CN102560657A - Chromium and praseodymium co-doped erbium-activated calcium lanthanum aluminate novel medium-wave infrared laser crystal - Google Patents

Chromium and praseodymium co-doped erbium-activated calcium lanthanum aluminate novel medium-wave infrared laser crystal Download PDF

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CN102560657A
CN102560657A CN201110263333XA CN201110263333A CN102560657A CN 102560657 A CN102560657 A CN 102560657A CN 201110263333X A CN201110263333X A CN 201110263333XA CN 201110263333 A CN201110263333 A CN 201110263333A CN 102560657 A CN102560657 A CN 102560657A
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laser
crystal
wave infrared
praseodymium
chromium
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涂朝阳
李坚富
游振宇
朱昭捷
王燕
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

A kind of novel medium wave infrared laser crystal of erbium activated aluminic acid lanthanum calcium that chromium praseodymium is co-doped with, is related to field of laser crystal materials. The chemical formula of the crystalline material is Cr3+:Er3+:Pr3+:CaLaAlO4, belongs to tetragonal crystal system I4/mmm, cell parameter is
Figure DDA0000089133450000011
Figure DDA0000089133450000012
V=170.26cm3, Dx=5.266g/cm3. Using La2O3, Cr2O3, Er2O3, Pr2O3 and analytically pure Al2O3, CaCO3 of 4N as raw material, Cr3+:Er3+:Pr3+:CaLaAlO4 raw material is obtained by high temperature solid state reaction, uses Czochralski grown crystal under an inert atmosphere. The material for the efficient laser output of 2.5~3.0um medium-wave infrared wave band, be applied to free space optical communication, remote sensing, Airborne IR directional jamming source, thermal infrared imager, laser radar, remote sensing chemical sensor, topographic survey, air pollution control, etc. fields.

Description

The novel medium wave infrared laser of the erbium activated lanthanum aluminate calcium crystal that a kind of chromium praseodymium is mixed altogether
Technical field
The present invention relates to field of laser crystal materials.
Background technology
In infrared 2.5 μ m～3 mu m waveband lasers contained atmospheric main light transmission window, free space optical communication, remote sensing, Airborne IR directional jamming source, thermal infrared imager, lidar, remote sensing chemical sensor, topographical surveying, air pollution control, etc. the field have important application.For this wave band of laser, vapor in the atmosphere and other gases comprise CO, CO 2And N 2There is strong vibration absorption peak in O etc., so this wave band also is called as atmosphere " molecular fingerprint " wave band.Therefore, this wave band of laser can be widely used in surveying the formation topsoil of lower concentration and the gas molecule of greenhouse gases effect, in atmosphere environment supervision and anti-chemical warfare, plays a significant role; Can also be used to monitoring human breathing gas, carry out medical diagnosis.In addition, this wave band of laser also comprises in medically application and organizes cutting and stitching, ophthalmology, Neurological Surgery etc.
At present, this wave band of laser mainly adopts by laser crystals is directly sharp and penetrates generation and adopt nonlinear optics methods such as optical parametric oscillator and difference frequency to obtain.Semiconductor laser also possibly be a kind of light source of simple and high performance-price ratio, still, except few cases, they need cool off and output rating limited.And Solid State Laser is expected to the very high power of output under high light beam quality and narrow linewidth.Utilize the near infrared semiconductor laser pumping, can provide stable, efficient, compact and wide spectrum to cover and the device of tuning range, and this to be semiconductor laser be difficult to accomplish.Therefore, the practicability of room temperature semiconductor laser pumping Solid State Laser as the simple and compact alternative source of light of this wave band, is used significant for remote sensing and trace gas detection etc.And, not only requiring the laser single-frequency, but also require frequency stabilization with laser applications in fields such as biology, atmospheric environment detection, laser ranging and photoelectronic warfares, this also is that semiconductor laser is difficult to accomplish.In addition, the wide gain band of some laser crystals also will be realized ultra-short pulse laser, and this makes this wave band of laser can further be applied to fields such as optical frequency standard, optical coherence tomography.In a word, along with the development of Solid State Laser, will be of value to numerous Application Areass of mid-infrared laser.
With compare through the method that adopts these wave band of laser of nonlinear optics generation such as optical parametric oscillator and difference frequency; By laser crystals directly swash penetrate produce this wave band of laser method aspect the easy of beam quality, stability and device; Has certain advantage; And determined the working level of this wave band of laser device with the generation of this wave band of laser and the research and development of changing closely-related gain, be the basic substance of this band laser widespread use; Therefore, also be a research focus in current photoelectron material field.Simultaneously, crystalline functional property and application and its crystalline structure are formed has substantial connection.
Directly swashing the main limited problem of penetrating the efficient mid-infrared laser output of generation by laser crystals is: because the energy of mid-infrared laser photon is lower; With the lattice vibration frequency of many famous laser crystalss be that the phonon vibration frequency is suitable; Caused the strong competition of quick radiationless relaxation and Laser emission like this; Therefore, caused the high passive loss of laser.In order to overcome this problem, must select material with low phonon vibrational frequency, directly swash by laser crystals and penetrate the generation mid-infrared laser, not only require the phonon energy of laser host little, phonon energy is more little, and then radiationless relaxation probability is also more little.Simultaneously, the spectrum of laser host is wanted high at 2.5 μ m～3.0 μ m and is passed through, and will have high optic damage threshold value and good physical and chemical performance, and the active ions that are doped in the gain media then will have bigger emission cross section (σ Em＞10 -21～10 -20Cm 2).
At present, 2.5 μ m～3 mu m waveband lasers are to be badly in need of most and are one of LASER Light Sources that lacks most, particularly～2.7 the LASER Light Source of mu m waveband.Since water for～2.7 μ m LASER Light Sources have very strong absorption (its uptake factor be water right～more than 200 times of 2.0 μ m LASER Light Source uptake factors); So the difficulty of relevant research for this wave band of laser crystal and device thereof is very big; So the research of relevant this respect report is all fewer; Level is not high yet, particularly at home, does not also see systematic research.
In addition, as active ions, rare earth or transition group ion-activated laser crystals can produce 2.5 μ m～3.0 μ m mid-infrared lasers, Er 3+, Ho 3+Deng being effective active ions.
Er wherein 3+Ion has abundant energy level, and it is corresponding 4I 11/2→ 4I 13/2Transition can produce the laser of 2.5～3.0 mu m wavebands.Usually, under the effect of crystal field, each main energy level can divide more sub-energy level, correspondingly Er 3+Ion can produce the fluorescent emission of a plurality of wavelength, usually, and Er 3+The activated crystal is at the fluorescence emission spectrum of 2.5～3.0 mu m wavebands, exists～2.6 μ m, 2.7 μ m, 2.8 μ m and a plurality of emission peaks of 2.9 mum wavelengths.Certainly, for the different laser substrate material, its crystal field intensity all has bigger difference with relevant parameter, makes that the division situation of energy level is also variant, causes the wavelength of each emission peak and relative power to change.
Document has report Er:YAlO at present 3(YAP), Er:Y 3Al 5O 12(YAG), Er:Gd 3Ga 5O 12(GGG), Er:Y 3Sc 2Ga 3O 12(YSGG), Er:LiYF 4(LYF) etc. crystal has been realized the laser output of these wave band hundred milliwatt magnitudes and even watt level.
Because Er 3+Ion has abundant energy level and transition channel, can produce simultaneously 1.54 mu m wavebands luminous (corresponding to 4I 13/2→ 4I 15/2Transition) and 2.5～3.0 mu m wavebands luminous (corresponding to 4I 11/2→ 4I 13/2Transition); Two luminescent transition channels form the intensive competition, make 2.5～3.0 mu m wavebands luminous a little less than, in order to improve 2.5～3.0 mu m waveband luminous intensities; Must seek out and can effectively suppress the luminous method of other wave band, wherein one of effective means is to mix Pr altogether 3+Sensitized ions can make Er 3+Laser lower level 4I 13/2Life-span reduce and reach the effect that intensifies, suppress Er 3+Produce 1.54um laser 4I 13/2→ 4I 15/2The competition of transition, thus help the output of 2.5～3.0um wave band of laser, improved quantum yield widely.In addition, mix Cr altogether 3+Sensitized ions can improve pumping efficiency.Cr 3+→ Er 3+→ Pr 3+Sensitization Mechanism see shown in Figure 1.
CaLaAlO 4<cLaAO>Crystal belongs to tetragonal system, has good physical and chemical performance, is insoluble to strong acid and strong base; Hardness is big; Have high thermal and laser damage threshold, crystal congruent melting when 1720 ℃ temperature can be adopted Czochralski grown large size gem-quality crystal; Crystal 2 .5～3.0um medium wave infrared band has high transmitance, and crystal has lower phonon energy and (is about 400cm -1), Er 3+Ion-activated crystal has bigger absorption and emission cross section at corresponding wave band, is the outstanding substrate material of 2.5～3.0um medium wave infrared laser gain media potential therefore.The Cr that from accompanying drawing 2 and accompanying drawing 3, is tested 3+: Er 3+: Pr 3+: CaLaAlO 4Crystalline absorb with the emitting fluorescence spectrogram in, can see that crystal has stronger absorption in xenon lamp emission light wave scope, have a plurality of emission peaks at 2.5～3.0um medium wave infrared band, its emission cross section is～10 -20Cm 2, help realizing the infrared efficient laser operation of 2.5～3.0um medium wave, so Cr 3+: Er 3+: Pr 3+: CLAO will be the outstanding medium wave infrared laser of an a kind of potential crystal.
Summary of the invention
The objective of the invention is to disclose a kind of laser crystal material Cr that can realize the efficient laser output of 2.5～3.0um medium wave infrared band 3+: Er 3+: Pr 3+: CaLaAlO 4
Realize the object of the invention technical scheme:
1. the novel medium wave infrared laser of erbium activated lanthanum aluminate calcium crystal that the chromium praseodymium is mixed altogether, the chemical formula of this crystalline material is Cr 3+: Er 3+: Pr 3+: CaLaAlO 4, belonging to tetragonal system I4/mmm, unit cell parameters does
Figure BDA0000089133430000041
Figure BDA0000089133430000042
V=170.26cm 3, Dx=5.266g/cm 3
2. the preparation method of the laser crystal material of an item 1 is characterized in that: the La that adopts 4N 2O 3, Cr 2O 3, Er 2O 3, Pr 2O 3With analytically pure Al 2O 3, CaCO 3As raw material, obtain Cr through high temperature solid state reaction 3+: Er 3+: Pr 3+: CaLaAlO 4Raw material adopts Czochralski grown crystal under inert atmosphere.
3. the purposes of the laser crystal material of an item 1; This material is used for the output of the efficient laser of 2.5～3.0um medium wave infrared band, be applied to free space optical communication, remote sensing, Airborne IR directional jamming source, thermal infrared imager, lidar, remote sensing chemical sensor, topographical surveying, air pollution control, etc. the field.
Description of drawings
Accompanying drawing 1 is ion sensitized mechanism;
Accompanying drawing 2 is a crystalline room temperature abosrption spectrogram;
Accompanying drawing 3 is crystalline room temperature fluorescence emmission spectrum figure;
Accompanying drawing 4 is the Laser Experiments device.1.Cr wherein 3+: Er 3+: Pr 3+: CaLaAlO 4Laser crystal bar; 2. xenon flash lamp pumping source; 3. resonator cavity total reflective mirror; 4. resonator cavity laser output mirror; 5. laser energy/resistance dynamometer.
Embodiment:
Embodiment one: Cr 3+: Er 3+: Pr 3+: CaLaAlO 4The crystalline growing and preparing
The used instrument of crystal pulling growth is the intermediate frequency lifting furnace of DJL-400, and the intermediate frequency power supply model is KGPF25-0.3-2.5.Adopt the thermopair of Pt/Pt-Rh and the Ou Lubiao temperature control that model is 815EPC.The crucible that is adopted is the iridium crucible of Φ 55mm * 50mm, and used raw material is the La of 4N 2O 3, Er 2O 3, Cr 2O 3, Pr 2O 3With analytically pure Al 2O 3, CaCO 3As raw material.According to following reaction formula preparation raw material:
(1-y-z)La 2O 3+xCr 2O 3+zEr 2O 3+yPr 2O 3+2CaCO 3+(1-x)Al 2O 3
→2CaLa (1-y-z)?Cr xPr yEr zAl (1-x)O 4+2CO 2x＝1at％～20at％，y＝0at％～50at％，z＝0at％～50at％。Even raw materials mix, be pressed into sheet, put platinum crucible into; Insert in the ordinary sinter stove, slowly be warmed up to 1080 ℃, keep 48h with 150 ℃/h; Repeat this process; Put into high temperature sintering furnace then at 1350 ℃ of following constant temperature sintering 72h, take out polycrystal, until X-ray powder diffraction with till standard card conforms to fully.
Pack raw material in the iridium crucible of Φ 55mm * 50mm into; For fear of the oxidation of iridium crucible, at first extract the air in the stove out, make that the air pressure in the stove reaches-0.01Pa; Charging into high-purity reducing gas again makes air pressure reach 0.04MPa; Be warmed up to the temperature higher 50 ℃ than fusing point then, constant temperature 1～2 hour makes the raw material fusing fully.With the crystal of platinoiridita silk nature nucleating growth as the large-sized gem-quality crystal of seeded growth.In the process of growth; The rate of pulling of seed rod is 1.3～1.5mm/h, and rate of temperature fall is 2～10 ℃/h, and the slewing rate of seed rod is 12～20r.p.m.; Behind the growth ending crystal is lifted from liquid level; Speed with 10～30 ℃/h is reduced to room temperature, obtains being of a size of the transparent crystals of φ 50mm * 30mm, then at N 2-H 2High temperature annealing is to eliminate oxygen defect under the mixed atmosphere.
Embodiment two: Cr 3+: Er 3+: Pr 3+: CaLaAlO 4The crystalline Laser Experiments
Process the high-quality Cr that is of a size of 3+: Er 3+: Pr 3+: CaLaAlO 4The crystal bar device adopts xenon lamp as pumping source, carries out Laser Experiments.Xenon flash lamp pumping Laser Experiments device is shown in accompanying drawing 4.In Laser Experiments, the xenon lamp that is adopted is of a size of ф 6mm * 90mm, PW 220 μ s; Repetition rate has 1Hz and 10Hz, and the laser resonance cavity length is 120mm, adopts Ping-Ping chamber mirror; Outgoing mirror and input mirror are thoroughly high at 2.64 μ m and 2.79 μ m～3.0 mu m wavebands; Input mirror is at～2.7 mu m wavebands high anti-(＞99.8%), and outgoing mirror is 5%～6% in the transmitance of～2.7 mu m wavebands, and the energy probe that is adopted adds the filtration eyeglass; Filtering eyeglass at＜1.8 mu m wavebands high anti-(reflectivity＞99%), is 75% in the transmitance of＞1.8 mu m wavebands.

Claims (2)

1. the novel medium wave infrared laser of erbium activated lanthanum aluminate calcium crystal that the chromium praseodymium is mixed altogether, it is characterized in that: the chemical formula of this crystalline material is Cr 3+: Er 3+: Pr 3+: CaLaAlO 4, belonging to tetragonal system I4/mmm, unit cell parameters does
Figure FDA0000089133420000011
Figure FDA0000089133420000012
V=170.26cm 3, Dx=5.266g/cm 3
2. the purposes of the laser crystal material of a claim 1; This material is used for the output of the efficient laser of 2.5～3.0um medium wave infrared band, be applied to free space optical communication, remote sensing, Airborne IR directional jamming source, thermal infrared imager, lidar, remote sensing chemical sensor, topographical surveying, air pollution control, etc. the field.
CN201110263333XA 2010-12-16 2011-09-06 Chromium and praseodymium co-doped erbium-activated calcium lanthanum aluminate novel medium-wave infrared laser crystal Pending CN102560657A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073294A (en) * 2013-01-17 2013-05-01 上海大学 Preparation method of Er3+ and Pr3+ co-doped yttrium lanthanum oxide scintillating material transparent ceramic material
WO2014006879A1 (en) * 2012-07-02 2014-01-09 国立大学法人北海道大学 Laser medium, laser oscillation device and laser oscillation method
WO2016208174A1 (en) * 2015-06-26 2016-12-29 日本電気株式会社 Ceramic, method for producing same, emitter and thermophotovoltaic power generator
CN107142108B (en) * 2017-07-17 2018-05-11 中南大学 A kind of composite fluorescent material for mixing dysprosium yttrium-calcium aluminate and its preparation method and application

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101619492A (en) * 2008-07-03 2010-01-06 中国科学院福建物质结构研究所 Chromium and praseodymium sensitized ions co-doped gadolinium gallium garnet novel laser crystal activated by erbium ions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101619492A (en) * 2008-07-03 2010-01-06 中国科学院福建物质结构研究所 Chromium and praseodymium sensitized ions co-doped gadolinium gallium garnet novel laser crystal activated by erbium ions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014006879A1 (en) * 2012-07-02 2014-01-09 国立大学法人北海道大学 Laser medium, laser oscillation device and laser oscillation method
CN103073294A (en) * 2013-01-17 2013-05-01 上海大学 Preparation method of Er3+ and Pr3+ co-doped yttrium lanthanum oxide scintillating material transparent ceramic material
WO2016208174A1 (en) * 2015-06-26 2016-12-29 日本電気株式会社 Ceramic, method for producing same, emitter and thermophotovoltaic power generator
CN107142108B (en) * 2017-07-17 2018-05-11 中南大学 A kind of composite fluorescent material for mixing dysprosium yttrium-calcium aluminate and its preparation method and application

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Application publication date: 20120711