CN102888655B - Middle-infrared laser gain medium codoped bivalent chromium and cobalt ion II-VI crystal - Google Patents
Middle-infrared laser gain medium codoped bivalent chromium and cobalt ion II-VI crystal Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 132
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001429 cobalt ion Inorganic materials 0.000 title claims abstract description 38
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001430 chromium ion Inorganic materials 0.000 title claims abstract description 31
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Abstract
Description
技术领域 technical field
本发明涉及全固态激光增益介质技术,尤其涉及一种中红外宽谱可调谐激光增益介质双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体的制备方法,属于全固态激光介质领域。 The invention relates to all-solid-state laser gain medium technology, in particular to a method for preparing mid-infrared wide-spectrum tunable laser gain medium doubly doped with divalent chromium and cobalt ion II-VI crystals, belonging to the field of all-solid-state laser medium.
背景技术 Background technique
随着各种光学测试技术的发展,对于用途广泛、价格低廉的中红外激光光源的需求正日益增加。中红外激光器的波长可以覆盖 “分子指纹区”,它有着广泛的用途,包括大气遥感测试、非伤害性医学诊断、激光雷达、石油勘探以及各种诸如目标标定、故障排除和红外线对抗等军事应用。 With the development of various optical testing techniques, there is an increasing demand for versatile and inexpensive mid-infrared laser sources. The wavelength of mid-infrared lasers can cover the "molecular fingerprint region", which has a wide range of uses, including atmospheric remote sensing testing, non-invasive medical diagnosis, lidar, oil exploration and various military applications such as target calibration, troubleshooting and infrared countermeasures .
可以实现中红外波段激光输出的光源主要有:CO2气体激光器,其输出波长10~12 μm、铅盐异质节激光器其输出波长3~30 μm、量子级联半导体激光器其输出波长大于或等于3.7 μm,或者通过相对复杂的非线性光学转换技术来实现中红外波段激光输出的光源,如差频振荡激光器(DFG)、光参量振荡激光器(OPO)等。但是以上的中红外激光光源都遇到了限制其作为坚固耐用、低成本中红外激光光源使用的基本问题,如CO2气体激光器设备复杂且巨大,差频振荡激光器与光参量振荡激光器等都需要使用昂贵的光学器件,且也不稳定;铅盐异质节激光器与量子级联半导体激光器的激光输出功率较低。因此,迄今为止,以上所述激光器光源存在的缺陷使之尚不能在诸如遥感测试等高功率的应用中被使用。 The light sources that can realize laser output in the mid-infrared band mainly include: CO 2 gas lasers, whose output wavelength is 10-12 μm, lead-salt heterojunction lasers, whose output wavelength is 3-30 μm, and quantum cascade semiconductor lasers, whose output wavelength is greater than or equal to 3.7 μm, or a light source that realizes laser output in the mid-infrared band through a relatively complex nonlinear optical conversion technology, such as difference frequency oscillation laser (DFG), optical parametric oscillation laser (OPO), etc. However, the above mid-infrared laser sources have encountered basic problems that limit their use as durable, low-cost mid-infrared laser sources. For example, CO 2 gas laser equipment is complex and huge, and both difference frequency oscillation lasers and optical parametric oscillation lasers need to be used. Expensive optics, and unstable; lead-salt heterojunction lasers and quantum cascade semiconductor lasers have low laser output power. Therefore, the drawbacks of the above-mentioned laser sources have so far prevented their use in high-power applications such as remote sensing testing.
与上述激光器光源形成对比的是,基于过渡金属离子(TM2+)掺杂的Ⅱ--Ⅵ晶体ZnS、ZnSe、CdS以及CdSe等的全固态激光器正逐渐成为宽谱可调谐、高功率、高稳定性中红外激光光源。对过渡金属离子(TM2+),如Cr2+、Co2+、Fe2+掺杂的II-VI晶体的详细研究始于上世纪60年代。过渡金属离子进入半导体后在其能隙中会形成深能级,而且还会出现多重价态,因此早期的研究中将这种杂质离子看作荧光“克星”。这也是尽管过渡金属离子掺杂的II-VI晶体引起了人们相当大的兴趣,但其激光效应却是到上世纪90年代才有报道的原因。在20世纪90年代中期,美国Lawrence Livermore国家实验室的De Loach等人(L.D. DeLoach, R.H. Page, G.D. Wilke, S.A. Payne, W.F. Krupke, Transition metal-doped zinc chalcogenides: Spectroscopy and laser demonstration of a new class of gain media, Journal Name: IEEE Journal of Quantum Electronics; Journal Volume: 32; Journal Issue: 6; Other Information: PBD: Jun 1996, (1996) Medium: X; Size: pp. 885-895.)最先报道了过渡金属离子掺杂的II-VI晶体研究的突破性进展:他们研究了Cr2+、Co2+、Ni2+和Fe2+掺杂的各种锌硫族化合物的吸收与发射特性,认为此类化合物很有希望成为中红外激光介质的潜质,并且基于Cr2+:ZnSe和Cr2+:ZnS在室温下实现了2.4 μm的激光输出。 In contrast to the above-mentioned laser light sources, all-solid-state lasers based on transition metal ion (TM 2+ ) doped II-VI crystals ZnS, ZnSe, CdS, and CdSe are gradually becoming broadband tunable, high-power, and high-efficiency lasers. Stable mid-infrared laser light source. The detailed research on II-VI crystals doped with transition metal ions (TM 2+ ), such as Cr 2+ , Co 2+ , and Fe 2+ , began in the 1960s. Transition metal ions will form deep energy levels in the energy gap after entering the semiconductor, and there will also be multiple valence states. Therefore, this impurity ion was regarded as the "nemesis" of fluorescence in early studies. This is why, despite considerable interest in transition metal ion-doped II-VI crystals, their lasing effects were not reported until the 1990s. In the mid-1990s, De Loach et al. (LD DeLoach, RH Page, GD Wilke, SA Payne, WF Krupke, Transition metal-doped zinc chalcogenides: Spectroscopy and laser demonstration of a new class of Lawrence Livermore National Laboratory of the United States) gain media, Journal Name: IEEE Journal of Quantum Electronics; Journal Volume: 32; Journal Issue: 6; Other Information: PBD: Jun 1996, (1996) Medium: X; Size: pp. 885-895.) first reported A breakthrough in the research of II-VI crystals doped with transition metal ions: They studied the absorption and emission properties of various zinc chalcogenides doped with Cr 2+ , Co 2+ , Ni 2+ and Fe 2+ , and believed that Such compounds have great potential as mid-infrared laser media, and based on Cr 2+ :ZnSe and Cr 2+ :ZnS, a laser output of 2.4 μm has been achieved at room temperature.
常用的II-VI晶体主要有ZnS以及ZnSe。II-VI晶体具有优异的热机械性能,又具有较强的抗热冲击性能和优良的热传导性能,这就为过渡金属离子掺杂II-VI晶体激光器在大功率上的应用提供了必要条件。 Commonly used II-VI crystals mainly include ZnS and ZnSe. II-VI crystals have excellent thermomechanical properties, strong thermal shock resistance and excellent thermal conductivity, which provide the necessary conditions for the high-power application of transition metal ion-doped II-VI crystal lasers.
至于光谱和激光性能,过渡金属离子掺杂II-VI晶体非常接近于掺钛蓝宝石(Ti-S)激光器。可以预料,类似于掺钛蓝宝石激光器,过渡金属离子掺杂的II-VI晶体将能够通过多种多样的振荡方式发光,并且具有可用InGaAsP或InGaNAs二极管阵列的直接泵浦等优点。Fazzio等人对多重态能级的计算研究以及从实验上对ZnS、ZnSe中掺杂的V2+、Cr2+、Mn2+、Fe2+、Co2+、Ni2+离子的低衰变能级的验证都解释了大部分的研究都集中在Cr2+、Co2+、Fe2+离子的原因。Cr2+、Co2+、Fe2+离子的光谱范围分别是是2~3 μm、2.6~4 μm和3.7~5.2 μm,具有较宽的可调谐范围。这类激光器发出的光源代表了现在最简单、最实惠的中红外激光光源。 As for the spectral and lasing properties, transition metal ion doped II-VI crystals are very close to those of titanium-doped sapphire (Ti-S) lasers. It can be expected that, similar to Ti:sapphire lasers, transition metal ion-doped II-VI crystals will be able to emit light through a variety of oscillation modes, and have the advantage of direct pumping with InGaAsP or InGaNAs diode arrays. Computational study of multiple state energy levels by Fazzio et al. and experimental study on the low decay of V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ ions doped in ZnS and ZnSe The verification of energy levels explains why most of the researches focus on Cr 2+ , Co 2+ , Fe 2+ ions. The spectral ranges of Cr 2+ , Co 2+ , and Fe 2+ ions are 2-3 μm, 2.6-4 μm, and 3.7-5.2 μm, respectively, and have a wide tunable range. Sources from these lasers represent the simplest and most affordable mid-infrared laser sources available today.
尽管对于过渡金属离子掺杂的II-VI激光介质已经有了较为深入的研究,但是利用双掺杂或多掺杂过渡金属离子掺进II-VI晶体以增大激光器可调谐激光增益介质范围的研究却鲜有涉及。 Although the II-VI laser medium doped with transition metal ions has been studied in depth, the use of double-doped or multi-doped transition metal ions doped into II-VI crystals to increase the range of laser tunable laser gain media Research has rarely been involved.
发明内容 Contents of the invention
本发明的目的是要提供一种中红外宽谱可调谐激光增益介质双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体的制备方法;该双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体是利用安瓿双端置掺杂物真空热扩散传输法,或利用晶体双面镀掺杂物薄膜真空热扩散传输法;再通过二价铬与钴双掺杂离子重叠的吸收波长进行泵浦,可以同时实现两种离子受激激发,从而获得中红外宽谱可调谐激光增益介质-双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体。本发明提供这种新型掺杂晶体完全有望成为理想的宽波段中红外可调谐激光增益介质。 The purpose of the present invention is to provide a method for preparing a mid-infrared wide-spectrum tunable laser gain medium doped with divalent chromium and cobalt ions II--VI crystal; the double-doped divalent chromium and cobalt ions II--VI The crystal is vacuum thermal diffusion transmission method using double-ended dopants in ampoules, or vacuum thermal diffusion transmission method using dopant film on both sides of the crystal; and then pumped by the overlapping absorption wavelength of divalent chromium and cobalt double-doped ions , two kinds of ions can be excited and excited at the same time, so as to obtain mid-infrared broad-spectrum tunable laser gain medium-double doped divalent chromium and cobalt ion II-VI crystal. The invention provides that the novel doped crystal is fully expected to become an ideal broadband mid-infrared tunable laser gain medium.
本发明的另一目的是提供一种基于中红外宽谱可调谐激光增益介质双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体构建的激光输出实验装置,该实验装置采用双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体作为激光输出介质,实现1.6~4.2 μm中红外宽光谱波段可调谐的激光输出。 Another object of the present invention is to provide a laser output experimental device based on a mid-infrared wide-spectrum tunable laser gain medium doped with divalent chromium and cobalt ion II-VI crystals. Chromium and cobalt ion II-VI crystals are used as the laser output medium to achieve tunable laser output in the mid-infrared wide spectral band of 1.6-4.2 μm.
为实现上述目的,本发明是采用以下技术措施构成的技术方案来实现的。 In order to achieve the above purpose, the present invention is realized by adopting the technical solution composed of the following technical measures.
本发明一种中红外激光增益介质双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体的制备方法,其特征在于利用安瓿双端置掺杂物真空热扩散传输法制备双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体,包括以下具体工艺步骤: The invention discloses a method for preparing a mid-infrared laser gain medium double-doped divalent chromium and cobalt ion II-VI crystal, which is characterized in that the double-doped divalent chromium is prepared by using the vacuum thermal diffusion transmission method of dopants placed at both ends of an ampoule Cobalt ion II-VI crystals, including the following specific process steps:
(1)将Ⅱ--Ⅵ晶体薄圆片,置于由中间大、两端小的由三截石英管组成的石英安瓿中间,取单质Co粉末与单质Cr粉末分别置于石英安瓿的两端,且Co与Cr两种单质粉末各自与Ⅱ--Ⅵ晶体薄圆片之间的距离相等; (1) Place the Ⅱ-Ⅵ crystal thin disc in the middle of a quartz ampoule composed of three quartz tubes with a large middle and small ends, and place the simple Co powder and the simple Cr powder on the two ends of the quartz ampoule respectively. , and the distances between the Co and Cr two kinds of elemental powders and the Ⅱ--Ⅵ crystal thin discs are equal;
(2)将步骤(1)所述三截石英管组成的石英安瓿利用氢氧焰高温粘合在一起,并将其抽真空为10-3~10-5Pa后密封; (2) The quartz ampoule composed of three sections of quartz tubes described in step (1) is bonded together at high temperature with an oxygen-hydrogen flame, and then sealed after vacuumizing to 10 -3 ~ 10 -5 Pa;
(3)将步骤(2)密封好的石英安瓿放置于由多组加热棒加热的高温炉中,在温度为700~1300℃的条件下,热扩散1~15天,即得双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体激光增益介质样品; (3) Place the sealed quartz ampoule in step (2) in a high-temperature furnace heated by multiple sets of heating rods, and conduct thermal diffusion for 1 to 15 days at a temperature of 700-1300°C to obtain double-doped di Valence chromium and cobalt ions Ⅱ-Ⅵ crystal laser gain medium samples;
(4)最后将步骤(3)掺杂完成的二价铬与钴离子Ⅱ--Ⅵ晶体激光增益介质样品进行抛光、切割,即获得中红外宽谱可调谐激光增益介质双掺杂Cr2+,Co2+:Ⅱ--Ⅵ晶体。 (4) Finally, polish and cut the divalent chromium and cobalt ions II-VI crystal laser gain medium sample doped in step (3) to obtain mid-infrared broad-spectrum tunable laser gain medium double-doped Cr 2+ , Co 2+ : Ⅱ--Ⅵ crystal.
上述方案中,所述Ⅱ--Ⅵ晶体薄圆片是ZnS、或ZnSe、或ZnTe、或CdS、或CdSe或CdTe晶体薄圆片。 In the above solution, the II-VI crystal thin discs are ZnS, or ZnSe, or ZnTe, or CdS, or CdSe or CdTe crystal thin discs.
上述方案中,所述的单质钴粉末与单质铬粉末其纯度为99.99%以上;所述Ⅱ--Ⅵ晶体薄圆片其纯度为99.999%以上。 In the above solution, the purity of the elemental cobalt powder and elemental chromium powder is above 99.99%; the purity of the II-VI crystal thin discs is above 99.999%.
上述方案中,所述掺杂离子的浓度分别为Cr2+为1×1018 cm-3~1×1020 cm-3、Co2+为1×1018 cm-3~1×1020 cm-3。 In the above scheme, the concentrations of the dopant ions are respectively 1×10 18 cm -3 to 1×10 20 cm -3 for Cr 2+ and 1×10 18 cm -3 to 1×10 20 cm for Co 2+ -3 .
本发明一种中红外宽谱可调谐激光增益介质双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体的制备方法,其特征在于利用晶体双面镀铬薄膜和钴薄膜真空热扩散法制备双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体,包括以下具体工艺步骤: The invention discloses a method for preparing a mid-infrared wide-spectrum tunable laser gain medium double-doped with divalent chromium and cobalt ions II-VI crystal, which is characterized in that the double-doped crystal is prepared by vacuum thermal diffusion method of double-sided chromium-plated thin film and cobalt thin film. Heterovalent chromium and cobalt ion II-VI crystals, including the following specific process steps:
(1)利用溅射法或蒸镀法在Ⅱ--Ⅵ晶体薄圆片的两晶面分别镀上单质Co薄膜与单质Cr薄膜,其两晶面镀薄膜厚度为100~500nm; (1) Use the sputtering method or evaporation method to coat the two crystal surfaces of the II-VI crystal wafers with an elemental Co film and an elemental Cr film, respectively, and the thickness of the coating film on the two crystal surfaces is 100-500nm;
(2)将步骤(1)已镀好薄膜的Ⅱ--Ⅵ晶体薄圆片放入石英安瓿中,并将其抽真空为10-3~10-5Pa后密封; (2) Put the thin film-coated II-VI crystal discs in step (1) into a quartz ampoule, vacuumize it to 10 -3 ~ 10 -5 Pa and seal it;
(3)将步骤(2)密封好的石英安瓿放置于由多组加热棒加热的高温炉中,在温度为700~1300℃的条件下,热扩散1~15天,即获得双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体激光增益介质样品; (3) Place the sealed quartz ampoule in step (2) in a high-temperature furnace heated by multiple sets of heating rods, and conduct thermal diffusion at a temperature of 700-1300°C for 1-15 days to obtain a double-doped Valence chromium and cobalt ions Ⅱ-Ⅵ crystal laser gain medium samples;
(4)最后将步骤(3)掺杂完成的二价铬与钴离子Ⅱ--Ⅵ晶体激光增益介质样品进 行抛光、切割,即获得中红外宽谱可调谐激光增益介质双掺杂Cr2+,Co 2+:Ⅱ--Ⅵ晶体。 (4) Finally, polish and cut the divalent chromium and cobalt ions II-VI crystal laser gain medium sample doped in step (3) to obtain mid-infrared broad-spectrum tunable laser gain medium double-doped Cr 2+ , Co 2+ : Ⅱ--Ⅵ crystal.
上述方案中,所述Ⅱ--Ⅵ晶体薄圆片是ZnS、或ZnSe、或ZnTe、或CdS、或CdSe或CdTe晶体薄圆片。 In the above solution, the II-VI crystal thin discs are ZnS, or ZnSe, or ZnTe, or CdS, or CdSe or CdTe crystal thin discs.
上述方案中,所述单质钴薄膜和单质铬薄膜其纯度均为99.99%以上;所述Ⅱ--Ⅵ晶体薄圆片的纯度为99.999%以上。 In the above solution, the purity of the elemental cobalt thin film and elemental chromium thin film are both above 99.99%; the purity of the II-VI crystal thin discs is above 99.999%.
上述方案中,所述掺杂离子的浓度分别为Cr2+为1×1018 cm-3~1×1020 cm-3、Co2+为1×1018 cm-3~1×1020 cm-3。 In the above scheme, the concentrations of the dopant ions are respectively 1×10 18 cm -3 to 1×10 20 cm -3 for Cr 2+ and 1×10 18 cm -3 to 1×10 20 cm for Co 2+ -3 .
本发明一种基于中红外宽谱可调谐激光增益介质双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体构建的激光输出实验装置,其特征在于包括激光泵浦源、泵浦光束、密封箱、密封通光孔、输入腔镜、激光增益介质、输出腔镜、输出激光光束;从激光泵浦源输出的泵浦光束通过密封箱的密封通光孔进入输入腔镜,泵浦光束经输入腔镜到达激光增益介质,增益介质产生光转换实现光放大,然后到输出腔镜,经输出腔镜的激光再经密封通光孔输出激光光速。 The present invention is a laser output experimental device based on a mid-infrared wide-spectrum tunable laser gain medium doped with divalent chromium and cobalt ion II-VI crystals, which is characterized in that it includes a laser pump source, a pump beam, and a sealed box , sealed optical hole, input cavity mirror, laser gain medium, output cavity mirror, and output laser beam; the pump beam output from the laser pump source enters the input cavity mirror through the sealed optical hole of the sealed box, and the pump beam passes through the input The cavity mirror reaches the laser gain medium, and the gain medium generates light conversion to realize light amplification, and then reaches the output cavity mirror, and the laser light passing through the output cavity mirror outputs the laser light speed through the sealed optical hole.
上述方案中,所述泵浦光束波长为1.4~1.8μm;输出激光光束波长1.6~4.2μm,为使泵浦光束全透过而输出激光全反射,其输入腔镜镀膜;为使输出激光光束90%以上反射,其输出腔镜也镀膜。 In the above scheme, the wavelength of the pumping beam is 1.4-1.8 μm; the wavelength of the output laser beam is 1.6-4.2 μm. In order to make the pumping beam fully transmit and the output laser is totally reflected, the input cavity mirror is coated; in order to make the output laser beam More than 90% reflection, the output cavity mirror is also coated.
本发明所具有的特点及有益的技术效果如下: The characteristics and beneficial technical effects of the present invention are as follows:
本发明利用二价铬与钴离子双掺杂Ⅱ--Ⅵ晶体,获得了理想的中红外宽波段可调谐激光增益介质;其获得方法工艺步骤简单,易于操作与实现;具有中红外宽谱波段可调谐激光增益介质的Cr2+和Co2+双掺杂Ⅱ-Ⅵ晶体构建的激光输出实验装置,可输出1.6~4.2μm中红外宽谱可调谐激光;从而可大幅度增大激光器可调谐激光增益介质范围。 The present invention uses divalent chromium and cobalt ions double-doped II-VI crystals to obtain an ideal mid-infrared wide-band tunable laser gain medium; the obtaining method has simple process steps and is easy to operate and realize; it has a mid-infrared broad-spectrum band The laser output experimental device constructed of Cr 2+ and Co 2+ double-doped Ⅱ-Ⅵ crystals with tunable laser gain medium can output 1.6-4.2 μm mid-infrared wide-spectrum tunable laser; thus, the tunable laser can be greatly increased. Range of laser gain media.
本发明的基本原理是:利用安瓿双端置掺杂物真空热扩散传输法,或利用晶体双面镀掺杂物薄膜真空热扩散传输法,制备得到Cr2+和Co2+双掺杂Ⅱ--Ⅵ晶体;再利用二价铬与钴双掺杂离子重叠的吸收波长对增益介质进行泵浦,可以同时实现两种离子受激激发,从而获得1.6~4.2μm中红外宽谱可调谐激光输出。由于提供的1.6~4.2μm中红外宽谱可调谐激光输出的Cr2+和Co2+双掺杂Ⅱ-Ⅵ晶体激光增益介质,在这种激光介质中,Cr2+的5E→5T2跃迁吸收波长1.4~1.8 μm与Co2+的4A 2(F)→4T1(F) 跃迁吸收波长1.2~2.0 μm有重叠的波段1.4~1.8 μm,因此利用重叠范围内的某一波长,如1.55 μm,进行泵浦就能同时实现两种离子的受激激发;Cr2+的荧光光谱范围是1.6~2.8 μm,Co2+的荧光光谱为2.6~4.2 μm,从而得到1.6~4.2μm宽光谱可调谐激光输出。掺杂的 Cr2+和Co2+离子与周围离子之间的相互作用比较强,其电子状态参数与晶体密切相关,不同的晶体导致可调谐激光输出范围也会有不同。具体而言,Cr2+,Co2+:ZnS可调谐激光输出范围是1.6~3.6 μm,Cr2+,Co2+:ZnSe为1.8~3.8 μm,Cr2+,Co2+:CdS是2.0~3.9 μm,Cr2+,Co2+:CdSe为2.2~4.2μm。 The basic principle of the present invention is to prepare Cr 2+ and Co 2+ double-doped II by using the method of vacuum thermal diffusion transmission of dopants at both ends of the ampoule, or by using the method of vacuum thermal diffusion transmission of dopant films on both sides of the crystal. --Ⅵ crystal; the gain medium is pumped by the overlapping absorption wavelength of divalent chromium and cobalt doped ions, and the two ions can be stimulated and excited at the same time, so as to obtain a 1.6-4.2 μm mid-infrared broad-spectrum tunable laser output. Due to the 1.6-4.2μm mid-infrared broad-spectrum tunable laser gain medium of Cr 2+ and Co 2+ double-doped II-VI crystal laser gain medium, in this laser medium, the 5 E of Cr 2+ → 5 T 2 The transition absorption wavelength 1.4~1.8 μm and the 4 A 2 (F)→ 4 T 1 (F) transition absorption wavelength 1.2~2.0 μm of Co 2+ have an overlapping band 1.4~1.8 μm, so use a certain The wavelength, such as 1.55 μm, can realize the excitation of two kinds of ions at the same time by pumping; the fluorescence spectrum range of Cr 2+ is 1.6-2.8 μm, and the fluorescence spectrum of Co 2+ is 2.6-4.2 μm, thus obtaining 1.6- 4.2μm wide spectrum tunable laser output. The interaction between the doped Cr 2+ and Co 2+ ions and the surrounding ions is relatively strong, and their electronic state parameters are closely related to the crystal. Different crystals lead to different tunable laser output ranges. Specifically, the tunable laser output range of Cr 2+ , Co 2+ : ZnS is 1.6-3.6 μm, that of Cr 2+ , Co 2+ : ZnSe is 1.8-3.8 μm, and that of Cr 2+ , Co 2+ : CdS is 2.0 ~3.9 μm, Cr 2+ , Co 2+ : CdSe is 2.2~4.2 μm.
附图说明 Description of drawings
图1本发明实施例1和实施例2中利用石英安瓿双端置掺杂物真空热扩散传输法制备中红外宽谱可调谐激光增益介质二价铬与钴离子双掺杂Cr 2+,Co2+:ZnSe晶体和Cr2+,Co2+:CdS晶体过程示意图; Figure 1 In Example 1 and Example 2 of the present invention, the mid-infrared wide-spectrum tunable laser gain medium was prepared by using the double-terminal dopant vacuum thermal diffusion transfer method in the quartz ampoule . 2+ :ZnSe crystal and Cr 2+ ,Co 2+ :CdS crystal process diagram;
图2本发明实施例3和实施例4中通过晶体双面镀掺杂物膜真空热扩散传输法制备中红外宽谱可调谐激光增益介质二价铬与钴离子双掺杂Cr2+,Co2+:ZnTe晶体和Cr2+,Co2+:CdTe晶体过程示意图; Fig. 2 In Example 3 and Example 4 of the present invention, the mid-infrared wide-spectrum tunable laser gain medium was prepared by double-sided dopant film coating vacuum thermal diffusion transfer method in the present invention . 2+ :ZnTe crystal and Cr 2+ ,Co 2+ :CdTe crystal process diagram;
图3本发明实施例5基于中红外宽谱可调谐激光增益介质二价铬与钴离子双掺杂Cr2+,Co2+: ZnSe晶体构建的激光输出实验装置结构示意图。 Fig. 3 is a schematic diagram of the structure of a laser output experimental device constructed based on a mid-infrared wide-spectrum tunable laser gain medium divalent chromium and cobalt ions double-doped Cr 2+ , Co 2+ : ZnSe crystal according to Example 5 of the present invention.
图中,1 Co粉末,2加热棒,3石英安瓿,4晶体薄圆片,5 Cr粉末,6 Cr薄膜,7 Co薄膜,8 激光泵浦源,9 泵浦光束,10 密封箱,11密封通光孔,12输入腔镜,13激光增益介质,14输出腔镜,15输出激光光束。 In the figure, 1 Co powder, 2 heating rod, 3 quartz ampoule, 4 crystal thin disc, 5 Cr powder, 6 Cr thin film, 7 Co thin film, 8 laser pump source, 9 pump beam, 10 sealed box, 11 sealed Optical hole, 12 input cavity mirrors, 13 laser gain medium, 14 output cavity mirrors, 15 output laser beams.
具体实施方式 Detailed ways
下面结合附图并用具体实施例对本发明作进一步详细说明,但并不意味着是对本发明保护内容的任何限定。 The present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments, but it does not mean any limitation to the protection content of the present invention.
实施例1: Example 1:
利用安瓿双端置掺杂物真空热扩散传输法制备Cr2+,Co2+:ZnSe晶体 Preparation of Cr 2+ , Co 2+ : ZnSe Crystals by Vacuum Thermal Diffusion Transport of Ampoule Double-terminal Dopants
本实例选择Cr2+,Co2+: ZnSe作为制备Cr2+,Co2+: ZnSe晶体的原料,纯度99.99%以上的单质铬粉与钴粉、以及纯度99.999%以上的ZnSe晶体。 In this example, Cr 2+ , Co 2+ : ZnSe is selected as the raw material for preparing Cr 2+ , Co 2+ : ZnSe crystal, elemental chromium powder and cobalt powder with a purity of more than 99.99%, and ZnSe crystal with a purity of more than 99.999%.
本实例中,选择其纯度为99.99%以上的单质Cr粉末5和单质Co粉末1、以及其纯度为99.999%以上的ZnSe晶体薄圆片4作为制备Cr2+,Co2+:ZnSe双掺杂晶体的原料。 In this example, select the elemental Cr powder 5 and the elemental Co powder 1 whose purity is more than 99.99%, and the ZnSe crystal wafer 4 whose purity is more than 99.999% as the preparation of Cr 2+ , Co 2+ : ZnSe double-doped Crystal raw material.
首先将一块ZnSe晶体薄圆片4,其直径2 cm,厚度0.2 cm,置于由中间大、两端小的三截石英管组成的石英安瓿3中间位置,再取单质Co粉末1与单质Cr粉末5,其重量各为0.1 g,分别置于石英安瓿3两端位置,所述石英安瓿3两端的单质Co粉末与单质Cr粉末放置位置分别与石英安瓿3中间的ZnSe晶体薄圆片之间的距离相等,然后利用氢氧焰高温,将三截石英管粘合在一起,并将其抽真空为10-5 Pa后密封,如图1 所示;将密封好的石英安瓿3放置于由多组加热棒2加热的高温炉中,在温度为700℃的条件下热扩散15天,得双掺杂Cr2+,Co2+:ZnSe晶体激光增益介质样品,其掺杂离子的浓度分别为Cr2+为1×1018 cm-3、Co2+为1×1018 cm-3~1×1018 cm-3;最后将掺杂完成的双掺杂Cr2+,Co2+:ZnSe晶体激光增益介质样品进行抛光,切割,得到质地优良的激光增益介质Cr2+,Co2+: ZnSe晶体。 First, a thin ZnSe crystal disc 4 with a diameter of 2 cm and a thickness of 0.2 cm was placed in the middle of a quartz ampoule 3 composed of three quartz tubes with a large middle and small ends, and then the elemental Co powder 1 and the elemental Cr The powder 5, each of which weighs 0.1 g, is respectively placed at the two ends of the quartz ampoule 3, and the elemental Co powder and the elemental Cr powder at the two ends of the quartz ampoule 3 are respectively placed between the ZnSe crystal thin disc in the middle of the quartz ampoule 3 The distances are equal, and then the three sections of quartz tubes are glued together at high temperature by hydrogen-oxygen flame, and sealed after being vacuumed to 10 -5 Pa, as shown in Figure 1; the sealed quartz ampoule 3 is placed in the In a high-temperature furnace heated by multiple sets of heating rods 2, thermal diffusion was performed at a temperature of 700°C for 15 days to obtain a double-doped Cr 2+ , Co 2+ :ZnSe crystal laser gain medium sample, and the concentration of doped ions was respectively Cr 2+ is 1×10 18 cm -3 , Co 2+ is 1×10 18 cm -3 ~ 1×10 18 cm -3 ; finally the double doped Cr 2+ , Co 2+ : The ZnSe crystal laser gain medium sample is polished and cut to obtain a laser gain medium Cr 2+ , Co 2+ : ZnSe crystal with excellent texture.
实施例2: Example 2:
利用安瓿双端置掺杂物真空热扩散传输法制备Cr2+,Co2+:CdS晶体 Preparation of Cr 2+ , Co 2+ :CdS Crystals by Vacuum Thermal Diffusion Transport of Dopants in Ampoule
本实例中,选择其纯度为99.99%以上的单质Cr粉末5和单质Co粉末1、以及纯度为99.999%以上的CdS晶体薄圆片4作为制备Cr2+,Co2+:CdS双掺杂晶体的原料。 In this example, the elemental Cr powder 5 and the elemental Co powder 1 with a purity of more than 99.99% and the CdS crystal wafer 4 with a purity of more than 99.999% are selected as the preparation of Cr 2+ , Co 2+ :CdS double-doped crystal raw materials.
首先将一块CdS晶体薄圆片4,其直径2 cm,厚度0.2 cm,置于由中间大、两端小的三截石英管组成的石英安瓿3中间位置,再取单质Co粉末1与单质Cr粉末5,其重量各为0.3 g,分别置于石英安瓿3两端位置,所述石英安瓿3两端的单质Co粉末与单质Cr粉末放置位置分别与石英安瓿3中间的CdS晶体薄圆片4之间的距离相等,然后利用氢氧焰高温,将三截石英管粘合在一起,并将其抽真空为10-5 Pa后密封,如图1所示;将密封好的石英安瓿3放置于由多组加热棒2加热的高温炉中,在温度为1300℃的条件下热扩散2天,得双掺杂Cr2+,Co2+:CdS晶体激光增益介质样品,其掺杂离子的浓度分别为Cr2+为1×1020 cm-3、Co2+为1×1018 cm-3~1×1020 cm-3;最后将掺杂完成的双掺杂Cr2+,Co2+:CdS晶体激光增益介质样品进行抛光,切割,得到质地优良激光增益介质的Cr 2+,Co2+:CdS晶体。 First, a thin CdS crystal disc 4 with a diameter of 2 cm and a thickness of 0.2 cm was placed in the middle of a quartz ampoule 3 composed of three quartz tubes with a large middle and small ends, and then the elemental Co powder 1 and the elemental Cr The powders 5, each weighing 0.3 g, are respectively placed at the two ends of the quartz ampoule 3, and the placement positions of the simple substance Co powder and the simple substance Cr powder at the two ends of the quartz ampoule 3 are respectively in the middle of the CdS crystal wafer 4 in the middle of the quartz ampoule 3. The distances between them are equal, and then the three sections of quartz tubes are glued together at high temperature by hydrogen-oxygen flame, and sealed after vacuumizing to 10 -5 Pa, as shown in Figure 1; the sealed quartz ampoule 3 is placed in In a high-temperature furnace heated by multiple sets of heating rods 2, thermal diffusion was performed at a temperature of 1300°C for 2 days to obtain a double-doped Cr 2+ , Co 2+ :CdS crystal laser gain medium sample. The concentration of doped ions was Cr 2+ is 1×10 20 cm -3 , Co 2+ is 1×10 18 cm -3 ~ 1×10 20 cm -3 ; finally the double doped Cr 2+ , Co 2+ :CdS crystal laser gain medium samples were polished and cut to obtain Cr 2+ , Co 2+ :CdS crystals with good quality laser gain medium.
实施例3: Example 3:
利用晶体双面镀掺杂物薄膜真空热扩散传输法制备Cr2+,Co2+:ZnTe晶体 Preparation of Cr 2+ , Co 2+ : ZnTe Crystals by Vacuum Thermal Diffusion Transport Method of Dopant Thin Films Plated on Both Sides of Crystals
本实例中,选择其纯度为99.99%以上的单质Cr粉末5与单质Co粉末1、以及纯度为99.999%以上的ZnTe晶体薄圆片4作为制备Cr2+,Co2+:ZnTe双掺杂晶体的原料。 In this example, the elemental Cr powder 5 and the elemental Co powder 1 with a purity of more than 99.99% and the ZnTe crystal wafer 4 with a purity of more than 99.999% are selected as the preparation of Cr 2+ , Co 2+ : ZnTe double-doped crystal raw materials.
首先利用溅射镀膜方法在直径2 cm,厚度2mm的ZnTe晶体薄圆片4的两晶面分别镀上单质Co薄膜7与Cr薄膜6,镀膜厚度均为100 nm,将已镀膜的ZnTe晶体薄圆片4放入石英安瓿3中,将石英安瓿3抽真空约为10-5Pa,然后密封,如图2所示;密封完成后的石英安瓿3放置于由多组加热棒2加热的高温炉中,在温度为900℃的条件下热扩散13天,得双掺杂Cr2+,Co2+:ZnTe晶体激光增益介质样品,其掺杂离子的浓度分别为Cr 2+为1×1020 cm-3、Co2+为1×1020 cm-3;最后将掺杂完成的双掺杂Cr2+,Co2+:ZnTe晶体激光增益介质样品进行抛光、切割,得到质地优良的激光增益介质Cr2+,Co2+:ZnTe晶体。 Firstly, the two crystal surfaces of the thin ZnTe crystal wafer 4 with a diameter of 2 cm and a thickness of 2 mm were coated with an elemental Co thin film 7 and a Cr thin film 6 respectively by sputtering coating method, and the coating thickness was 100 nm. The wafer 4 is put into the quartz ampoule 3, the quartz ampoule 3 is evacuated to about 10 -5 Pa, and then sealed, as shown in Figure 2; the sealed quartz ampoule 3 is placed in a high temperature heated by multiple sets of heating rods 2 In the furnace, under the condition of 900 ℃ thermal diffusion for 13 days , double-doped Cr 2+ , Co 2+ :ZnTe crystal laser gain medium samples were obtained, and the concentration of doped ions was 1×10 20 cm -3 , Co 2+ is 1×10 20 cm -3 ; finally, the doped double-doped Cr 2+ , Co 2+ :ZnTe crystal laser gain medium sample is polished and cut to obtain a laser with excellent texture Gain medium Cr 2+ , Co 2+ : ZnTe crystal.
实施例4: Example 4:
利用晶体双面镀掺杂物薄膜真空热扩散传输法制备Cr2+,Co2+:CdTe晶体 Preparation of Cr 2+ , Co 2+ : CdTe Crystals by Vacuum Thermal Diffusion Transport Method of Dopant Thin Films Plated on Both Sides of Crystals
本实例中,选择纯度为99.99%以上的单质Cr粉末5和单质Co粉末1、以及纯度为99.999%以上的CdTe晶体作为制备Cr2+,Co2+:CdTe双掺杂晶体的原料。 In this example, elemental Cr powder 5 and elemental Co powder 1 with a purity of more than 99.99% and a CdTe crystal with a purity of more than 99.999% were selected as raw materials for preparing Cr 2+ , Co 2+ :CdTe double-doped crystals.
首先利用蒸镀法在直径2 cm,厚度2mm的CdTe晶体薄圆片4的两晶面分别镀上单质Co薄膜7与Cr薄膜6,镀膜厚度均为500 nm,将已镀薄膜的CdTe晶体薄圆片4放入石英安瓿3中,将石英安瓿3抽真空约为10-5Pa,然后密封,如图2所示;密封完成后的石英安瓿3放置于由多组加热棒2加热的高温炉中,在温度为1300℃的条件下热扩散1天,得双掺杂Cr 2+,Co2+:CdTe晶体激光增益介质样品,其掺杂离子的浓度分别为Cr2+为1×1020 cm-3、Co2+为1×1020 cm-3;最后将掺杂完成的双掺杂Cr2+,Co2+:CdTe晶体激光增益介质样品进行抛光、切割,得到质地优良的激光增益介质Cr2+,Co2+:CdTe晶体。 Firstly, the two crystal surfaces of a thin CdTe crystal wafer 4 with a diameter of 2 cm and a thickness of 2 mm were coated with an elemental Co thin film 7 and a Cr thin film 6 respectively by evaporation method, and the coating thickness was 500 nm. The wafer 4 is put into the quartz ampoule 3, the quartz ampoule 3 is evacuated to about 10 -5 Pa, and then sealed, as shown in Figure 2; the sealed quartz ampoule 3 is placed in a high temperature heated by multiple sets of heating rods 2 In the furnace, the temperature is 1300 ℃ under the condition of thermal diffusion for 1 day, and the double-doped Cr 2+ , Co 2+ :CdTe crystal laser gain medium sample is obtained, and the concentration of the doping ions is respectively 1×10 Cr 2+ 20 cm -3 , Co 2+ is 1×10 20 cm -3 ; finally, the doped double-doped Cr 2+ , Co 2+ :CdTe crystal laser gain medium sample is polished and cut to obtain a laser with excellent texture Gain medium Cr 2+ , Co 2+ : CdTe crystal.
本发明一种基于中红外宽谱可调谐激光增益介质双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体构建的激光输出实验装置,如图3所示,包括激光泵浦源8,泵浦光束9,密封箱10,密封通光孔11,输入腔镜12,激光增益介质13,输出腔镜14,输出激光光束15;从激光泵浦源8输出的泵浦光束9通过密封箱10的密封通光孔11进入输入腔镜12,泵浦光束9经输入腔镜12后到达由双掺杂二价铬与钴离子Ⅱ--Ⅵ晶体的激光增益介质13,然后到输出腔镜14,经输出腔镜14的激光再经密封通光孔11输出激光光束15。 The present invention is a laser output experimental device based on mid-infrared wide-spectrum tunable laser gain medium doped with divalent chromium and cobalt ion II-VI crystals, as shown in Figure 3, including laser pumping source 8, pumping Beam 9, sealed box 10, sealed optical hole 11, input cavity mirror 12, laser gain medium 13, output cavity mirror 14, output laser beam 15; the pump beam 9 output from the laser pump source 8 passes through the sealed box 10 The sealed optical hole 11 enters the input cavity mirror 12, and the pump beam 9 reaches the laser gain medium 13 made of double-doped divalent chromium and cobalt ion II-VI crystals after passing through the input cavity mirror 12, and then to the output cavity mirror 14, The laser output through the cavity mirror 14 is then output through the sealed light hole 11 to output the laser beam 15 .
实施例5: Example 5:
本发明将上述制备方法得到的其中之一优质的激光增益介质Cr2+,Co2+: ZnSe晶体,作为激光输出实验装置中对吸收光谱和发射光谱进行研究;这里确定具体Cr2+,Co2+: ZnSe晶体的泵浦波长为1.55 μm、Cr2+,Co2+: ZnSe晶体的发射波长是1.8~3.7 μm。选择平凹腔作为激光谐振腔镜,采用半导体激光器(LD)作为泵浦源进行泵浦,实现1.8~3.7 μm的可调谐中红外激光输出。以输出激光的波长3.2 μm为例,设计出的激光谐振腔系统。如图3所示,激光泵浦源8波长是1.55 μm,输出的泵浦光束9,其输入腔镜12镀膜,对1.55 μm全透过,对3.2 μm波长光全反射,激光增益介质13为Cr2+,Co2+: ZnSe,其输出腔镜14镀膜,对3.2 μm波长90%反射, 输出激光15其输出波长为3.2 μm。值得注意的是,当输出激光选择输出波长为2.9 μm附近时,处于水的强吸收带,因此激光实验装置中需要排除水气对激光谐振腔的影响,此时可将激光谐振腔置于真空中、或将激光谐振腔充保护气体于密封箱10中即可消除此影响。 In the present invention, one of the high-quality laser gain medium Cr 2+ , Co 2+ : ZnSe crystal obtained by the above preparation method is used as the laser output experimental device to study the absorption spectrum and emission spectrum; here, the specific Cr 2+ , Co 2+ : the pump wavelength of ZnSe crystal is 1.55 μm, Cr 2+ , Co 2+ : the emission wavelength of ZnSe crystal is 1.8~3.7 μm. A flat concave cavity is selected as the laser resonator mirror, and a semiconductor laser (LD) is used as the pumping source for pumping to achieve a tunable mid-infrared laser output of 1.8-3.7 μm. Taking the output laser with a wavelength of 3.2 μm as an example, the laser resonator system is designed. As shown in Figure 3, the wavelength of the laser pump source 8 is 1.55 μm, and the output pump beam 9 is coated with the input cavity mirror 12, which is completely transparent to 1.55 μm and totally reflective to 3.2 μm wavelength light. The laser gain medium 13 is Cr 2+ , Co 2+ : ZnSe, the output cavity mirror 14 is coated with a film, which reflects 90% of the wavelength of 3.2 μm, and the output wavelength of the output laser 15 is 3.2 μm. It is worth noting that when the output laser is selected to have an output wavelength near 2.9 μm, it is in the strong absorption band of water. Therefore, it is necessary to exclude the influence of water vapor on the laser resonator in the laser experimental device. At this time, the laser resonator can be placed in a vacuum This effect can be eliminated by filling the laser resonator cavity with protective gas in the sealed box 10.
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| Growth of Cr- and Co-Doped CdSe Crystals from High-Temperature Selenium Solutions;O.O. ADETUNJI et al;《Journal of ELECTRONIC MATERIALS》;20021231;第31卷(第7期);795-798 * |
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