taking-up
But, grind, obtain divalent europium and the europium-doped fluoaluminate substrate fluorescent powder of trivalent；
Wherein, the calcium nitrate, europium nitrate, aluminum nitrate are according to a certain amount of Ca of synthesis12-xAl14O32F2:Each element in xEu
Learn metering ratio to weigh, the ammonium fluoride is pressed and synthesis Ca12-xAl14O32F2:The amount of xEu is with mol ratio as 4-8:1 weighs, the urine
Element is by the gross mass with nitrate with mass ratio as 1.5-2.0:1 weighs, and the nitrate refers to calcium nitrate, europium nitrate and nitric acid
Aluminium, the boric acid is pressed and synthesis Ca12-xAl14O32F2:The amount of xEu is with mol ratio as 0.1-0.3:1 weighs.
2. Eu as claimed in claim 12+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, it is characterised in that
Preset temperature is 800-900 DEG C in the step 2.
3. Eu as claimed in claim 12+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, it is characterised in that
Burn 10min in the step 2.
4. Eu as claimed in claim 12+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, it is characterised in that
The ammonium fluoride is pressed and synthesis Ca12-xAl14O32F2:The amount of xEu with mol ratio be 6:1 weighs.
5. Eu as claimed in claim 12+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, it is characterised in that
The urea by with the gross mass of nitrate with mass ratio be 1.5:1 weighs.
6. Eu as claimed in claim 12+-Eu3+The synthetic method of codope fluoaluminate substrate fluorescent powder, it is characterised in that
The boric acid is pressed and synthesis Ca12-xAl14O32F2:The amount of xEu with mol ratio be 0.3:1 weighs.
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 CN105219382A (en) | 2016-01-06 |
| CN105219382B true 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) |
Families Citing this family (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 |
| 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 |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484112B (en) * | 2013-09-05 | 2014-12-10 | 青岛大学 | Rare-earth europium-activated single-component white-light fluorescent powder and preparation method thereof |
| CN104119888B (en) * | 2014-08-06 | 2016-08-24 | 广西师范学院 | A kind of europium doped with fluorine aluminate substrate fluorescent powder and preparation method thereof |
-
2015
- 2015-10-10 CN CN201510650628.0A patent/CN105219382B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105219382A (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105219382B (en) | Eu2+ Eu3+ codope fluoaluminate substrate fluorescent powders and its synthetic method and application | |
| Shi et al. | Blue-light excitable La2Ce2O7: Eu3+ red phosphors for white light-emitting diodes | |
| Kuo et al. | Synthesis and luminescence properties of Eu3+, Ce3+ and Tb3+-activated Sr3La2 (BO3) 4 under UV excitation | |
| Li et al. | Green emitting Ba1. 5Lu1. 5Al3. 5Si1. 5O12: Ce3+ phosphor with high thermal emission stability for warm WLEDs and FEDs | |
| Guo et al. | Blue-white-yellow tunable emission from Ce3+ and Eu2+ Co-doped BaSiO3 phosphors | |
| 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 | |
| Jia et al. | Long persistent light emitting diode | |
| CN114958351A (en) | Ultraviolet excited bluish violet fluorescent powder, preparation method and luminescent device | |
| 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 | |
| Wang et al. | Synthesis and optical properties of novel apatite-type NaCa3Bi (PO4) 3F: Dy3+ yellow-emitting fluorophosphate phosphors for white LEDs | |
| CN107353900A (en) | A kind of niobates fluorescent material, its preparation method and light emitting diode | |
| CN101760191B (en) | High-brightness barium-silicate-based blue-green fluorescent powder for LED and high-temperature reducing preparation method thereof | |
| WO2014206250A1 (en) | Fluorescent powder and light emitting apparatus comprising same | |
| CN103275705A (en) | Fluorescent powder, preparation method thereof and light-emitting device comprising same | |
| CN106634996A (en) | Fluorophor and application method thereof | |
| CN104232081B (en) | A kind of light converting function material and its preparation method and application | |
| CN106753346A (en) | Nitrogen oxides fluorophor and its luminescent device | |
| CN109957403A (en) | A kind of Eu3+Activate fluoboric acid strontium barium red fluorescence powder and its preparation and application | |
| CN102399554B (en) | Nitride red luminescence material, and luminescent part and luminescent device containing the same | |
| CN104830335A (en) | Europium-doped borate fluorescent powder and preparing method thereof | |
| CN104893720A (en) | Blue-green phosphor for white LED, preparation method of blue-green phosphor and white LED light-emitting device | |
| CN103320130A (en) | Nitride fluorescent powder and preparation method thereof, light-emitting device comprising nitride fluorescent powder | |
| CN104910916B (en) | A kind of glow color adjustable New Phosphorus lime stone structure light-emitting material and application thereof | |
| Jin et al. | The Luminescence Properties of the Interstitial Eu2+ in SrB2O4 for UV Light‐Emitting Diode |
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 |