CN108384541A - A kind of rare-earth-doped fluoride base bi-directional conversion luminescent material and preparation method thereof - Google Patents
A kind of rare-earth-doped fluoride base bi-directional conversion luminescent material and preparation method thereof Download PDFInfo
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- CN108384541A CN108384541A CN201810434203.XA CN201810434203A CN108384541A CN 108384541 A CN108384541 A CN 108384541A CN 201810434203 A CN201810434203 A CN 201810434203A CN 108384541 A CN108384541 A CN 108384541A
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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Abstract
The invention discloses a kind of rare-earth-doped fluoride base bi-directional conversion luminescent material, general formula is (Pb1‑xMx)F2:R, Yb, wherein 0≤x≤1, M=Ba, Bi, La, Ca；R=Er, Tm, Ho, Nd, the luminescent material are in powder morphology, and preparation method includes the following steps：Raw material includes PbF2And/or BaF2、BiF3、LaF3、CaF2, YbF3And/or ErF3、TmF3、HoF3、NdF3And NaF；Calcination reaction occurs after raw material is fully ground at a temperature of 550 DEG C~650 DEG C, obtains (Pb1‑xMx)F2:R, Yb fluorescent powder；(the Pb by described in1‑xMx)F2:R, Yb fluorescent powder use the emission spectrum of UV, visible light fluorescence spectrophotometry coupling 808nm, 980nm, 1064nm and 1550nm laser test sample at room temperature.Preparation method of the present invention is simple, and luminescent properties are good, 378nm ultraviolet lights and 808nm, 980nm, 1064nm, 1550nm it is infrared ray excited under, can send out visible light, the light utilization efficiency and transfer efficiency of solar cell can be effectively improved.
Description
Technical field
The present invention relates to fluorescent material field, specifically a kind of rare-earth-doped fluoride base bi-directional conversion luminescent material and its
Preparation method.
Background technology
Solar cell is the most potential novel energy product acted on based on photovoltaic.Improve solar cell
Transfer efficiency is current urgent problem to be solved, and a key factor for influencing transfer efficiency raising is that the spectrum of sunlight utilizes
Range is inadequate.The theoretical efficiency upper limit of semiconductor homojunction single layer battery is 31% at present, the main reason is that each material is all
It is finite response, the range of response wave length is very low to ultraviolet, infrared light utilization rate mainly in visible region.In recent years, will
Some spectrum transition materials are applied on solar cell, include mainly the luminescent materials such as upper conversion, quantum-cutting and lower conversion.
Infrared light is converted to using up-conversion luminescent material the visible light easily absorbed, maximum conversion efficiency can be increased to 47.6%.
By transition material under increasing by one layer in solar cell front surface, transfer efficiency can be improved to 38.6%.But turn in realization
Change and lower conversion performance realize often by two class materials, need on the solar cell applied in two coats spectral translation it is thin
Film, it is complex process, of high cost.
Therefore, for the above present situation, there is an urgent need to develop a kind of rare-earth-doped fluoride base bi-directional conversion luminescent material and
Preparation method, to overcome the shortcomings of in currently practical application.
Invention content
The purpose of the present invention is to provide a kind of rare-earth-doped fluoride base bi-directional conversion luminescent material and preparation method thereof,
To solve the problems mentioned in the above background technology.
To achieve the above object, the present invention provides the following technical solutions：
A kind of rare-earth-doped fluoride base bi-directional conversion luminescent material, general formula are (Pb1-xMx)F2:R, Yb, wherein 0≤x
≤ 1, M=Ba, Bi, La, Ca；R=Er, Tm, Ho, Nd, the luminescent material are in powder morphology, and preparation method includes following step
Suddenly：
A, raw material includes PbF2And/or BaF2、BiF3、LaF3、CaF2, YbF3And/or ErF3、TmF3、HoF3、NdF3With
NaF；
B, calcination reaction occurs after being fully ground the raw material of step A at a temperature of 550 DEG C~650 DEG C, obtains (Pb1- xMx)F2:R, Yb fluorescent powder；
C, (the Pb by described in1-xMx)F2:R, Yb fluorescent powder use UV, visible light fluorescence spectrophotometry to couple at room temperature
The emission spectrum of 808nm, 980nm, 1064nm and 1550nm laser test sample.
As a further solution of the present invention：In step, NaF is fluxing agent and charge compensator；(Pb1-xMx)F2:
RF3:YbF3=78%~87%:1%~2%:12%~20%, wherein 0≤x≤1, M=Ba, Bi, La, Ca；R=Er, Tm,
Ho, Nd.
As a further solution of the present invention：In step, the molar fraction of NaF is 10%~20%.
As a further solution of the present invention：In stepb, raw material is fully ground 10min in mortar.
As a further solution of the present invention：In stepb, calcination reaction carries out in Muffle furnace, and 5 DEG C of heating rate/
Min, sintering time 1.5 hours.
Compared with prior art, the beneficial effects of the invention are as follows：The method of manufacturing fluorescent material is simple, and luminescent properties are good
It is good, 378nm ultraviolet lights and 808nm, 980nm, 1064nm, 1550nm it is infrared ray excited under, can send out visible light, can
Effectively improve the light utilization efficiency and transfer efficiency of solar cell.
Description of the drawings
Fig. 1 is the preparation flow schematic diagram of the present invention.
Fig. 2 is the down-conversion fluorescent spectrogram of the lower sample of 378nm excitations.
Fig. 3 is the up-conversion fluorescence spectrogram of the lower sample of 808nm excitations.
Fig. 4 is the up-conversion fluorescence spectrogram of the lower sample of 980nm excitations.
Fig. 5 is the up-conversion fluorescence spectrogram of the lower sample of 1064nm excitations.
Fig. 6 is the up-conversion fluorescence spectrogram of the lower sample of 1550nm excitations.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Please refer to Fig.1~6, in the embodiment of the present invention, a kind of rare-earth-doped fluoride base bi-directional conversion luminescent material leads to
Formula is (Pb1-xMx)F2:R, Yb, wherein 0≤x≤1, M=Ba, Bi, La, Ca；R=Er, Tm, Ho, Nd, the rear-earth-doped fluorination
Object base bi-directional conversion luminescent material is in powder morphology, and preparation method includes the following steps：
A, raw material includes PbF2And/or BaF2、BiF3、LaF3、CaF2, YbF3And/or ErF3、TmF3、HoF3、NdF3With
NaF；
B, calcination reaction occurs after being fully ground the raw material of step A at a temperature of 550 DEG C~650 DEG C, obtains (Pb1- xMx)F2:R, Yb fluorescent powder；
C, (the Pb by described in1-xMx)F2:R, Yb fluorescent powder use UV, visible light fluorescence spectrophotometry to couple at room temperature
The emission spectrum of 808nm, 980nm, 1064nm and 1550nm laser test sample.
Rare-earth-doped fluoride base bi-directional conversion luminescent material made from the method for the present invention, preparation method is simple, rare earth
Ion enters parent lattice structure, occupies Pb2+The lattice position of ion, prepare sample be pure phase, fluorescent powder good luminous performance,
Lower/upper conversion luminous intensity under ultraviolet light and different-waveband infrared excitation is high, such as red in 378nm ultraviolet lights and 980nm
Emission spectrum 550nm peak strengths are up to shown in 1000a.u., following Fig. 2 and Fig. 4 under outer light stimulus.
Embodiment 1
A, raw material includes PbF2And/or BaF2、BiF3、LaF3、CaF2, YbF3And/or ErF3、TmF3、HoF3、NdF3With
NaF, wherein NaF are fluxing agent and charge compensator；(Pb1-xMx)F2:RF3:YbF3=78%~87%:1%~2%:12%
~20%, wherein 0≤x≤1, M=Ba, Bi, La, Ca；The molar fraction of R=Er, Tm, Ho, Nd, NaF are 10%~20%；
B, reaction is sintered after being fully ground the fluoride raw material in Muffle furnace, 5 DEG C/min of heating rate is burnt
550 DEG C~650 DEG C of junction temperature, sintering time 1.5 hours obtain corresponding fluorescent powder；
C, by the fluorescent powder at room temperature use UV, visible light fluorescence spectrophotometry coupling 808nm, 980nm,
The emission spectrum of 1064nm and 1550nm laser test samples.
Embodiment 2
A, raw material includes analyzing pure PbF2、YbF3、ErF3, three kinds of material molar ratios are 80:18:2, fluxing agent NaF's
Molar fraction is 16%；
B, by the raw material PbF2、YbF3、ErF3, NaF is fully ground 10min in mortar, then the material powder is existed
Heat up 1.5h in Muffle furnace, 650 DEG C, sintering time 1.5h of sintering temperature, obtains PbF2:2%Er, 18%Yb fluorescent powder；
C, by the PbF2:2%Er, 18%Yb fluorescent powder use UV, visible light fluorescence spectrophotometry to couple at room temperature
The emission spectrum of 808nm, 980nm, 1064nm and 1550nm laser test sample.
The PbF2:2%Er, 18%Yb bi-directional conversion fluorescent powder are in the red of 808nm, 980nm, 1064nm, 1550nm
Up-conversion emission spectral emissions peak under outer light stimulus is respectively positioned on 540~550nm green lights band and 650~660nm red bands, and
The emission peak of lower conversion spectrum under uv light induction is located at 409nm blue light stripes, and 540~550nm green lights band and 650~
660nm red bands.
It is an object of the invention to obtain a kind of rare earth luminescent material, under ultraviolet light and different-waveband infrared excitation
Can be exchanged into can be by the visible light that solar cell makes full use of, so as to effectively widen the absorption light model of solar cell
It encloses, improves the light utilization efficiency and transfer efficiency of solar cell.
The method of manufacturing fluorescent material is simple, and luminescent properties are good, 378nm ultraviolet lights and 808nm, 980nm,
1064nm, 1550nm it is infrared ray excited under, can send out visible light, can effectively improve battery light utilization efficiency and conversion imitate
Rate.
The bi-directional conversion luminescent material of this technology development, upper conversion and lower conversion performance are realized simultaneously, by ultraviolet, infrared light
It is converted into the higher feux rouges of protosun energy battery utilization rate and green Region is further carried with improving the utilization scope of solar spectrum
The transfer efficiency of high solar battery, while reducing the heat loss of the subband loss and ultraviolet light of solar cell mid-infrared light.
The above are merely the preferred embodiment of the present invention, it is noted that for those skilled in the art, not
Under the premise of being detached from present inventive concept, several modifications and improvements can also be made, these should also be considered as the protection model of the present invention
It encloses, these all do not interfere with the effect and patent practicability that the present invention is implemented.
Claims (5)
1. a kind of rare-earth-doped fluoride base bi-directional conversion luminescent material, general formula is (Pb1-xMx)F2:R, Yb, wherein 0≤x≤
1, M=Ba, Bi, La, Ca；R=Er, Tm, Ho, Nd, which is characterized in that the luminescent material is in powder morphology, and preparation method includes
Following steps：
A, raw material includes PbF2And/or BaF2、BiF3、LaF3、CaF2, YbF3And/or ErF3、TmF3、HoF3、NdF3And NaF；
B, calcination reaction occurs after being fully ground the raw material of step A at a temperature of 550 DEG C~650 DEG C, obtains (Pb1-xMx)F2:
R, Yb fluorescent powder；
C, (the Pb by described in1-xMx)F2:R, Yb fluorescent powder at room temperature use UV, visible light fluorescence spectrophotometry coupling 808nm,
The emission spectrum of 980nm, 1064nm and 1550nm laser test sample.
2. rare-earth-doped fluoride base bi-directional conversion luminescent material according to claim 1, which is characterized in that in step A
In, NaF is fluxing agent and charge compensator；(Pb1-xMx)F2:RF3:YbF3=78%~87%:1%~2%:12%~20%, wherein 0
≤ x≤1, M=Ba, Bi, La, Ca；R=Er, Tm, Ho, Nd.
3. rare-earth-doped fluoride base bi-directional conversion luminescent material according to claim 1 or 2, which is characterized in that in step
In rapid A, the molar fraction of NaF is 10%~20%.
4. rare-earth-doped fluoride base bi-directional conversion luminescent material according to claim 1, which is characterized in that in step B
In, raw material is fully ground 10min in mortar.
5. rare-earth-doped fluoride base bi-directional conversion luminescent material according to claim 1 or 4, which is characterized in that in step
In rapid B, calcination reaction carries out in Muffle furnace, 5 DEG C/min of heating rate, sintering time 1.5 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113308241A (en) * | 2021-02-02 | 2021-08-27 | 广东工业大学 | Dual-mode luminescent material and preparation method and application thereof |
| CN114686230A (en) * | 2022-03-14 | 2022-07-01 | 中国科学院长春光学精密机械与物理研究所 | Method for enhancing luminous intensity of rare earth fluoride fluorescent powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719252A (en) * | 2012-06-12 | 2012-10-10 | 北京工业大学 | Up-and-down-conversion luminescent high-transmittance amorphous fluoride film and preparation method thereof |
| CN103525415A (en) * | 2013-10-08 | 2014-01-22 | 长春理工大学 | 1064nm lead fluoride based up-conversion luminescence material and preparation method thereof |
| CN103865538A (en) * | 2014-02-23 | 2014-06-18 | 复旦大学 | Up/down conversion dual-mode fluorescent nanomaterial for Nd<3+> sensitization and synthesis method thereof |
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2018
- 2018-05-08 CN CN201810434203.XA patent/CN108384541A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719252A (en) * | 2012-06-12 | 2012-10-10 | 北京工业大学 | Up-and-down-conversion luminescent high-transmittance amorphous fluoride film and preparation method thereof |
| CN103525415A (en) * | 2013-10-08 | 2014-01-22 | 长春理工大学 | 1064nm lead fluoride based up-conversion luminescence material and preparation method thereof |
| CN103865538A (en) * | 2014-02-23 | 2014-06-18 | 复旦大学 | Up/down conversion dual-mode fluorescent nanomaterial for Nd<3+> sensitization and synthesis method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113308241A (en) * | 2021-02-02 | 2021-08-27 | 广东工业大学 | Dual-mode luminescent material and preparation method and application thereof |
| CN114686230A (en) * | 2022-03-14 | 2022-07-01 | 中国科学院长春光学精密机械与物理研究所 | Method for enhancing luminous intensity of rare earth fluoride fluorescent powder |
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