WO2020253337A1 - Tunable laser chromium-doped gadolinium scandate crystal and preparation method therefor - Google Patents

Tunable laser chromium-doped gadolinium scandate crystal and preparation method therefor Download PDF

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WO2020253337A1
WO2020253337A1 PCT/CN2020/084453 CN2020084453W WO2020253337A1 WO 2020253337 A1 WO2020253337 A1 WO 2020253337A1 CN 2020084453 W CN2020084453 W CN 2020084453W WO 2020253337 A1 WO2020253337 A1 WO 2020253337A1
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crystal
chromium
growth
doped
scandate
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徐军
王东海
李纳
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南京同溧晶体材料研究院有限公司
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/34—Edge-defined film-fed crystal-growth using dies or slits
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/24—Complex oxides with formula AMeO3, wherein A is a rare earth metal and Me is Fe, Ga, Sc, Cr, Co or Al, e.g. ortho ferrites

Definitions

  • the invention relates to the technical field of optoelectronic functional materials, in particular to a laser crystal material as a working substance in a tunable solid-state laser.
  • Tunable laser refers to a laser whose laser wavelength can be continuously changed within a certain wavelength range (that is, within a wide spectral interval). Tunable laser technology is of great significance in science and technology and national defense construction. Tunable lasers are the main technical equipment for the research of various laser spectroscopy technologies, and they are also important light sources for research in optics, optoelectronics, medicine, and biology. In the military, tunable lasers will be one of the important laser light sources for optoelectronic countermeasures in the future, such as lidar, laser communication, laser underwater detection and communication, laser remote sensing, and laser blinding.
  • the most researched and applied tunable laser crystals are Cr 3+ : BeAl 2 O 4 (Alexandrite), Ti 3+ : Al 2 O 3 (Titanium-doped sapphire) and Cr 3+ : LiCaAlF 6 , Cr 3+ : LiSrAlF 6 , but considering the tunable wavelength range of the crystal, absorption coefficient, emission cross-section, pumping mode and growth process of the crystal, there is no crystal that can well meet people's needs.
  • the main disadvantages of Cr 3+ :BeAl 2 O 4 (Alexandrite) crystals are: the tuning range is between 700 and 800 nm, the emission cross section is small (6 ⁇ 10 -21 cm 2 ), the required pump threshold is high, and It also has the disadvantages of high damage rate and high thermal lens effect. In addition, because BeO is highly toxic, it also brings great difficulties to growth.
  • Ti 3+ :Al 2 O 3 crystal The main disadvantage of Ti 3+ :Al 2 O 3 crystal is: the appearance of Ti 3+ -Ti 4+ ion pairs in the crystal makes absorption appear in the laser output band, that is, the near-infrared band, which affects its laser performance. Its laser upper energy level life is short (only 3.2 ⁇ s), requiring short pulse lasers, Q-switched lasers, continuous wave lasers or flash lamp pumps that generate particularly short pulses, which further limits its applications.
  • the purpose of the present invention is to provide a chromium-doped gadolinium scandate laser crystal whose chemical formula is Gd (Sc 1-x Cr x )O 3 , where the value range of x is 0.00001 ⁇ 0.3.
  • a method for preparing the above-mentioned chromium-doped gadolinium scandate laser crystal is also provided.
  • the method adopts the guided mode method or the pulling method to grow, and the specific steps are:
  • the initial raw materials are Cr 2 O 3 , Sc 2 O 3 and Gd 2 O 3 with a purity of 4N or 5N.
  • step (3) Take out the cake material obtained in step (2) and put it into the crucible of the crystal growth furnace to prepare for growth;
  • the crucible material used in step (3) is tungsten or molybdenum.
  • the thermal field insulation material of the crystal growth furnace used in step (3) is graphite hard felt or soft felt, and the heater is a graphite heater.
  • the chromium-doped gadolinium scandate laser crystal provided by the present invention with the chemical formula Gd(Sc 1-x Cr x )O 3 , is used in tunable solid-state lasers.
  • the corresponding preparation method is also provided, using guided mode or The pulling method is suitable for tungsten or molybdenum crucibles.
  • the produced crystals have good quality and moderate mechanical properties.
  • the characteristics of tunable laser band width can be
  • Figure 1 is a photo of a rod-shaped GdScO 3 crystal grown by the guided mode method
  • Figure 2 is a photo of a sheet-shaped GdScO3 crystal grown by the guided mode method
  • Figure 3 shows the emission spectra of 0.1% Cr 3+ :GdScO 3 and 0.5% Cr 3+ :GdScO 3 crystals at room temperature from 1000 nm to 1150 nm.
  • Gadolinium scandate (Cr 3+ :GdScO 3 ) crystal belongs to the orthorhombic system and is an ideal laser matrix material.
  • the phonon energy is as low as 452, which helps reduce the probability of multi-phonon relaxation.
  • Scandium ion (Sc 3+ ) forms an octahedral coordination with oxygen ion (O 2+ ) in the crystal lattice, which can be replaced by chromium ion (Cr 3+ ), chromium-doped gadolinium scandate (Cr 3+ :GdScO 3 ) crystal It is expected to become a new type of tunable laser crystal material.
  • the chemical formula of the crystal in the present invention is Gd(Sc 1-x Cr x )O 3 , where the value of x ranges from 0.00001 to 0.3.
  • the Cr 3+ :GdScO 3 crystal with good quality and larger size is grown. This crystal has the advantages of moderate mechanical properties and wide tunable laser band. It is a good tunable laser crystal material with a tunable range Between 650 and 1100nm.
  • the initial raw materials are Cr 2 O 3 , Sc 2 O 3 and Gd 2 O 3 with a purity of 4N or 5N, and the value of x is selected.
  • Gd(Sc 1-x Cr x ) O 3 According to the molecular formula of chromium-doped gadolinium scandate laser crystal, Gd(Sc 1-x Cr x ) O 3 , accurately weighed, and do the ingredients.
  • Figure 1-2 is the appearance of the grown rod-shaped GdScO 3 and sheet-shaped GdScO 3.
  • Figure 3 performs performance test experiments on the crystals, and obtains 0.1% Cr 3+ : GdScO 3 , 0.5% Cr 3+ : GdScO 3 crystals at 1000nm at room temperature ⁇ 1150nm emission spectrum, the available tuning range is between 650 ⁇ 1100nm.
  • the chromium-doped gadolinium scandate laser crystal of the present invention can be grown using tungsten or molybdenum crucibles, which has a low cost advantage compared with iridium crucible growth.

Abstract

Provided is a tunable laser chromium-doped gadolinium scandate crystal and a preparation method therefor. The crystal has a chemical formula represented by Gd(Sc 1-xCr x)O 3, where in the value of x ranges from 0.00001 to 0.3. The crystal belongs to the orthorhombic crystal system, with a=5.45, b=5.75, and c=7.93. Edge-defined film-fed growth or Czochralski method is used, and the growth atmosphere is high-purity argon. A Cr 3+:GdScO 3 crystal with improved quality and larger size is grown. The crystal has the advantages of having appropriate mechanical properties and wide tunable laser waveband. The tuning range is between 650 nm and 1100 nm. Compared with the prior art, the chromium-doped gadolinium scandate crystal can be grown using tungsten crucible or molybdenum crucible and has the advantage of low cost compared with growth using iridium crucible.

Description

一种可调谐激光晶体掺铬钪酸钆及其制备方法Tunable laser crystal chromium-doped gadolinium scandate and preparation method thereof 技术领域Technical field
本发明涉及光电子功能材料技术领域，尤其是涉及一种作为可调谐固态激光器中工作物质的激光晶体材料。The invention relates to the technical field of optoelectronic functional materials, in particular to a laser crystal material as a working substance in a tunable solid-state laser.
背景技术Background technique
可调谐激光是指在一定波长范围内(即宽光谱间隔内)激光波长可以连续改变的激光。可调谐激光技术，在科学技术和国防建设上具有十分重要的意义。可调谐激光器是各种激光光谱技术研究的主要技术设备，也是光学、光电子学、医学、生物学等研究的重要光源。在军事上，可调谐激光器将是未来光电子对抗的重要激光光源之一，如激光雷达，激光通信，激光水下探测和通信，激光遥感，激光致盲等。Tunable laser refers to a laser whose laser wavelength can be continuously changed within a certain wavelength range (that is, within a wide spectral interval). Tunable laser technology is of great significance in science and technology and national defense construction. Tunable lasers are the main technical equipment for the research of various laser spectroscopy technologies, and they are also important light sources for research in optics, optoelectronics, medicine, and biology. In the military, tunable lasers will be one of the important laser light sources for optoelectronic countermeasures in the future, such as lidar, laser communication, laser underwater detection and communication, laser remote sensing, and laser blinding.
自1963年L.F.Johnson等人采用闪光灯泵浦，在掺Ni 2+的MgF 2晶体中实现了第一个固态可调谐激光运转以来，人们发现了很多可调谐激光晶体，如Ti 3+:Al 2O 3、Cr 3+:Mg 2SiO 4、Cr 3+:LiSrAlF 6、Cr 3+:BeAl 2O 4等，但由于各种原因，大多数可调谐激光晶体只限于作实验室工具，无法推向工业应用。目前研究最多的、已进入应用领域的可调谐激光晶体是Cr 3+:BeAl 2O 4(紫翠宝石)、Ti 3+:Al 2O 3(掺钛蓝宝石)和Cr 3+:LiCaAlF 6、Cr 3+:LiSrAlF 6，但是从晶体的可调谐波长范围、吸收系数、发射截面、泵浦方式和生长工艺等因素来综合考虑，目前还没有一种晶体能够很好地满足人们的需求。 Since LF Johnson et al. used flash lamp pumping in 1963 and realized the first solid-state tunable laser operation in Ni 2+ doped MgF 2 crystals, people have discovered many tunable laser crystals, such as Ti 3+ :Al 2 O 3. Cr 3+ : Mg 2 SiO 4 , Cr 3+ : LiSrAlF 6 , Cr 3+ : BeAl 2 O 4, etc. However, due to various reasons, most tunable laser crystals are limited to laboratory tools and cannot be pushed to Industrial applications. At present, the most researched and applied tunable laser crystals are Cr 3+ : BeAl 2 O 4 (Alexandrite), Ti 3+ : Al 2 O 3 (Titanium-doped sapphire) and Cr 3+ : LiCaAlF 6 , Cr 3+ : LiSrAlF 6 , but considering the tunable wavelength range of the crystal, absorption coefficient, emission cross-section, pumping mode and growth process of the crystal, there is no crystal that can well meet people's needs.
Cr 3+:BeAl 2O 4(紫翠宝石)晶体的主要缺点是：调谐范围在700～800nm之间，发射截面小(6×10 -21cm 2)，所需的泵浦阈值高，而且还具有高损伤率和高热透镜效应等缺点，另外由于BeO剧毒，也给生长带来很大困难。 The main disadvantages of Cr 3+ :BeAl 2 O 4 (Alexandrite) crystals are: the tuning range is between 700 and 800 nm, the emission cross section is small (6×10 -21 cm 2 ), the required pump threshold is high, and It also has the disadvantages of high damage rate and high thermal lens effect. In addition, because BeO is highly toxic, it also brings great difficulties to growth.
Ti 3+:Al 2O 3晶体的主要缺点是：该晶体中Ti 3+-Ti 4+离子对的出现，使得在激光输出波段，即近红外波段出现吸收，影响了其激光性能，而且由于其激光上能级寿命短(只有3.2μs)，需用短脉冲激光、Q开关激光、连续波激光或产生特别短脉冲的闪光灯泵浦，也进一步限制了它的应用。 The main disadvantage of Ti 3+ :Al 2 O 3 crystal is: the appearance of Ti 3+ -Ti 4+ ion pairs in the crystal makes absorption appear in the laser output band, that is, the near-infrared band, which affects its laser performance. Its laser upper energy level life is short (only 3.2μs), requiring short pulse lasers, Q-switched lasers, continuous wave lasers or flash lamp pumps that generate particularly short pulses, which further limits its applications.
Cr3+:LiCaAlF6、Cr 3+:LiSrAlF 6晶体尽管具有调谐范围较宽，发射截面大，所需的泵浦阈值低等诸多优点。但也存在着吸收系数小、LD泵浦的激光效率低等问题。因此，寻找可调谐范围更宽，且能够直接使用闪光灯和LD泵浦的可调谐激光晶体材料成为目前激光晶体研究领域的热点之一。 Cr3 +: LiCaAlF6, Cr 3+: LiSrAlF 6 crystal despite having a wide tuning range, large emission cross section, the desired advantages of low pump threshold. However, there are also problems such as low absorption coefficient and low efficiency of LD pumped laser. Therefore, looking for a tunable laser crystal material that has a wider tunable range and can directly use flash lamps and LD pumps has become one of the current hot spots in the field of laser crystal research.
发明内容Summary of the invention
针对现有技术中存在的如何解决开发一种成本低、易工业化且成长性良好的激光晶体的技术难题，本发明的目的是提供一种掺铬钪酸钆激光晶体，该晶体的化学式为Gd(Sc 1-xCr x)O 3，其中x的取值范围为0.00001～0.3。 Aiming at the technical problem of how to develop a laser crystal with low cost, easy industrialization and good growth in the prior art, the purpose of the present invention is to provide a chromium-doped gadolinium scandate laser crystal whose chemical formula is Gd (Sc 1-x Cr x )O 3 , where the value range of x is 0.00001～0.3.
同时，还提供了一种上述掺铬钪酸钆激光晶体的制备方法，该方法采用导模法或提拉法生长，具体步骤为：At the same time, a method for preparing the above-mentioned chromium-doped gadolinium scandate laser crystal is also provided. The method adopts the guided mode method or the pulling method to grow, and the specific steps are:
(1)初始原料采用纯度为4N或5N的Cr 2O 3、Sc 2O 3和Gd 2O 3，选定x的取值后，根据掺铬 钪酸钆激光晶体分子式Gd(Sc 1-xCr x)O 3，按照摩尔比x：(1-x)精确称量，其中x的取值范围为0.00001～0.3，进行配料； (1) The initial raw materials are Cr 2 O 3 , Sc 2 O 3 and Gd 2 O 3 with a purity of 4N or 5N. After selecting the value of x, according to the molecular formula of chromium-doped scandate gadolinium laser crystal Gd(Sc 1-x Cr x )O 3 , which is accurately weighed according to the molar ratio x: (1-x), where the value of x is in the range of 0.00001 to 0.3, and the batching is carried out;
(2)将原料在玛瑙研钵中充分混合均匀后，使用油压机将其压成饼料，油压压力为180-250MPa，时长1.5-4.5min，然后放入高温退火炉中，1400℃-1700℃高温烧结20-26小时；(2) After fully mixing the raw materials in an agate mortar, use a hydraulic press to press them into cakes. The hydraulic pressure is 180-250MPa, and the duration is 1.5-4.5min. Then, they are put into a high temperature annealing furnace at 1400℃-1700 High temperature sintering at ℃ for 20-26 hours;
(3)将步骤(2)获得的饼料取出，装入长晶炉的坩埚中准备生长；(3) Take out the cake material obtained in step (2) and put it into the crucible of the crystal growth furnace to prepare for growth;
(4)充入高纯惰性气体作为保护气氛，按照如下生长步骤：升温化料、引晶、缩颈、放肩、等径生长以及收尾进行生长，而后缓慢降温至室温，获得掺铬钪酸钆单晶。(4) Filling with high-purity inert gas as a protective atmosphere, and following the growth steps: heating up the material, seeding, necking, shouldering, isodiametric growth and finishing for growth, and then slowly cooling to room temperature to obtain chromium doped scandium Gadolinium single crystal.
作为改进，步骤(3)中所用坩埚材料为钨或钼。As an improvement, the crucible material used in step (3) is tungsten or molybdenum.
作为改进，步骤(3)中所用长晶炉的热场保温材料为石墨硬毡或软毡，加热器为石墨加热器。As an improvement, the thermal field insulation material of the crystal growth furnace used in step (3) is graphite hard felt or soft felt, and the heater is a graphite heater.
有益效果：本发明提供的掺铬钪酸钆激光晶体，化学式为Gd(Sc 1-xCr x)O 3，用于可调谐固态激光器中，还提供了对应的制备方法，采用导模法或提拉法，适用于钨或钼的坩埚，与现有的铱金坩埚热场制备方法相比具有低成本的优势，更有利于产业化。同时生成的晶体质量优良、机械性能适中。可调谐激光波段宽的特点，能够成 Beneficial effects: The chromium-doped gadolinium scandate laser crystal provided by the present invention, with the chemical formula Gd(Sc 1-x Cr x )O 3 , is used in tunable solid-state lasers. The corresponding preparation method is also provided, using guided mode or The pulling method is suitable for tungsten or molybdenum crucibles. Compared with the existing iridium-gold crucible thermal field preparation method, it has the advantage of low cost and is more conducive to industrialization. At the same time, the produced crystals have good quality and moderate mechanical properties. The characteristics of tunable laser band width can be
为一种可产业化、低成本且质量精度高的激光晶体生长方法。It is an industrialized, low-cost and high-quality laser crystal growth method.
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。The above description is only an overview of the technical solution of the present invention. In order to understand the technical means of the present invention more clearly and implement it in accordance with the content of the description, the preferred embodiments of the present invention are described in detail below with the accompanying drawings.
附图说明Description of the drawings
图1为导模法生长的棒状GdScO 3晶体的照片； Figure 1 is a photo of a rod-shaped GdScO 3 crystal grown by the guided mode method;
图2为导模法生长的片状GdScO3晶体的照片；Figure 2 is a photo of a sheet-shaped GdScO3 crystal grown by the guided mode method;
图3为0.1％Cr 3+:GdScO 3、0.5％Cr 3+:GdScO 3晶体室温下1000nm～1150nm发射光谱。 Figure 3 shows the emission spectra of 0.1% Cr 3+ :GdScO 3 and 0.5% Cr 3+ :GdScO 3 crystals at room temperature from 1000 nm to 1150 nm.
具体实施方式Detailed ways
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。The specific embodiments of the present invention will be described in further detail below in conjunction with the drawings and embodiments. The following examples are used to illustrate the present invention, but not to limit the scope of the present invention.
钪酸钆(Cr 3+:GdScO 3)晶体属于正交晶系，是一种较为理想的激光基质材料。声子能量低为452，有利于减少多声子弛豫发生的概率。钪离子(Sc 3+)在晶格中与氧离子(O 2+)形成八面体配位，可以被铬离子(Cr 3+)取代，掺铬钪酸钆(Cr 3+:GdScO 3)晶体有望成为一种新型的可调谐激光晶体材料。 Gadolinium scandate (Cr 3+ :GdScO 3 ) crystal belongs to the orthorhombic system and is an ideal laser matrix material. The phonon energy is as low as 452, which helps reduce the probability of multi-phonon relaxation. Scandium ion (Sc 3+ ) forms an octahedral coordination with oxygen ion (O 2+ ) in the crystal lattice, which can be replaced by chromium ion (Cr 3+ ), chromium-doped gadolinium scandate (Cr 3+ :GdScO 3 ) crystal It is expected to become a new type of tunable laser crystal material.
本发明中晶体的化学式为Gd(Sc 1-xCr x)O 3，其中x的取值范围为0.00001～0.3，该晶体属于正交晶系，a＝5.45，b＝5.75，c＝7.93。采用导模法或提拉法，生长气氛为高纯氩。生长出质量较好、尺寸较大的Cr 3+:GdScO 3晶体，该晶体具有机械性能适中、可调谐激光波段宽的优点，是一种较好的可调谐激光晶体材料，其可调谐范围在650～1100nm之间。 The chemical formula of the crystal in the present invention is Gd(Sc 1-x Cr x )O 3 , where the value of x ranges from 0.00001 to 0.3. The crystal belongs to the orthorhombic system, a=5.45, b=5.75, and c=7.93. Guided mold method or pulling method is used, and the growth atmosphere is high-purity argon. The Cr 3+ :GdScO 3 crystal with good quality and larger size is grown. This crystal has the advantages of moderate mechanical properties and wide tunable laser band. It is a good tunable laser crystal material with a tunable range Between 650 and 1100nm.
实施例1Example 1
(1)初始原料采用纯度为4N或5N的Cr 2O 3、Sc 2O 3和Gd 2O 3，选定x的值，根据掺铬钪酸钆激光晶体分子式Gd(Sc 1-xCr x)O 3，精确称量，进行配料。(2)将原料在玛瑙研钵中充分混合均匀后，使用油压机将其压成饼料，油压压力为220MPa，时长3min，然后放入高温退火炉中， 1550℃高温烧结24小时。(3)将(2)中获得的饼料取出，装入长晶炉的坩埚中准备生长。(4)充入高纯惰性气体作为保护气氛，按照如下生长步骤：升温化料、引晶、缩颈、放肩、等径生长以及收尾进行生长，而后缓慢降温至室温，获得掺铬钪酸钆单晶。 (1) The initial raw materials are Cr 2 O 3 , Sc 2 O 3 and Gd 2 O 3 with a purity of 4N or 5N, and the value of x is selected. According to the molecular formula of chromium-doped gadolinium scandate laser crystal, Gd(Sc 1-x Cr x ) O 3 , accurately weighed, and do the ingredients. (2) After fully mixing the raw materials in an agate mortar, use a hydraulic press to press them into cakes. The hydraulic pressure is 220 MPa and the duration is 3 minutes. Then, they are placed in a high temperature annealing furnace and sintered at 1550°C for 24 hours. (3) Take out the cake material obtained in (2) and put it into the crucible of the crystal growth furnace to prepare for growth. (4) Filling with high-purity inert gas as a protective atmosphere, and following the growth steps: heating up the material, seeding, necking, shouldering, iso-diameter growth and finishing for growth, and then slowly cooling to room temperature to obtain chromium-doped scandium acid Gadolinium single crystal.
图1-2为生长的棒状GdScO 3、片状GdScO 3的外观图，图3对晶体进行性能测试实验，获得0.1％Cr 3+:GdScO 3、0.5％Cr 3+:GdScO 3晶体室温下1000nm～1150nm发射光谱，可得调谐范围在650～1100nm之间。该与现有技术相比，本发明掺铬钪酸钆激光晶体可采用钨或钼坩埚生长，与铱坩埚生长相比具有低成本优势。 Figure 1-2 is the appearance of the grown rod-shaped GdScO 3 and sheet-shaped GdScO 3. Figure 3 performs performance test experiments on the crystals, and obtains 0.1% Cr 3+ : GdScO 3 , 0.5% Cr 3+ : GdScO 3 crystals at 1000nm at room temperature ～1150nm emission spectrum, the available tuning range is between 650～1100nm. Compared with the prior art, the chromium-doped gadolinium scandate laser crystal of the present invention can be grown using tungsten or molybdenum crucibles, which has a low cost advantage compared with iridium crucible growth.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several embodiments of the present invention, and the descriptions are more specific and detailed, but they should not be understood as limiting the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (4)

  1. 一种掺铬钪酸钆激光晶体，其特征在于，该晶体的化学式为Gd(Sc 1-xCr x)O 3，其中x的取值范围为0.00001～0.3。 A chromium-doped gadolinium scandate laser crystal is characterized in that the chemical formula of the crystal is Gd(Sc 1-x Cr x )O 3 , and the value of x is in the range of 0.00001 to 0.3.
  2. 一种如权利要求1所述的掺铬钪酸钆激光晶体的制备方法，其特征在于，该方法采用导模法或提拉法生长，具体步骤为：A method for preparing a chromium-doped gadolinium scandate laser crystal according to claim 1, characterized in that the method adopts a guided mode method or a pulling method to grow, and the specific steps are:
    (1)初始原料采用纯度为4N或5N的Cr 2O 3、Sc 2O 3和Gd 2O 3，选定x的取值后，根据掺铬钪酸钆激光晶体分子式Gd(Sc 1-xCr x)O 3，按照摩尔比x：(1-x)精确称量，其中x的取值范围为0.00001～0.3，进行配料； (1) The initial raw materials are Cr 2 O 3 , Sc 2 O 3 and Gd 2 O 3 with a purity of 4N or 5N. After selecting the value of x, according to the molecular formula of chromium-doped scandate gadolinium laser crystal Gd(Sc 1-x Cr x )O 3 , which is accurately weighed according to the molar ratio x: (1-x), where the value of x is in the range of 0.00001 to 0.3, and the batching is carried out;
    (2)将原料在玛瑙研钵中充分混合均匀后，使用油压机将其压成饼料，油压压力为180-250MPa，时长1.5-4.5min，然后放入高温退火炉中，1400℃-1700℃高温烧结20-26小时；(2) After fully mixing the raw materials in an agate mortar, use a hydraulic press to press them into cakes. The hydraulic pressure is 180-250MPa, and the duration is 1.5-4.5min. Then, they are put into a high temperature annealing furnace at 1400℃-1700 High temperature sintering at ℃ for 20-26 hours;
    (3)将步骤(2)获得的饼料取出，装入长晶炉的坩埚中准备生长；(3) Take out the cake obtained in step (2) and put it into the crucible of the crystal growth furnace to prepare for growth;
    (4)充入高纯惰性气体作为保护气氛，按照如下生长步骤：升温化料、引晶、缩颈、放肩、等径生长以及收尾进行生长，而后缓慢降温至室温，获得掺铬钪酸钆单晶。(4) Filling with high-purity inert gas as a protective atmosphere, and following the growth steps: heating up the material, seeding, necking, shouldering, iso-diameter growth and finishing for growth, and then slowly cooling to room temperature to obtain chromium-doped scandium acid Gadolinium single crystal.
  3. 根据权利要求2所述的掺铬钪酸钆激光晶体的制备方法，其特征在于：步骤(3)中所用坩埚材料为钨或钼。The method for preparing a chromium-doped gadolinium scandate laser crystal according to claim 2, wherein the crucible material used in step (3) is tungsten or molybdenum.
  4. 根据权利要求2所述的掺铬钪酸钆激光晶体的制备方法，其特征在于：步骤(3)中所用长晶炉的热场保温材料为石墨硬毡或软毡，加热器为石墨加热器。The method for preparing a chromium-doped gadolinium scandate laser crystal according to claim 2, wherein the thermal field insulation material of the crystal growth furnace used in step (3) is graphite hard felt or soft felt, and the heater is a graphite heater .
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CN114108072A (en) * 2020-08-28 2022-03-01 中国科学院上海光学精密机械研究所 Rare earth ion doped GdScO3Laser crystal preparation and application thereof
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