CN109181684B - Crystal material for realizing white light emission through up-conversion and preparation method thereof - Google Patents
Crystal material for realizing white light emission through up-conversion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a crystal material for realizing white light emission through up-conversion and a preparation method thereof, wherein the up-conversion crystal material is Yb3+、Er3+And Tm3+CaF co-doped as a dopant ion2Crystals of, in which Yb3+Has a doping concentration of 1-10%, Er3+Has a doping concentration of 0.1% -1.0%, Tm3+The doping concentration of (A) is 0.01% -0.5%; the doping concentration is the percentage of the doping ions in the total mole of the cations in the up-conversion crystal material.
Description
Technical Field
The invention relates to a crystal material for realizing white light emission through up-conversion and a preparation method thereof, and belongs to the technical field of artificial crystals and up-conversion light emission.
Background
Since the phosphor excited by short wavelength and high energy photons is easy to age, resulting in light decay, shortening the lifetime and accompanying with the ultraviolet components harmful to human eyes, these disadvantages have led researchers to shift their eyes from down-conversion phosphors to up-conversion phosphors. The up-conversion white light material can be excited by a commercial grade cheap near-infrared LED, generates three primary colors of red, green and blue through a nonlinear multiphoton process to obtain mixed white light, has the advantages of energy conservation, environmental protection, good color rendering property, long service life and the like, and is an ideal material applied to the white light LED technology.
Currently, among various upconversion luminescent matrix materials, alkaline earth metal fluorides are widely studied due to their low energy phonons and high chemical stability. In alkaline earth metal fluorides, CaF2Has high transparency (0.2-10 μm) and low energy phonon (450 cm)-1) And a suitable absorption threshold (12eV) is considered to be an ideal up-conversion material. CaF2The materials are mainly researched on the up-conversion property, and are rare earth doped inorganic polycrystalline powder and glass substrates. For single crystals, rare earth ions are present in CaF due to difficulty in growth2Up-conversion luminescence processes in single crystals have also been reported less frequently than powders and glasses, especially in CaF2No report has been made on the study of upconversion white light emission using crystals as a matrix.
Disclosure of Invention
Therefore, the invention provides a single crystal material for realizing white light emission through up-conversion and a preparation method thereof for the first time.
In one aspect, the present invention provides a single crystal material for white light emission by up-conversion of Yb3+、Er3+And Tm3+CaF co-doped as a dopant ion2Crystals of, in which Yb3+Has a doping concentration of 1-10%, Er3+Has a doping concentration of 0.1% -1.0%, Tm3+The doping concentration of (A) is 0.01% -0.5%; the doping concentration is the percentage of the doping ions in the total mole of the cations in the up-conversion crystal material.
In the present invention, CaF2Co-doping Yb into the crystal matrix3+、Er3+And Tm3+Ion, Er under excitation of 980nm near infrared3+Ion emission Green and Red fluorescence, Tm3+The ions emit blue light and green light to obtain tricolor light required by white light, and the concentration (Yb) of rare earth ions is adjusted3+Has a doping concentration of 1-10%, Er3+Has a doping concentration of 0.1% -1.0%, Tm3+The doping concentration of the light source is 0.01% -0.5%), and the intensity of the three primary color spectrum is further regulated and controlled.
Preferably, the up-conversion crystal material realizes white light emission under excitation of 980nm laser.
In another aspect, the present invention also provides a method for preparing the single crystal material for realizing white light emission through up-conversion, which comprises mixing YbF3Powder and ErF3Powder, Tmf3Powder and CaF2The powder is used as raw material powder and is prepared from the following components in a molar ratio of (0.01-0.1): (0.001-0.1): (0.0001-0.005): 1, preparing materials, and growing the single crystal material in a protective atmosphere or a vacuum atmosphere by adopting a Bridgman method or a temperature gradient method.
Preferably, PbF is added to the raw powder2The powder is used as an oxygen scavenger, and the PbF2The addition amount of the powder is MF20.1 to 2.0wt% of the powder.
Preferably, the crystal is grown by a Bridgman method or a temperature gradient method, and the crucible is made of high-purity graphite or platinum. Further, it is preferable that no seed crystal is added to the bottom of the crucible or the crucible is placed so that the normal direction of the end face is [111 ] by orientation with an X-ray diffractometer]CaF of2The single crystal rod serves as a seed crystal.
Preferably, the protective atmosphere is an Ar atmosphere and/or a fluorine-containing atmosphere.
Preferably, the fluorine-containing atmosphere is CF4And/or HF gas, or CF4And/or a mixture of HF gas and argon gas.
In still another aspect, the present invention also provides a white LED device comprising the single crystal material for white light emission by up-conversion as described above.
The invention is realized by the pair Yb3+/Er3+/Tm3+:CaF2The proportion of the up-conversion three-primary-color luminous intensity is adjusted by regulating and controlling the concentration of doped ions in the single crystal, so that up-conversion white light emission, namely the illumination of a white light LED, is realized. Specifically, a single crystal material which realizes white light emission through up-conversion is excited by laser of 980nm, and has obvious blue light peaks around 478nm, green light peaks around 523nm and 540nm and red light spectra around 650nm and 656nm, and the intensity of each spectrum changes along with the change of the concentration of trivalent cations. In addition, the large-size bulk crystal prepared in the invention has the following advantages for up-conversion white light output: 1) the defects are few, and the up-conversion activity of the crystal is strong under the same power. Under the power of 45mW, the upconversion luminous intensity of the crystal prepared by the invention is about 20 times of that of the nano powder; 2) when the device is prepared, organic glue is not needed, and the service life of the LED is prolonged.
Drawings
FIG. 1 is a graph of 10% Yb/0.1% Er/0.05% Tm: CaF prepared in example 32Crystals and samples used for up-conversion characterization after polishing;
FIG. 2 shows the 10% Yb/0.1% Er/0.05% Tm: CaF prepared in example 32An X-ray diffraction pattern of the crystal;
FIG. 3 shows 10% Yb/0.1% Er/CaF prepared according to the present invention2Crystals (red line), 10% Yb/0.05% Tm: CaF2Crystal (blue line) and 10% Yb/0.1% Er/0.05% Tm: CaF2Up-conversion luminescence spectrum of crystal (black line);
FIG. 4 shows 10% Yb/0.1% Er: CaF prepared by the present invention2Crystalline material, 10% Yb/0.05% Tm: CaF2Crystal material and 10% Yb/0.1% Er/0.05% Tm CaF2A color gamut map and apparent color of the crystalline material;
FIG. 5 is a graph of 10% Yb/0.1% Er/0.05% Tm: CaF prepared in example 32A HAADF map of the crystal;
FIG. 6 shows 10% Yb/0.1% Er/0.05% Tm: CaF prepared in comparative example 12The nano-powder (a) was compared with 10% Yb/0.1% Er/0.05% Tm prepared in example 3, CaF2Up-conversion luminescence spectrum of the crystal (b).
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, the single crystal material that can achieve white light emission by up-conversion is a trivalent rare earth cation doped alkaline earth calcium fluoride crystal, such as Yb3+Ion, Er3+Ion and Tm3+Ion co-doping of CaF2And (4) crystals. Wherein Yb3+The doping concentration of the ions can be 1-10%, Er3+The doping concentration of the ions can be 0.1% -1.0%, Tm3+The doping concentration of the ions can be 0.01% -0.5%. Wherein the doping concentration means the percentage of doping ions in the total mole of cations in the upconverting crystal material.
In the present disclosure, by co-doping a trivalent cation (the trivalent rare earth cation is ytterbium ion (Yb))3+) Trivalent erbium ion (Er)3+) And trivalent thulium ion (Tm)3+) In alkaline earth CaF2In the crystal, under the excitation of 980nm near-infrared light, tricolor light required by white light is obtained, and the up-conversion white light emission of the material is realized by regulating and controlling the concentration of co-doped trivalent cations.
The following is an exemplary illustration of a single crystal material (Yb/Er/Tm: CaF) that achieves white light emission by upconversion2Single crystal).
YbF3Powder and ErF3Powder, Tmf3Powder and CaF2The powder is used as raw material powder, and the molar ratio of the powder to the raw material powder is 0.01-0.1: 0.001 to 0.010: 0.0001 to 0.005: 1, mixing and then growing Yb/Er/Tm: CaF in a crucible by adopting a melt method2A single crystal.
In an alternative embodiment, CaF is added to the raw powder in mass20.1 to 2 wt% (preferably 0.5 to 1 wt%) of PbF2The powder is used as an oxygen scavenger.
In one embodiment of the present invention, all the raw materials are weighed according to the formula proportion of the raw material powder, fully ground and uniformly mixed, and then loaded into a porous crucible, and the crystal growth method can be a temperature gradient method or a crucible descent method.
In an alternative embodiment, for the temperature gradient method, the crucible material is high-purity graphite or platinum, and no seed crystal or the crucible bottom is placed in the normal direction of the directional end face of the X-ray diffractometer as [111 ]]CaF of2And (3) a single crystal rod, wherein crystals grow under high vacuum degree or in high-purity Ar atmosphere. Wherein the growth atmosphere may also be a fluorine-containing atmosphere, e.g. may be CF4And/or HF gas, or CF4And/or a mixture of HF gas and argon gas. Wherein, the parameters of the temperature gradient method further comprise: 1295-1315 ℃ and starting to grow crystals, wherein the growth rate of the crystals after cooling is 0.5-1.5 ℃/h, and the growth of the crystals is finished after 120-160 hours. Then the temperature can be reduced to the room temperature according to the speed of 10-30 ℃/h.
In an alternative embodiment, for the Bridgman method, the crucible material is platinum or high-purity graphite, and no seed crystal or a directional end face with normal direction of [111 ] is placed at the bottom of the crucible]CaF of2And (3) a single crystal rod, wherein crystals grow under high vacuum degree or in high-purity Ar atmosphere. Wherein the growth atmosphere may also be a fluorine-containing atmosphere, e.g. may be CF4And/or HF gas, or CF4And/or a mixture of HF gas and argon gas. Wherein, the parameters of the crucible descending method further comprise: melting the raw materials at 1350-1440 ℃ and starting to grow crystals, wherein the descending speed of the crucible is 0.5-1 mm/h, and the crystal growth is finished after 150-200 h. And then cooling to room temperature at the speed of 8-20 ℃/h.
In the present invention, Yb, Er, Tm, CaF2The single crystal is cut into pieces, room temperature emission spectrum is tested on an FLsP960 fluorescence spectrometer after optical-grade polishing, and a pumping source adopts laser with the wavelength of 980 nm.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
CaF of 1% Yb by Bridgman method2、3％Yb:CaF2、5％Yb:CaF2And 10% Yb: CaF2Crystal:
the materials are weighed according to the respective mixture ratio, fully mixed in a vacuum glove box and placed in a platinum crucible. The crystal is grown by Bridgman method under high vacuum and vacuum degree of 2.5 × 10-3Pa, melting the raw materials at 1400 ℃ and starting to grow, wherein the descending speed of the crucible is 1.5mm/h, after 120h, finishing the crystal growth, and then cooling to room temperature at the speed of 20 ℃/h;
(1)1％Yb:CaF2crystal: weighing YbF in proportion3(5N)2.89g，CaF2(5N)97.11g；
(2)3％Yb:CaF2Crystal: weighing YbF in proportion3(5N)8.35g，CaF2(5N)91.65g；
(3)5％Yb:CaF2Crystal: weighing YbF in proportion3(5N)13.42g，CaF2(5N)86.58g；
(4)10％Yb:CaF2Crystal: weighing YbF in proportion3(5N)24.66g，CaF2(5N)75.34g。
Example 2
Growing 10% Yb0.1% Er: CaF by temperature gradient method2Crystal and 10% Yb0.5% Tm: CaF2Crystal:
weighing in proportion, mixing in vacuum glove box, placing in graphite crucible, and inoculating with seed crystal<111>Directionally pure CaF2Crystal, seed size phi 6 x 30 mm. Adopting a temperature gradient method, wherein the atmosphere is high vacuum, melting the raw materials at 1400 ℃ and starting to grow, the growth rate of cooling is 1.5 ℃/h, the crystal growth is completed after 120h, and then cooling to room temperature according to 20 ℃/h;
(1)10％Yb/0.1％Er:CaF2crystal: weighing YbF in proportion3(5N)24.62g，ErF3(5N)0.2400g，CaF2(5N)75.14g；
(2)10％Yb/0.5％Tm:CaF2Crystal: weighing YbF in proportion3(5N)24.47g，TmF3(5N)1.2016g，CaF2(5N)144.79g。
Example 3
Growth by Bridgman method, 10% Yb/0.1% Er/0.05% Tm: CaF2Crystal of 10% Yb/0.1% Er/0.1% Tm CaF2Crystal of 10% Yb/0.1% Er/0.3% Tm CaF2Crystal and 10% Yb/0.1% Er/0.5% Tm CaF2Crystal:
weighing the materials according to the proportion of the respective ingredients. Placing the crucible in a platinum crucible. Growing the crystal by adopting a Bridgman method, wherein the atmosphere is high vacuum, the vacuum degree is 2.5 multiplied by 10 < -3 > Pa, the raw materials are melted at 1400 ℃, the crystal starts to grow, the Bridgman method has the Bridgman method that the Bridgman method descends at the speed of 1.5mm/h, the crystal growth is finished after 120h, and then the temperature is reduced to the room temperature at the speed of 20 ℃/h;
(1)10％Yb/0.1％Er/0.05％Tm:CaF2crystal: weighing YbF in proportion3(5N)24.60g，ErF3(5N)0.2399g，TmF3(5N)0.1208g，CaF2(5N)75.04g；
(2)10％Yb/0.1％Er/0.1％Tm:CaF2Crystal: weighing YbF in proportion3(5N)24.58g，ErF3(5N)0.2397g，TmF3(5N)0.2415g，CaF2(5N)74.93g；
(3)10％Yb/0.1％Er/0.3％Tm:CaF2Crystal: weighing YbF in proportion3(5N)24.51g，ErF3(5N)0.2389g，TmF3(5N)0.7220g，CaF2(5N)74.53g；
(4)10％Yb/0.1％Er/0.5％Tm:CaF2Crystal: weighing YbF in proportion3(5N)24.43g，ErF3(5N)0.2382g，TmF3(5N)1.1997g，CaF2(5N)74.13g。
FIG. 1 is a graph of 10% Yb/0.1% Er/0.05% Tm: CaF prepared in example 32A crystal, sliced into single wafers with a radius of about 20mm and a thickness of 1.0mm and polished for up-conversion characterization;
FIG. 2 shows CaF as 10% Yb/0.1% Er/0.05% Tm prepared in example 32The X-ray diffraction pattern of the crystal shows that the product has no impurity peak and has strong diffraction peak;
FIG. 3 is a schematic view ofExamples 2 and 3 prepared samples of 10% Yb/0.1% Er CaF2Crystals (red line), 10% Yb/0.05% Tm: CaF2Crystal (blue line) and 10% Yb/0.1% Er/0.05% Tm: CaF2The up-conversion luminescence spectrum of the crystal (black line) shows that the crystal has 10% Yb/0.1% Er: CaF2The crystal (red line) has the red light from Er at 523nm, 540nm (green light) and 656nm3+Of ions (A), (B)2H11/2,4S3/2)→4I15/2And4F9/2→4I15/2a transition in energy level; CaF for 10% Yb/0.05% Tm2The crystal (blue line) luminescence center is located at 478nm (blue light) and 650nm (red light) respectively from Tm3+Of ions1G4→3H6And1G4→3F4transition of energy level and 10% Yb/0.1% Er/0.05% Tm CaF2The crystal (black line) not only contains Er3+The luminescent center of the ion further contains Tm3+A luminescent center of the ion;
FIG. 4 shows the results of examples 2 and 3 for 10% Yb/0.1% Er: CaF2Crystal, 10% Yb/0.05% Tm: CaF2Crystal and 10% Yb/0.1% Er/0.05% Tm CaF2CIE diagram and apparent color of the crystal. As can be seen from the graph, 10% Yb/0.1% Er: CaF2The crystals showed yellow light, 10% Yb/0.05% Tm: CaF2The crystal showed blue light, while 10% Yb/0.1% Er/0.05% Tm: CaF2The crystal displays white light;
FIG. 5 shows 10% Yb/0.1% Er/0.05% Tm: CaF2The HAADF of the crystal shows that the edge of the crystal is smooth and has no impurity, which indicates that the crystal has less defects.
Comparative example 110% Yb/0.1% Er/0.05% Tm CaF2Preparation of nano-powder
With CaCl2Powder of Yb2O3Powder and Er2O3Powder and Tm2O3The powder was dissolved in hydrochloric acid (37%) in a molar ratio as a raw material powder, and the mixture was uniformly mixed to obtain a solution. Then 1mL of hydrofluoric acid (40%) was added dropwise to the above solutionStirring for 30 minutes, then transferring the mixture into a 50mL reaction kettle to react for 12 hours at the temperature of 200 ℃, cooling the mixture to room temperature, and then centrifuging, washing and drying the mixture to obtain 10 percent Yb/0.1 percent Er/0.05 percent Tm: CaF2And (3) nano powder.
Activity test for upconversion: the 10% Yb/0.1% Er/0.05% Tm: CaF prepared in example 3 was used2The crystal is cut into a wafer 1 with the thickness of 1mm and the diameter of 20 mm. The 10% Yb/0.1% Er/0.05% Tm: CaF prepared in comparative example 1 above was added2The nano powder is pressed into a wafer 2 with the same thickness and size as the wafer 1. And testing the sample by using a low-temperature absorption spectrometer, wherein under the irradiation of laser with the wavelength of 980nm, the power is 45mW, the test waveband is an up-conversion luminescence waveband of 400-720 nm, and the up-conversion luminescence intensities of the wafer 1 and the wafer 2 are compared. As can be observed from FIG. 6, CaF, 10% Yb/0.1% Er/0.05% Tm prepared in example 32The up-conversion luminous intensity of the crystal is far greater than that of the nano powder prepared by the comparison document 1, and is about 10% of Yb/0.1% of Er/0.05% of Tm: CaF 220 times of the nano powder.
Claims (8)
1. A bulk single crystal material for white light emission by up-conversion, characterized in that Yb is used as the bulk single crystal material for white light emission by up-conversion3+、Er3+And Tm3+CaF co-doped as a dopant ion2Crystals of, in which Yb3+Has a doping concentration of 1-10%, Er3+Has a doping concentration of 0.1% -1.0%, Tm3+The doping concentration of (A) is 0.01% -0.5%; the doping concentration is the percentage content of doping ions in the total mole of the positive ions in the massive single crystal material which realizes white light emission through up-conversion;
the preparation method of the massive single crystal material for realizing white light emission through up-conversion comprises the following steps: YbF3Powder and ErF3Powder, Tmf3Powder and CaF2The powder is used as raw material powder and is prepared from the following components in a molar ratio of (0.01-0.1): (0.001-0.1): (0.0001-0.005): 1, preparing materials, and growing the single crystal material in a protective atmosphere or a vacuum atmosphere by adopting a Bridgman method or a temperature gradient method.
2. The bulk single crystal material for white light emission by up-conversion according to claim 1, wherein the bulk single crystal material for white light emission by up-conversion realizes white light emission under excitation of 980nm laser light.
3. Bulk mono-crystalline material for white light emission by up-conversion according to claim 1, characterized in that PbF is added to the raw powder2The powder is used as an oxygen scavenger, and the PbF2The addition amount of the powder is MF20.1 to 2.0wt% of the powder.
4. Bulk monocrystalline material for white light emission by upconversion according to claim 1 characterized in that the crystal is grown by a crucible descent method or a temperature gradient method, the crucible being made of high purity graphite or platinum.
5. The bulk single crystal material for white light emission by upconversion according to claim 4, wherein no seed crystal is added to the bottom of the crucible or the normal direction of the end face oriented by X-ray diffractometer is [111 ]]CaF of2The single crystal rod serves as a seed crystal.
6. Bulk single crystal material for white light emission by upconversion according to any of claims 1 to 5, characterized in that the protective atmosphere is an Ar atmosphere and/or a fluorine containing atmosphere.
7. Bulk mono-crystalline material for white light emission by up-conversion as claimed in claim 6, wherein the fluorine-containing atmosphere is CF4And/or HF gas, or CF4And/or a mixture of HF gas and argon gas.
8. A white LED device comprising the bulk single crystal material for white light emission by upconversion as claimed in any of claims 1 to 7.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000281493A (en) * | 1999-03-30 | 2000-10-10 | Canon Inc | Treatment of crystal, crystal and optical part and exposure device |
| CN105969347A (en) * | 2016-05-31 | 2016-09-28 | 吉林大学 | Method for acquiring up-conversion white light |
| CN106048721A (en) * | 2016-07-20 | 2016-10-26 | 中国科学院上海硅酸盐研究所 | Spectral property adjustable rare-earth ion doped alkali earth fluoride laser crystal and preparation method thereof |
| CN106085423A (en) * | 2016-05-31 | 2016-11-09 | 吉林大学 | Conversion of white light material C aF in one2: Yb3+/ Eu3+/ Y3+ |
-
2018
- 2018-08-17 CN CN201810943027.2A patent/CN109181684B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000281493A (en) * | 1999-03-30 | 2000-10-10 | Canon Inc | Treatment of crystal, crystal and optical part and exposure device |
| CN105969347A (en) * | 2016-05-31 | 2016-09-28 | 吉林大学 | Method for acquiring up-conversion white light |
| CN106085423A (en) * | 2016-05-31 | 2016-11-09 | 吉林大学 | Conversion of white light material C aF in one2: Yb3+/ Eu3+/ Y3+ |
| CN106048721A (en) * | 2016-07-20 | 2016-10-26 | 中国科学院上海硅酸盐研究所 | Spectral property adjustable rare-earth ion doped alkali earth fluoride laser crystal and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Up-conversion white light of Tm3+/Er3+/Yb3+ tri-doped CaF2 phosphors";Chunyan Cao et al.,;《Optics Communications》;20171207;第281卷(第6期);第1716-1719页 * |
| Chunyan Cao et al.,."Up-conversion white light of Tm3+/Er3+/Yb3+ tri-doped CaF2 phosphors".《Optics Communications》.2017,第281卷(第6期), * |
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