CN102051682A - Dysprosium-doped lead fluoride crystal and preparation method thereof - Google Patents
Dysprosium-doped lead fluoride crystal and preparation method thereof Download PDFInfo
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- CN102051682A CN102051682A CN 201010530649 CN201010530649A CN102051682A CN 102051682 A CN102051682 A CN 102051682A CN 201010530649 CN201010530649 CN 201010530649 CN 201010530649 A CN201010530649 A CN 201010530649A CN 102051682 A CN102051682 A CN 102051682A
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- 239000013078 crystal Substances 0.000 title claims abstract description 59
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 title claims abstract 6
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 239000000155 melt Substances 0.000 claims abstract 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 9
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 230000007704 transition Effects 0.000 description 7
- 208000005156 Dehydration Diseases 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 241000209456 Plumbago Species 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- -1 rare earth ion Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
一种镝掺杂的氟化铅晶体，该晶体分子式为：DyxPbF2+3x，其中x为Dy3+的掺杂浓度，x＝0.1～10mol％。该晶体采用熔体法生长，该方法包括下列步骤：①选定x的取值，在晶体生长配方中初始原料为DyF3和PbF2，根据分子式DyxPbF2+3x按化学计量比称量原料，其中x＝0.1～10mol％；②按上述比例称取的原料充分混合均匀，真空烘干并压制成块，放入石墨或铂金坩埚中，采用PbF2晶体作为籽晶，生长气氛为氩气或者CF4等气体。本发明镝掺杂的氟化铅晶体具有较低的声子能量、较长的荧光寿命、较大的吸收和发射截面。该晶体有望在全固态2～5μm波段激光器中应用。
A dysprosium-doped lead fluoride crystal, the crystal molecular formula is: Dy x PbF 2+3x , wherein x is the doping concentration of Dy 3+ , x=0.1-10mol%. The crystal is grown by a melt method, the method comprising the following steps: ① selecting the value of x, the initial raw materials in the crystal growth formula are DyF 3 and PbF 2 , the raw materials are weighed according to the molecular formula Dy x PbF 2+3x according to the stoichiometric ratio, wherein x=0.1-10mol%; ② the raw materials weighed according to the above ratio are fully mixed, vacuum dried and pressed into blocks, put into a graphite or platinum crucible, PbF 2 crystal is used as a seed crystal, and the growth atmosphere is argon or CF 4 and other gases. The dysprosium-doped lead fluoride crystal of the present invention has lower phonon energy, longer fluorescence lifetime, and larger absorption and emission cross-sections. The crystal is expected to be used in all-solid-state 2-5μm band lasers.
Description
Technical field
The present invention relates to laser crystals, especially a kind of dysprosium mixes and fluoridizes leading crystal and preparation method thereof.
Background technology
The middle-infrared band of 2～5 μ m covers H
2O, CO
2, CO, CH
4With several important molecular absorption bands such as HF, so it has important use at aspects such as medical science, remote sensing, lidar and optical communications.The laser of 2 mu m wavebands, in view of its easily transmission and in atmosphere to the characteristic of eye-safe, 2 μ m laser are considered to be applied to the perfect light source of medical treatment and eye-safe detection system, and this comprises the important application of aspects such as medical operation, atmosphere environment supervision, lidar, photoelectronic warfare.3～5 μ m are atmospheric windows, and this wave band of laser has stronger penetration power to dense fog, flue dust etc., and transmission is subjected on sea level gas molecule absorption and suspended substance scattering are little.Since the Gulf War, 80～90% aircraft operational loss is caused by shoulder-fired infrared guidance interceptor missile (SAM guided missile), comprises the unique ground force's attack helicopter that is shot down by Iraqi troops.Infrared guidance guided missile detection device is (as PbSi, InSb, HgCdTe etc.) responding range along with the diffusion of more advanced SAM guided missile and the appearance of the target-seeking device of advanced infrared starring array, presses for the LASER Light Source of this wave band at 3～5 mu m wavebands at the photoelectronic warfare of infrared seeker.
Dy
3+Therefore ion has abundant level structure, can produce the laser transition of a lot of wave bands and receives much concern, and utilizes
6F
11/2(
6H
9/2)-H
15/2With
6F
5/2-
6H
11/2Transition can obtain the fluorescence of 1.33 and 1.55 μ m, and these two wave bands are important communication ports of silica fibre signal transmission.
6H
11/2-
6H
13/2With
6H
13/2-
6H
15/2Energy level transition centre wavelength lays respectively at 4.36 and 2.86 μ m, can be with Dy
3+Ion is from ground state
6H
15/2Energy level is excited to
6F
5/2Energy level, by radiationless and radiative transition extremely
6F
11/2With
6F
13/2Realize the intermediate infrared radiation transition behind the energy level.And Dy
3+There is bigger absorption cross in ion near 800nm, can adopt near the comparatively cheap semiconductor laser of price that is operated in this wave band to come pumping, also be one of advantage that realizes its commercial applications, Chinese scholars is mixed at ion and has been done number of research projects aspect the Dy at present.
Compare with oxide compound, crystal of fluoride has low phonon energy, and this makes rare earth ion have lower radiationless decay by inter-stage, has improved the quantum yield of optical transition and has prolonged the life-span of last energy level, thereby helped energy storage.We discover the crystal of cubic structure plumbous fluoride recently, have lower phonon energy, and the probability that this has greatly reduced radiationless transition has improved the quantum yield of optical transition; Higher specific refractory power has strengthened the spontaneous radiation probability, makes rare earth ion have moderate emission cross section by inter-stage; In addition, broad see through wavelength band (0.25～12.5 μ m), preparation cost is lower, easily obtains advantages such as large size sample.Aspects such as adulterated plumbous fluoride crystal of dysprosium and growth method thereof all still are not reported at present.
Summary of the invention
The object of the invention is to provide a kind of dysprosium doping to fluoridize leading crystal and preparation method thereof, and this crystal is expected to use in 2～5 mu m waveband laser devices.
Technical solution of the present invention is as follows:
A kind of dysprosium mixes and fluoridizes leading crystal, and this crystal molecule formula is: Dy
xPbF
2+3x, wherein x is Dy
3+Doping content, the span of x is 0.1～10mol%.
The growth method that described dysprosium mixes and fluoridizes leading crystal, this method comprises the following steps:
1. select the value of x, initial feed is DyF in the crystal growth prescription
3And PbF
2, according to molecular formula Dy
xPbF
2+3xAnd by stoichiometric ratio raw materials weighing, wherein x=0.1～10mol%;
2. the raw material thorough mixing that takes by weighing according to the above ratio is even, and vacuum drying and briquetting are put into graphite or platinum crucible, adopts PbF
2Crystal is as seed crystal, and growth atmosphere is argon gas or CF
4Deng gas, adopt melt method for growing.
Described melting method is warm terraced method or falling crucible method.
Technique effect of the present invention:
Show that through experiment and calculating dysprosium doping the fluoridizing leading crystal of the present invention's growth has lower phonon energy, long fluorescence lifetime, bigger absorption and emission cross section.Be expected in all solid state 2～5 mu m waveband laser devices, use.
Description of drawings
Fig. 1 is Dy of the present invention
0.02PbF
2.06Crystal Raman spectrum at room temperature
Fig. 2 and Fig. 3 are Dy of the present invention
0.02PbF
2.06Crystal absorption spectrum at room temperature
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing, but should not limit protection scope of the present invention with this.
Embodiment 1: warm terraced method growth Dy
0.01PbF
2.03Crystal
With high pure raw material DyF
3And PbF
2By molecular formula Dy
0.01PbF
2.03Mol ratio even for the thorough mixing of preparing burden, 130 ℃ the dehydration 12 hours, charge cask is a tetrafluoroethylene.Take out the back briquetting, put into plumbago crucible, growth atmosphere is an argon gas, add a cover at the crucible top, temperature rises to 940 ℃ of insulations after 6 hours with 40 ℃/hour, with 5 ℃/hour cooling growing crystal, behind the growth ending with 30 ℃/hour rate of temperature fall cool to room temperature.
Embodiment 2: warm terraced method growth Dy
0.05PbF
2.15Crystal
Present embodiment is with high pure raw material DyF
3And PbF
2By molecular formula Dy
0.05PbF
2.15Carry out proportioning, raw material is put into plumbago crucible 120 ℃ of dehydrations after 14 hours, and crucible bottom is placed PbF
2Crystal is as seed crystal, and growth atmosphere is CF
4Shielding gas, add a cover at the crucible top, temperature rises to 960 ℃ of constant temperature after 3 hours with 50 ℃/hour, with 4 ℃/hour cooling growing crystal, behind the growth ending with 40 ℃/hour rate of temperature fall cool to room temperature.
Embodiment 3: warm terraced method growth Dy
0.1PbF
2.3Crystal
Present embodiment is with high pure raw material DyF
3And PbF
2By molecular formula Dy
0.1PbF
2.3Carry out proportioning,, raw material is put into plumbago crucible 150 ℃ of dehydrations after 10 hours, and crucible bottom is placed PbF
2Crystal is as seed crystal, and growth atmosphere is an argon gas, and add a cover at the crucible top, and temperature rises to 980 ℃ of constant temperature after 3 hours with 45 ℃/hour, with 6 ℃/hour cooling growing crystal, behind the growth ending with 25 ℃/hour rate of temperature fall cool to room temperature.
Embodiment 4: Bridgman-Stockbarge method for growing Dy
0.01PbF
2.03Crystal
Present embodiment is with high pure raw material DyF
3And PbF
2By molecular formula Dy
0.01PbF
2.03Carry out proportioning, with high pure raw material DyF
3And PbF
2Mol ratio by molecular formula is even for the thorough mixing of preparing burden, in drying baker through 150 ℃ of dehydrations in 12 hours, even briquetting then.Use diameter to be 30mm, long in the platinum crucible of the sharp end of 150mm, reductor is a tetrafluoroethylene.960 ℃ of melt temperature, constant temperature 4 hours.Crystal solid-liquid growth interface thermograde is provided with 35 ℃/cm, with 1mm/ speed at one hour rating decline crucible, behind the growth ending with 30 ℃/hour rate of temperature fall cool to room temperature.
Embodiment 5: Bridgman-Stockbarge method for growing Dy
0.02PbF
2.06Crystal
Present embodiment is with high pure raw material TmF
3And PbF
2By molecular formula Tm
0.02PbF
2.06Carry out proportioning, raw material in drying baker through 140 ℃ of dehydrations in 14 hours, even briquetting then.Put into the flat platinum crucible that is of a size of 35mm * 35mm * 210mm, crucible bottom is placed PbF
2Crystal is as seed crystal, and reductor is a rubber.940 ℃ of melt temperature, constant temperature 6 hours.Crystal solid-liquid growth interface thermograde is set to 40 ℃/cm, with 0.8mm/ speed at one hour rating decline crucible, behind the growth ending with 30 ℃/hour rate of temperature fall cool to room temperature.Crystal takes out post-treatment and becomes 10 * 10 * 1mm
3Sample carry out spectrum test, crystal Raman spectrum at room temperature as shown in Figure 1, the phonon energy of this crystal maximum is about 260cm
-1Absorption spectrum under the room temperature draws this crystal by the J-O Theoretical Calculation and has bigger absorption and emission cross section as shown in Figures 2 and 3, finds also that simultaneously this crystal has long fluorescence lifetime, is expected to use in all solid state 2～5 mu m waveband laser devices.
Embodiment 6: Bridgman-Stockbarge method for growing Dy
0.1PbF
2.3Crystal
Present embodiment is with high pure raw material DyF
3And PbF
2By molecular formula Dy
0.1PbF
2.3Carry out proportioning, raw material in drying baker through 120 ℃ of dehydrations in 16 hours, even briquetting then.Using diameter is 40, and length is that crucible bottom is placed PbF in 180 the platinum crucible of the sharp end
2Crystal is as seed crystal, and reductor is a tetrafluoroethylene.920 ℃ of melt temperature, constant temperature 6 hours.The crystal growth temperature gradient is provided with 25 ℃/cm, with 1.2mm/ speed at one hour rating decline crucible, reduces to room temperature naturally with behind 30 ℃/hour the rate of temperature fall to 300 ℃ behind the growth ending.
The spectrum of the foregoing description has the similar result with embodiment 5.
Experiment and calculating show: the adulterated plumbous fluoride crystal of dysprosium of the present invention has low phonon energy, long fluorescence lifetime, bigger absorption and emission cross section, is expected to use in all solid state 2～5 mu m waveband laser devices.
Claims (3)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106702488A (en) * | 2016-12-15 | 2017-05-24 | 中国科学院上海硅酸盐研究所 | Praseodymium activated lead fluoride scintillation crystal material and preparation method thereof |
| CN109023523A (en) * | 2018-07-26 | 2018-12-18 | 暨南大学 | Infrared ytterbium erbium dysprosium three mixes lead fluoride laser crystal and preparation method thereof in a kind of 2.7-3 micron waveband |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580272A (en) * | 2009-06-09 | 2009-11-18 | 中国科学院上海光学精密机械研究所 | Ytterbium alkali co-doped lead fluoride crystal and preparation method thereof |
-
2010
- 2010-11-03 CN CN 201010530649 patent/CN102051682A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580272A (en) * | 2009-06-09 | 2009-11-18 | 中国科学院上海光学精密机械研究所 | Ytterbium alkali co-doped lead fluoride crystal and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《Solid State Ionics》 20090216 Elizabeth Dologlou Interconnection of the parameters obtained from thermally stimulated depolarization currents in beta- PbF2 doped with rare Earth ions 18-21 1-3 第180卷, 第1期 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106702488A (en) * | 2016-12-15 | 2017-05-24 | 中国科学院上海硅酸盐研究所 | Praseodymium activated lead fluoride scintillation crystal material and preparation method thereof |
| CN109023523A (en) * | 2018-07-26 | 2018-12-18 | 暨南大学 | Infrared ytterbium erbium dysprosium three mixes lead fluoride laser crystal and preparation method thereof in a kind of 2.7-3 micron waveband |
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Application publication date: 20110511 |