WO2018129962A1 - 碲酸盐晶体及其生长方法与应用 - Google Patents

碲酸盐晶体及其生长方法与应用 Download PDF

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WO2018129962A1
WO2018129962A1 PCT/CN2017/104972 CN2017104972W WO2018129962A1 WO 2018129962 A1 WO2018129962 A1 WO 2018129962A1 CN 2017104972 W CN2017104972 W CN 2017104972W WO 2018129962 A1 WO2018129962 A1 WO 2018129962A1
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crystal
crystals
phthalate
growth
teo
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PCT/CN2017/104972
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French (fr)
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陶绪堂
卢伟群
高泽亮
孙友轩
吴倩
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山东大学
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Priority to JP2018554742A priority Critical patent/JP6649508B2/ja
Priority to US16/313,031 priority patent/US11193219B2/en
Publication of WO2018129962A1 publication Critical patent/WO2018129962A1/zh

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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
    • 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
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/004—Oxides; Hydroxides
    • 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
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12—Salt solvents, e.g. flux growth
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/09—Processes or apparatus for excitation, e.g. pumping
    • H01S3/091—Processes or apparatus for excitation, e.g. pumping using optical pumping
    • H01S3/094—Processes or apparatus for excitation, e.g. pumping using optical pumping by coherent light
    • H01S3/0941—Processes or apparatus for excitation, e.g. pumping using optical pumping by coherent light of a laser diode
    • H01S3/09415—Processes or apparatus for excitation, e.g. pumping using optical pumping by coherent light of a laser diode the pumping beam being parallel to the lasing mode of the pumped medium, e.g. end-pumping
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/10—Controlling the intensity, frequency, phase, polarisation or direction of the emitted radiation, e.g. switching, gating, modulating or demodulating
    • H01S3/11—Mode locking; Q-switching; Other giant-pulse techniques, e.g. cavity dumping
    • H01S3/1123—Q-switching
    • H01S3/117—Q-switching using intracavity acousto-optic devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
    • H01S3/16—Solid materials
    • H01S3/1601—Solid materials characterised by an active (lasing) ion
    • H01S3/1603—Solid materials characterised by an active (lasing) ion rare earth
    • H01S3/1618—Solid materials characterised by an active (lasing) ion rare earth ytterbium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
    • H01S3/16—Solid materials
    • H01S3/163—Solid materials characterised by a crystal matrix

Definitions

  • the invention relates to a kind of silicate crystals and a growth method and application thereof, and belongs to the technical field of crystal materials.
  • the acousto-optic effect is to change the refractive index of the medium by ultrasonic waves to form a distribution that changes periodically with time and space. It is equivalent to a phase grating.
  • the incident laser passes through the medium modulated by the ultrasonic wave, it will produce diffraction, the frequency of the diffracted laser, The intensity, direction, etc. will change as the ultrasonic wave changes.
  • acousto-optic devices are not only widely used in the modulation of laser beams, but also have achieved remarkable achievements in the high-density, large-bandwidth real-time signal processing in the time domain and frequency domain, and gradually formed and developed an emerging Signal processing technology (acoustic and optical signal processing technology).
  • the performance of the acousto-optic device needs to be further improved, which not only depends on the improvement of the design method of the acousto-optic device, but more importantly, it is developed.
  • a new type of acousto-optic material with excellent performance.
  • the ideal acousto-optic material should have the following properties: 1 large sound and light figure of merit (the power of the diffracted light is proportional to the sound and light figure); 2 low sound attenuation; 3 wide transmission band and high transparency, incident Both the laser and the diffracted laser have good permeability; 4 high laser damage threshold, it is not easy to cause defects in the material under the action of strong laser; 5 easy to obtain large size, high optical quality crystal; 6 stable physical and chemical properties, not easy Deliquescence, decomposition; 7 easy to process, and low prices.
  • laser crystals have important and broad application requirements in a wide range of fields such as military, industrial, communications, and medical.
  • Laser crystals are the core component of all-solid-state lasers. The performance of all-solid-state lasers depends on the performance of the crystals.
  • a multi-functional composite crystal material which can combine the acousto-optic Q-switching performance and the laser performance, that is, a laser self-adjusting Q crystal, which can reduce the working loss of the composite all-solid-state laser and improve the compounding.
  • a laser self-adjusting Q crystal which can reduce the working loss of the composite all-solid-state laser and improve the compounding.
  • the TeO 2 crystal has a wide transmission range and a large sound and light excellent value
  • the bismuth silicate crystal obtained by combining the two in the present invention can be used as a new excellent high-frequency acousto-optic material.
  • the citrate crystal can be used as an excellent laser crystal, especially as an excellent laser self-adjusting Q crystal.
  • the present invention provides a novel class of phthalate crystals, while providing a method of growing citrate crystals and the use of such crystals.
  • crystals described in the present invention should all be construed as single crystals unless specifically stated to be polycrystalline.
  • a class of phthalate crystals having the chemical formula of MTe 3 O 8 , M Ti, Zr, Hf, belonging to the cubic system, the Ia-3 space group, the transmission band from visible to infrared, and the transparency ⁇ 70%.
  • the niobate crystal is further doped with a rare earth element (Re), and the doping amount of the rare earth element is controlled at 0 ⁇ Re/M ⁇ 1, a molar ratio, further preferably 5%;
  • the rare earth element is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or/and Lu.
  • the transmission band is 300 to 6500 nm.
  • the crystal in the above method of growing the niobate crystal, can be grown by a flux method, a pulling method or a crucible dropping method.
  • the crystal is grown by a flux method, and the steps are as follows:
  • the flux system is one of the following substances, but is not limited thereto:
  • the molar ratio of the citrate to the flux system is 1: (1 ⁇ 5);
  • the crystal growth material obtained in the step (1) is placed in a platinum crucible, rapidly heated to melt completely, fully stirred uniformly, and slowly cooled to promote spontaneous nucleation and growth of the crystal;
  • the crystal growth material obtained in the step (1) is placed in a platinum crucible, rapidly heated to melt completely, fully stirred uniformly, slowly cooled to the saturation point of the melt, and the niobate seed crystal is poured into the crystal. Slow cooling causes crystal growth;
  • the crystal growth temperature range is 750 to 900 ° C, and the temperature reduction rate is 0.01 to 5 ° C / h.
  • the crystal rotation parameter of the step (2) crystal growth of the niobate is: a rotation speed of 5 to 50 rd, an acceleration time of 1 to 10 s, an operation time of 30 to 180 s, and an intermittent time of 5 to 50s.
  • the step of lowering the crystal growth of the bismuth citrate in step (2) is: cooling at a rate of 0.01 to 4 ° C / h to 750 to 850 ° C, a growth period of 40 to 70 days .
  • the obtained bismuth silicate single crystal has a length of ⁇ 20 mm and a thickness of ⁇ 10 mm.
  • the crystal can also be grown by a melt method such as a pulling method or a helium dropping method, which can be carried out according to the prior art.
  • the rare earth element-doped silicate crystals are obtained by the growth in the step (2).
  • the bismuth silicate crystal is applied to the fabrication of an optical modulation device as an acousto-optic crystal; further preferably, the optical modulation device is an acousto-optic modulator, an acousto-optic deflector or an acousto-optic modulating device. Q device.
  • citrate crystals are as follows:
  • phthalate crystals as Raman laser crystals
  • phthalate crystals as a high energy particle detection material.
  • the method for growing crystals of the present invention requires simple growth conditions and is easy to implement; the obtained centimeter-scale citrate single crystal is sufficient for orientation processing, intrinsic property test; in addition, the chemistry used in the crystal growth method of the present invention Raw materials can be purchased directly at the market and are inexpensive.
  • the bismuth silicate single crystal grown by the method of the present invention has an experimental powder X-ray diffraction pattern which is consistent with the theoretical powder X-ray diffraction pattern obtained by theoretical calculation, indicating that the grown crystal is a cubic crystal of citrate crystal. .
  • the prior art is limited to the structure of a phthalate crystal.
  • the present invention has internationally grown a bismuth silicate single crystal, and has obtained a strontium hydride single crystal having a size and quality sufficient for practical use.
  • the phthalate single crystal of the invention has stable physical and chemical properties, does not deliquesce, and does not decompose.
  • the crystal growth cycle can be adjusted according to the actual situation, and the actual desired size of the tantalate single crystal can be obtained for related industrial applications.
  • Fig. 1 is a powder X-ray diffraction pattern of an experimental example of titanium polysilicate grown in Example 1 of the present invention and theoretical calculation results (a is an experimental powder X-ray diffraction pattern, and b is a theoretical calculation result).
  • Example 2 is a photograph of a titanium silicate seed crystal prepared in Example 1.
  • Example 3 is a photograph of a titanium single crystal film prepared in Example 2.
  • Example 4 is a photograph of a titanium single crystal film prepared in Example 3.
  • Figure 5 is a photograph of a titanium single crystal film prepared in Example 4.
  • Figure 6 is a schematic diagram of the operation of a typical acousto-optic crystal Q-switching.
  • Figure 7 is a schematic view of the operation of a typical laser crystal.
  • Figure 8 is a schematic diagram of the operation of a typical laser self-tuning Q crystal.
  • 1, 7, and 12 are laser diodes
  • 2, 8, and 13 are focusing systems
  • 3 and 14 are concave mirrors
  • 4 are Nd:YVO 4 /Nd:YAG laser crystals
  • 5 are TiTe 3 O 8 sounds.
  • the optical medium, 6, 9, 11, and 16 are plane mirrors
  • 10 is a Yb:TiTe 3 O 8 laser crystal
  • 15 is a Yb:TiTe 3 O 8 laser self-adjusting Q crystal.
  • the raw materials TiO 2 and TeO 2 are compounded according to the stoichiometric ratio of TiTe 3 O 8 and added to the flux system Li 2 CO 3 -TeO 2 (Li 2 CO 3 :TeO 2 molar ratio is 2:3), tannic acid
  • Li 2 CO 3 -TeO 2 Li 2 CO 3 -TeO 2 molar ratio is 2:3
  • tannic acid Li 2 CO 3 -TeO 2
  • the molar ratio of titanium to the flux system is 1:3, placed in a platinum crucible with a volume of ⁇ 50mm ⁇ 70mm, and the temperature is rapidly raised to 980°C to melt the raw material completely, and the mixture is fully stirred uniformly; the platinum rod is inserted and crystallized, and the temperature is slowly lowered.
  • the cooling rate is 0.55 ° C / h
  • the growth period is 5 days
  • the seed crystal rod is proposed to obtain orange-yellow polycrystal (as shown in Figure 2).
  • the powder X-ray diffraction pattern of the test was consistent with the theoretical calculation (as shown in Fig. 1), indicating that the cubic crystal of titanium citrate was obtained, from which small crystals of good quality were picked as growth sizes. Seed crystals of larger crystals.
  • the raw materials TiO 2 and TeO 2 are compounded according to the stoichiometric ratio of TiTe 3 O 8 and added to the flux system Li 2 CO 3 -TeO 2 (Li 2 CO 3 :TeO 2 molar ratio is 2:3), tannic acid
  • the molar ratio of titanium to the flux system is 1:3, placed in a platinum crucible with a volume of ⁇ 50mm ⁇ 70mm, and the temperature is rapidly increased to 980°C to completely melt the raw material, and the mixture is fully stirred; the temperature is slowly lowered to the saturation point of the melt to implement
  • the small crystal obtained in Example 1 was crystal grown for the seed crystal, and the temperature drop rate was 0.25 ° C / h, and the growth period was 10 days, that is, an orange-yellow bulk single crystal (as shown in FIG. 3 ) was obtained.
  • the powder X-ray diffraction pattern of the experiment was tested to be consistent with the theoretical calculation, indicating that a cubic crystal of titanium
  • the titanium tantalum single crystal obtained in Example 2 was subjected to orientation processing into a wafer of a desired size, and its transmission spectrum was examined, and it was found to have a wide transmission band (480 to 6000 nm).
  • the crystal was placed in the air for 6 months without deliquescent and did not decompose, indicating that the crystal was stable in physical and chemical properties.
  • the raw materials TiO 2 and TeO 2 are compounded according to the stoichiometric ratio of TiTe 3 O 8 and added to the flux system Li 2 CO 3 -TeO 2 (Li 2 CO 3 :TeO 2 molar ratio is 2:3), tannic acid
  • the molar ratio of titanium to the flux system is 1:3, placed in a platinum crucible with a volume of ⁇ 50mm ⁇ 70mm, and the temperature is rapidly raised to 980°C to completely melt the raw material, and the mixture is stirred sufficiently; the temperature is slowly lowered to the saturation point of the melt to [
  • the 100] direction crystal is used as a seed crystal for crystal growth, the temperature drop rate is 0.06 ° C / h, and the growth period is 20 days, that is, an orange-yellow bulk single crystal can be obtained (as shown in FIG. 4 ).
  • the powder X-ray diffraction pattern of the experiment was tested to be consistent with the theoretical calculation, indicating that a cubic crystal of titanium
  • the raw materials TiO 2 and TeO 2 are compounded according to the stoichiometric ratio of TiTe 3 O 8 and added to the flux system TeO 2 , the molar ratio of titanium ruthenate to the flux system is 1:3, and the volume is ⁇ 50 mm ⁇ 70 mm.
  • the temperature is rapidly increased to 1080 ° C to melt the raw material completely, and the mixture is fully stirred; the temperature is slowly lowered to the saturation point of the melt, and the crystal is grown as a seed crystal in the [100] direction, and the cooling rate is 0.05 ° C / h, and the growth is performed. With a period of 40 days, a bulk single crystal can be obtained (as shown in Figure 5).
  • the powder X-ray diffraction pattern of the experiment was tested to be consistent with the theoretical calculation, indicating that a cubic crystal of titanium niobate crystal was obtained.
  • the starting material TeO 2 and TiO 2 TiTe 3 O 8 according to the stoichiometric ratio of ingredients, Yb 2 O 3 and simultaneously added to the flux in the system TeO 2, Yb 2 O 3 and TiO 2 molar ratio of 0.05: 1, telluric acid titanium
  • the molar ratio to the flux system is 1:3, placed in a platinum crucible with a volume of ⁇ 50mm ⁇ 70mm, and the temperature is rapidly raised to 1100°C to melt the raw material completely, and the mixture is fully stirred; slowly cooling to the saturation point of the melt to [100
  • the crystal of the direction is crystal growth as a seed crystal, the temperature drop rate is 0.04 ° C / h, and the growth period is 50 days, that is, a Yb:TiTe 3 O 8 bulk single crystal can be obtained.
  • An acousto-optic Q-switched device was fabricated using the titanium germanium single crystal grown in Example 3, and the working schematic is shown in FIG. 1 is a laser diode whose output light passes through a focusing system 2 to a Nd:YVO 4 /Nd:YAG laser crystal 3.
  • the resonant cavity adopts a flat-concave structure, and the acousto-optic medium 5 uses a titanium single crystal of tantalum.
  • a laser device was fabricated using the Yb:TiTe 3 O 8 single crystal grown in Example 5, and the working schematic is shown in FIG. 7 is a laser diode whose output light passes through a focusing system 8 to a Yb:TiTe 3 O 8 laser crystal 10.
  • Example 8 Application of TiTe 3 O 8 Single Crystal as Laser Self-Tuning Q Crystal
  • a laser self-aligning Q device was fabricated using the Yb:TiTe 3 O 8 single crystal grown in Example 5, and the working schematic is shown in FIG. 12 is a laser diode whose output light passes through a focusing system 13 to a Yb:TiTe 3 O 8 laser self-tuning Q crystal 15.
  • the cavity is a flat-concave structure.
  • the raw materials ZrO 2 and TeO 2 are compounded according to the stoichiometric ratio of ZrTe 3 O 8 and added to the flux system TeO 2 , the molar ratio of zirconium silicate to the flux system is 1:4, and the volume is ⁇ 50 mm ⁇ 70 mm.
  • the temperature is rapidly increased to completely melt the raw material, and the mixture is fully stirred; the temperature is slowly lowered to the saturation point of the melt, and the crystal is grown as a seed crystal in the [100] direction, the cooling rate is 0.02 ° C / h, and the growth period is 40.
  • a zirconium citrate single crystal can be obtained.
  • the powder X-ray diffraction pattern of the experiment was tested to be consistent with the theoretical calculation, indicating that a cubic crystal of zirconium silicate single crystal was obtained.
  • the raw materials HfO 2 and TeO 2 are compounded according to the HfTe 3 O 8 stoichiometric ratio, and added to the flux system Li 2 CO 3 -TeO 2 (Li 2 CO 3 :TeO 2 molar ratio is 2:3), tannic acid
  • the molar ratio of bismuth to flux system is 1:4, placed in a platinum crucible with a volume of ⁇ 50mm ⁇ 70mm, and the temperature is raised rapidly to melt the raw material completely, and the mixture is fully stirred; slowly cool down to the saturation point of the melt, in the direction of [100]
  • the crystal grows as a seed crystal, the cooling rate is 0.02 ° C / h, and the growth period is 60 days, that is, a single crystal of ruthenium ruthenate can be obtained.
  • the powder X-ray diffraction pattern of the test was in agreement with the theoretical calculation, indicating that a cubic crystal of bismuth ruthenate single crystal was obtained.

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Abstract

碲酸盐晶体及其生长方法与应用，晶体的化学式为MTe 3O 8，M＝Ti、Zr、Hf，属于立方晶系，Ia-3空间群，透过波段从可见到红外，透明度≥70％。所述碲酸盐晶体的生长方法，可采用助熔剂法、提拉法或坩埚下降法生长晶体，所述碲酸盐晶体可作为声光晶体应用于光学调制器件的制作。碲酸盐单晶的尺寸和质量能够满足实际应用。

Description

[根据细则37.2由ISA制定的发明名称]　碲酸盐晶体及其生长方法与应用 技术领域
本发明涉及一类碲酸盐晶体及其生长方法与应用，属于晶体材料技术领域。
背景技术
声光效应是通过超声波改变介质的折射率，形成随时间和空间而周期性变化的分布，相当于一个位相光栅，当入射激光通过受到超声波调制的介质时会产生衍射，其衍射激光的频率、强度、方向等都会随着超声波的改变而改变的现象。
早在20世纪30年代初，德拜等人通过实验论证了声光效应，但当时所使用的声光互作用介质一般是各向同性的，如水和玻璃，光是普通的非相干光源。考虑到这种声光互作用所引起的光强度和光方向的变化可以忽略不计，没有多少实用的价值，因此没有得到足够的重视。
直到20世纪60年代世界上第一台固态红宝石激光器诞生以来，人们才开始重视致力于声光互作用的理论研究与应用开发。随着激光和微电子技术的迅猛发展，特别是性能优异的超声延迟线的出现，推动了声光器件的快速发展。目前，声光器件不仅被广泛应用于激光束的调制，而且在时域和频域的高密度、大带宽的实时信号处理过程中，已取得举世瞩目的成就，逐步形成和发展了一门新兴的信号处理技术(声光信号处理技术)。不过，要使声光信号处理技术获得更为广泛的应用前景，仍然需要声光器件的性能的进一步提升，这不仅依赖于声光器件的设计方法的改进，而且更为重要的是，研制出性能优异的新型声光材料。
理想的声光材料应具备以下的性质：①大的声光优值(衍射光的功率正比于声光优值)；②低的声衰减；③宽的透过波段和高的透明度，对入射激光和衍射激光都具有良好的透过性；④高的激光损伤阈值，在强激光作用下不易使材料产生缺陷；⑤易于获得大尺寸、高光学质量的晶体；⑥稳定的物理化学性能，不易潮解、分解；⑦易于加工，并且价格低廉等。
同时，激光晶体在军事、工业、通信、医疗等广泛的领域中具有重要而广阔的应用需求。激光晶体作为全固态激光器的核心组成部分，全固态激光器的工作特性的好坏取决于晶体的性能的优劣。
此外，一直以来人们期望获得多功能复合型的晶体材料，可以将声光调Q性能和激光性能结合在一起的晶体材料即激光自调Q晶体，能够减少复合全固态激光器的工作损耗，提高复合全固态激光器的工作效率，因此激光自调Q晶体是制造高效而紧凑的微小型复合 全固态激光器的理想材料。
因此，寻找具有优异的声光性能和激光性能的晶体势在必行。考虑到TeO2晶体具有宽的透过范围，大的声光优值；MO2(M＝Ti、Zr、Hf)晶体具有低的声衰减，出色的热学特性，高的化学稳定性。本发明将两者结合在一起得到的碲酸盐晶体可作为新的优异的高频声光材料。同时碲酸盐晶体由于具有宽的透过波段，低的声子能量，使其可作为优异的激光晶体，尤其是可作为优异的激光自调Q晶体。
发明内容
针对现有技术的不足，本发明提供一类新型碲酸盐晶体，同时提供碲酸盐晶体的生长方法与该类晶体的应用。
术语说明：
本发明中所描述的晶体均应该解释为单晶，除非特别陈述是多晶的状况外。
本发明的技术方案如下：
一类碲酸盐晶体，该类晶体的化学式为MTe3O8，M＝Ti、Zr、Hf，属于立方晶系，Ia-3空间群，透过波段从可见到红外，透明度≥70％。
根据本发明，优选的，所述的碲酸盐晶体还掺杂稀土元素(Re)，所述的稀土元素掺杂量控制在0＜Re/M≤1，摩尔比，进一步优选5％；掺杂稀土元素的碲酸盐晶体的化学式为Re：MTe3O8，M＝Ti、Zr、Hf；
进一步优选的，所述的稀土元素为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或/和Lu。
根据本发明，优选的，所述的透过波段为300～6500nm。
根据本发明，上述碲酸盐晶体的生长方法，可采用助熔剂法、提拉法或坩埚下降法生长晶体。
根据本发明碲酸盐晶体的生长方法，采用助熔剂方法生长晶体，包括步骤如下：
(1)将原料MO2(M＝Ti、Zr、Hf)和TeO2根据MTe3O8化学计量比进行配料，均匀混合，压片，500～650℃烧结20～40h，冷却，研磨，600～700℃烧结20～40h，得到纯相的碲酸盐多晶，将纯相的碲酸盐多晶添加到助熔剂体系中，得到晶体生长料；
或者，将原料MO2(M＝Ti、Zr、Hf)和TeO2根据MTe3O8化学计量比进行配料，直接添加到助熔剂体系中，均匀混合，得到晶体生长料；
所述的助熔剂体系为下列物质之一，然而不局限于此：
(a)TeO2；
(b)A2CO3-TeO2(A＝Li、Na、K、Rb或/和Cs)，其中M2CO3与TeO2摩尔比2:(1～5)；
(c)MoO3；
(d)B2O3；
(e)PbO-B2O3；
所述的碲酸盐与助熔剂体系的摩尔比为1：(1～5)；
(2)将步骤(1)得到的晶体生长料置于铂金坩埚中，快速升温使其熔化完全，充分搅拌均匀，缓慢降温促使晶体自发成核，生长；
或者，将步骤(1)得到的晶体生长料置于铂金坩埚中，快速升温使其熔化完全，充分搅拌均匀，缓慢降温至熔液的饱和点，下入碲酸盐籽晶并进行晶转，缓慢降温促使晶体生长；
所述晶体生长温度区间为750～900℃，降温速率为0.01～5℃/h。
根据本发明碲酸盐晶体的生长方法，优选的，步骤(2)碲酸盐晶体生长的晶转参数为：转速5～50rd，加速时间1～10s，运行时间30～180s，间歇时间5～50s。
根据本发明碲酸盐晶体的生长方法，优选的，步骤(2)碲酸盐晶体生长的降温程序为：按照0.01～4℃/h的速率降温至750～850℃，生长周期40～70天。
根据本发明，得到的碲酸盐单晶的长度≥20mm，厚度≥10mm。
本发明也可采用提拉法、坩埚下降法等熔体法生长晶体，按现有技术即可。
根据本发明碲酸盐晶体的生长方法，优选的，步骤(1)中将稀土元素材料Re2O3与MO2(M＝Ti、Zr、Hf)和TeO2根据比例一同配料，得掺杂稀土元素的晶体生长料。通过步骤(2)进行生长得到掺杂稀土元素的碲酸盐晶体。
根据本发明，所述的碲酸盐晶体作为声光晶体的应用，应用于光学调制器件的制作；进一步优选的，所述的光学调制器件是声光调制器、声光偏转器或声光调Q器。
优选的，所述的碲酸盐晶体还有的用途如下：
碲酸盐晶体作为激光基质材料的应用；
碲酸盐晶体作为拉曼激光晶体的应用；
碲酸盐晶体作为窗口材料的应用；
碲酸盐晶体作为棱镜材料的应用；
碲酸盐晶体作为单晶基片的应用；
碲酸盐晶体作为介电介质的应用；
碲酸盐晶体作为绝缘材料的应用；
碲酸盐晶体作为催化材料的应用；
碲酸盐晶体作为高能粒子探测材料的应用。
本发明生长晶体所采用的方法，所需要的生长条件简单且容易实施；得到的厘米级碲酸盐单晶，足够供定向加工，本征特性测试；此外，本发明晶体生长方法所使用的化学原料均可以直接在市场购买，而且价格低廉。
采用本发明的方法生长得到的碲酸盐单晶，其实验的粉末X射线衍射图谱与理论计算获得的标准的粉末X射线衍射图谱相吻合，表明生长的晶体为立方晶系的碲酸盐晶体。
本发明有益效果如下：
1.现有技术只局限于碲酸盐晶体的结构，本发明在国际上率先生长了碲酸盐单晶，并且得到了尺寸和质量足够满足实际应用的碲酸盐单晶。
2.利用所生长的大尺寸和高质量的碲酸盐单晶全面测试了其重要本征特性，具备广泛的应用前景。
3.本发明的碲酸盐单晶物理化学性能稳定，不潮解，不分解。可根据实际情况的需求调整晶体生长的周期，获得实际所需求尺寸的碲酸盐单晶，供应相关的工业应用。
附图说明
图1为本发明实施例1生长的碲酸钛多晶的实验的粉末X射线衍射图谱与理论计算获得的结果(a为实验的粉末X射线衍射图谱，b为理论计算获得的结果)。
图2为实施例1制备的碲酸钛籽晶照片。
图3为实施例2制备的碲酸钛单晶照片。
图4为实施例3制备的碲酸钛单晶照片。
图5为实施例4制备的碲酸钛单晶照片。
图6为典型的声光晶体调Q的工作示意图。
图7为典型的激光晶体的工作示意图。
图8为典型的激光自调Q晶体的工作示意图。
其中，1、7、12均为激光二极管，2、8、13均为聚焦系统，3、14均为凹镜，4为Nd：YVO4/Nd：YAG激光晶体，5为TiTe3O8声光介质，6、9、11、16均为平面镜，10为Yb：TiTe3O8激光晶体，15为Yb：TiTe3O8激光自调Q晶体。
具体实施方式
下面结合具体实施例对本发明采用的技术方案做进一步的说明，然而不局限于此。
实施例1、碲酸钛籽晶的生长
将原料TiO2和TeO2根据TiTe3O8化学计量比进行配料，添加到助熔剂体系Li2CO3-TeO2 (Li2CO3：TeO2的摩尔比为2：3)中，碲酸钛与助熔剂体系的摩尔比为1：3，置于容积为Φ50mm×70mm的铂金坩埚中，快速升温至980℃使原料熔化完全，充分搅拌均匀；下入铂金杆并进行晶转，缓慢降温至熔液的饱和点，降温速率为0.55℃/h，生长周期为5天，提出籽晶杆可以获得橙黄色的多晶(如图2所示)。测试其实验的粉末X射线衍射图谱与理论计算获得的结果一致(如图1所示)，表明获得的是立方晶系的碲酸钛晶体，从其中挑取质量较好的小晶体作为生长尺寸较大的晶体的籽晶。
实施例2、碲酸钛单晶的生长
将原料TiO2和TeO2根据TiTe3O8化学计量比进行配料，添加到助熔剂体系Li2CO3-TeO2(Li2CO3：TeO2的摩尔比为2：3)中，碲酸钛与助熔剂体系的摩尔比为1：3，置于容积为Φ50mm×70mm的铂金坩埚中，快速升温至980℃使原料熔化完全，充分搅拌均匀；缓慢降温至熔液的饱和点，以实施例1获得的小晶体为籽晶进行晶体生长，降温速率为0.25℃/h，生长周期为10天，即可以获得橙黄色的体块单晶(如图3所示)。测试其实验的粉末X射线衍射图谱与理论计算获得的结果一致，表明获得的是立方晶系的碲酸钛晶体。
将实施例2获得的碲酸钛单晶经过定向加工成所需要尺寸的晶片，测试其透过光谱，结果显示，其具有宽的透过波段(480～6000nm)。
该晶体放置于空气中6个月，不潮解，不分解，表明该晶体物理化学性能稳定。
实施例3、碲酸钛单晶的生长
将原料TiO2和TeO2根据TiTe3O8化学计量比进行配料，添加到助熔剂体系Li2CO3-TeO2(Li2CO3：TeO2的摩尔比为2：3)中，碲酸钛与助熔剂体系的摩尔比为1：3，置于容积为Φ50mm×70mm的铂金坩埚中，快速升温至980℃使原料熔化完全，充分搅拌均匀；缓慢降温至熔液的饱和点，以[100]方向的晶体作为籽晶进行晶体生长，降温速率为0.06℃/h，生长周期为20天，即可以获得橙黄色的体块单晶(如图4所示)。测试其实验的粉末X射线衍射图谱与理论计算获得的结果一致，表明获得的是立方晶系的碲酸钛晶体。
实施例4、碲酸钛单晶的生长
将原料TiO2和TeO2根据TiTe3O8化学计量比进行配料，添加到助熔剂体系TeO2中，碲酸钛与助熔剂体系的摩尔比为1：3，置于容积为Φ50mm×70mm的铂金坩埚中，快速升温至1080℃使原料熔化完全，充分搅拌均匀；缓慢降温至熔液的饱和点，以[100]方向的晶体作为籽晶进行晶体生长，降温速率为0.05℃/h，生长周期为40天，即可以获得体块单晶(如图5所示)。测试其实验的粉末X射线衍射图谱与理论计算获得的结果一致，表明获得的是立方晶系的碲酸钛晶体。
实施例5、Yb：TiTe3O8单晶的生长
将原料TiO2和TeO2根据TiTe3O8化学计量比进行配料，与Yb2O3同时添加到助熔剂体系TeO2中，Yb2O3与TiO2摩尔比为0.05：1，碲酸钛与助熔剂体系的摩尔比为1：3，置于容积为Φ50mm×70mm的铂金坩埚中，快速升温至1100℃使原料熔化完全，充分搅拌均匀；缓慢降温至熔液的饱和点，以[100]方向的晶体作为籽晶进行晶体生长，降温速率为0.04℃/h，生长周期为50天，即可以获得Yb：TiTe3O8体块单晶。
实施例6、碲酸钛单晶作为声光晶体的应用
用实施例3生长得到的碲酸钛单晶制作声光调Q器件，工作示意图如图6所示。1为激光二极管，其输出光经过聚焦系统2到Nd：YVO4/Nd：YAG激光晶体3上。谐振腔采用平-凹结构，声光介质5采用碲酸钛单晶。
实施例7、Yb：TiTe3O8单晶作为激光晶体的应用
利用实施例5生长得到的Yb：TiTe3O8单晶制作激光器件，工作示意图如图7所示。7为激光二极管，其输出光经过聚焦系统8到Yb：TiTe3O8激光晶体10上。
实施例8、Yb：TiTe3O8单晶作为激光自调Q晶体的应用
利用实施例5生长得到的Yb：TiTe3O8单晶制作激光自调Q器件，工作示意图如图8所示。12为激光二极管，其输出光经过聚焦系统13到Yb：TiTe3O8激光自调Q晶体15上。谐振腔采用平-凹结构。
实施例9、碲酸锆单晶的生长
将原料ZrO2和TeO2根据ZrTe3O8化学计量比进行配料，添加到助熔剂体系TeO2中，碲酸锆与助熔剂体系的摩尔比为1：4，置于容积为Φ50mm×70mm的铂金坩埚中，快速升温使原料熔化完全，充分搅拌均匀；缓慢降温至熔液的饱和点，以[100]方向的晶体作为籽晶进行晶体生长，降温速率为0.02℃/h，生长周期为40天，即可以获得碲酸锆单晶。测试其实验的粉末X射线衍射图谱与理论计算获得的结果一致，表明获得的是立方晶系的碲酸锆单晶。
实施例10、碲酸铪单晶的生长
将原料HfO2和TeO2根据HfTe3O8化学计量比进行配料，添加到助熔剂体系Li2CO3-TeO2(Li2CO3：TeO2的摩尔比为2：3)中，碲酸铪与助熔剂体系的摩尔比为1：4，置于容积为Φ50mm×70mm的铂金坩埚中，快速升温使原料熔化完全，充分搅拌均匀；缓慢降温至熔液的饱和点，以[100]方向的晶体作为籽晶进行晶体生长，降温速率为0.02℃/h，生长周期为60天，即可以获得碲酸铪单晶。测试其实验的粉末X射线衍射图谱与理论计算获得的结果一致，表明获得的是立方晶系的碲酸铪单晶。

Claims (10)

  1. 碲酸盐晶体，该晶体的化学式为MTe3O8，M＝Ti、Zr、Hf，属于立方晶系，Ia-3空间群，透过波段从可见到红外，透明度≥70％。
  2. 根据权利要求1所述的碲酸盐晶体，其特征在于，所述的碲酸盐晶体还可掺杂稀土元素(Re)，所述的稀土元素掺杂量控制在0＜Re/M≤1，摩尔比。
  3. 根据权利要求2所述的碲酸盐晶体，其特征在于，所述的稀土元素为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或/和Lu。
  4. 权利要求1所述的碲酸盐晶体的生长方法，采用助熔剂方法生长晶体，包括步骤如下：
    (1)将原料MO2(M＝Ti、Zr、Hf)和TeO2根据MTe3O8化学计量比进行配料，均匀混合，压片，500～650℃烧结20～40h，冷却，研磨，600～700℃烧结20～40h，得到纯相的碲酸盐多晶，将纯相的碲酸盐多晶添加到助熔剂体系中，得到晶体生长料；
    或者，将原料MO2(M＝Ti、Zr、Hf)和TeO2根据MTe3O8化学计量比进行配料，直接添加到助熔剂体系中，均匀混合，得到晶体生长料；
    所述的助熔剂体系为下列物质之一：
    (a)TeO2；
    (b)A2CO3-TeO2(A＝Li、Na、K、Rb和/或Cs)，其中M2CO3与TeO2摩尔比2:(1～5)；
    (c)MoO3；
    (d)B2O3；
    (e)PbO-B2O3；
    所述的碲酸盐与助熔剂体系的摩尔比为1：(1～5)；
    (2)将步骤(1)得到的晶体生长料置于铂金坩埚中，快速升温使其熔化完全，充分搅拌均匀，缓慢降温促使晶体自发成核，生长；
    或者，将步骤(1)得到的晶体生长料置于铂金坩埚中，快速升温使其熔化完全，充分搅拌均匀，缓慢降温至熔液的饱和点，下入碲酸盐籽晶并进行晶转，缓慢降温促使晶体生长；
    所述晶体生长温度区间为750～900℃，降温速率为0.01～5℃/h。
  5. 根据权利要求4所述的碲酸盐晶体的生长方法，其特征在于，步骤(2)碲酸盐晶体生长的晶转参数为：转速5～50rd，加速时间1～10s，运行时间30～180s，间歇时间5～50s。
  6. 根据权利要求4所述的碲酸盐晶体的生长方法，其特征在于，步骤(2)碲酸盐晶体 生长的降温程序为：按照0.01～4℃/h的速率降温至750～850℃，生长周期40～70天。
  7. 根据权利要求4所述的碲酸盐晶体的生长方法，其特征在于，生长得到的碲酸盐单晶的长度≥20mm，厚度≥10mm。
  8. 根据权利要求4所述的碲酸盐晶体的生长方法，其特征在于，步骤(1)中将稀土元素材料Re2O3与MO2(M＝Ti、Zr、Hf)和TeO2根据比例一同配料，得掺杂稀土元素的晶体生长料，通过步骤(2)进行生长得到掺杂稀土元素的碲酸盐晶体。
  9. 权利要求1-3任一项所述的碲酸盐晶体作为声光晶体的应用，应用于光学调制器件的制作。
  10. 权利要求1-3任一项所述的碲酸盐晶体的如下用途：
    碲酸盐晶体作为激光基质材料的应用；
    碲酸盐晶体作为拉曼激光晶体的应用；
    碲酸盐晶体作为窗口材料的应用；
    碲酸盐晶体作为棱镜材料的应用；
    碲酸盐晶体作为单晶基片的应用；
    碲酸盐晶体作为介电介质的应用；
    碲酸盐晶体作为绝缘材料的应用；
    碲酸盐晶体作为催化材料的应用；
    碲酸盐晶体作为高能粒子探测材料的应用。
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