CN104562204A - Cesium tungsten-tellurite crystal as well as flux growth method and application thereof - Google Patents

Cesium tungsten-tellurite crystal as well as flux growth method and application thereof Download PDF

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CN104562204A
CN104562204A CN201510016098.4A CN201510016098A CN104562204A CN 104562204 A CN104562204 A CN 104562204A CN 201510016098 A CN201510016098 A CN 201510016098A CN 104562204 A CN104562204 A CN 104562204A
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crystal
wolframic acid
caesium
teo
acid tellurium
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陶绪堂
赵鹏
孙友轩
张承乾
夏盛清
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Shandong University
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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
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/32—Titanates; Germanates; Molybdates; Tungstates
    • 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
    • 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
    • H01S3/1675—Solid materials characterised by a crystal matrix titanate, germanate, molybdate, tungstate

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  • Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention relates to a flux growth method and an application of a cesium tungsten-tellurite crystal. The cesium tungsten-tellurite crystal has a chemical formula of Cs2TeW3O12 and belongs to a hexagonal system, the space group refers to P63, the ultraviolet-visible-near infrared transmission spectrum and intermediate infrared transmission spectrum show that the crystal can penetrate through a wavelength range of 430-5350nm, and the transmittance can be over 80 percent under the uncoated condition; an infrared laser incidence crystal with the wavelength of 1064nm generated by using an Nd:YAG laser generates strong green light. Compared with the Cs2TeW3O12 polycrystalline synthetic technology reported in the existing literature, a flux growth method for growing high-quality Cs2TeW3O12 single crystals is provided at first internationally, the crystal structure is successfully analyzed, and the Cs2TeW3O12 single crystal of which the size is enough to meet the application is obtained.

Description

Wolframic acid tellurium caesium crystal and flux growth method thereof and application
Technical field
The present invention relates to a kind of novel nonlinear optical crystal and growth thereof and apply, particularly wolframic acid tellurium caesium crystal and flux growth method thereof and application, belong to crystalline material technical field.
Background technology
Non-linear optical effect is the result of molecule in incident light wave electric field and crystal or Interaction of substituents.Inorganic nonlinear optical crystal material occupies leading position in second-order non-linear optical materials, and many inorganic materials obtain commercialization all.Since the people such as P.A.Franken in 1961 pass through quartz crystal with ruby laser, since observing optical second harmonic the earliest, undergoing an unusual development of nonlinear optics is swift and violent, from technical field to research field, the application of nonlinear optics is all very widely, such as: 1. utilize various nonlinear crystal to make electrooptical switching, realize the modulation of laser; 2. utilize the generation of secondary and triple-frequency harmonics, second order and three rank optics and frequency to realize the conversion of laser frequency with difference frequency, obtain and be as short as ultraviolet, vacuum ultraviolet (VUV), grow to far various laser; Meanwhile, the difficulty at present in infrared receiver is overcome by the conversion realized in infrared frequency; 3. optical parametric oscillator is utilized to realize the tuning of laser frequency.At present, combine with frequency multiplication, frequency mixing technique can realize therefrom tuning in infrared until vacuum ultraviolet (VUV) broad range; 4. the phase conjugate feature utilizing output beam in some non-linear optical effects to have, carries out optical Information Processing, improves image quality and beam quality; 5. utilize various non-linear optical effect, particularly resonate non-linear optical effect and various transient state coherent optics effect, the highly excited level of research material and high-resolution spectra and material internal energy and the transfer process excited and other relaxation processes etc.And based on nonlinear optical material, further developing and applying along with laser technology, more and more diversified to the requirement of its performance, also more and more higher to its specification of quality.
Desirable nonlinear optical material should have following character: (1) have large nonlinear optical coefficients-for the nonlinear optical material of different-waveband, the requirement of its Clock Multiplier Factor is different again: infrared band (> 800nm) d eff≈ 100 × d 36(KDP); Visible light wave range (400 ~ 800nm) d eff≈ 10 × d 36(KDP); (2) can realize phase matched, preferably can realize noncritical phase matching; (3) there is high transparency and wide through wave band, to incident light wave and frequency multiplication light wave, all there is good perviousness; (4) the light injury threshold of material wants high, surface imperfection point not easily occurs under light laser, the defects such as crack, not easily the change of generating material specific refractory power; (5) the laser-conversion efficiency of crystal wants high, so that obtain high-power Laser output; (6) be easy to obtain large-sized, optical-quality homogeneous, transparent crystal; (7) the physicochemical stability of crystal is good, not easily decomposes, deliquescence or undergo phase transition; (8) crystal is easy to processing, and cheap etc.For adapting to dual-use needs, the research and development of the novel nonlinear optical crystal of excellent performance have become the focus of current Material Field.
2003, P.Shiv Halasyamani seminar used water heat transfer wolframic acid tellurium caesium polycrystalline first, but did not successfully resolve its crystalline structure due to crystal mass problem.We obtain the higher little monocrystalline of crystal mass first by case of flux methods, and have successfully resolved the single crystal structure of wolframic acid tellurium caesium crystal first, and wolframic acid tellurium caesium belongs to hexagonal system, P6 3spacer, unit cell parameters z=2.Because it does not have symmetry centre, and belong to polarity crystal class, therefore wolframic acid tellurium caesium crystal has non-linear effect, piezoelectricity and pyroelectric.Up to now, except the polycrystalline obtained by hydrothermal method in above-mentioned report, yet there are no the report about the growth of wolframic acid tellurium caesium crystal, property detection and application aspect both at home and abroad.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, the wolframic acid tellurium caesium monocrystalline of a kind of size and the enough performance tests of quality and application is provided; And a kind of flux growth method of wolframic acid tellurium caesium crystal and the purposes of this wolframic acid tellurium caesium crystal are provided.
Term illustrates: by the custom of this area, wolframic acid tellurium caesium crystal is abbreviated as CTW usually.In illustrating below the present invention except the situation that special instruction is polycrystalline, all the other CTW crystal are all interpreted as monocrystalline.
Technical scheme of the present invention is as follows:
Wolframic acid tellurium caesium crystal, chemical formula is Cs 2teW 3o 12, belong to hexagonal system, spacer is P6 3, ultraviolet-visible-near infrared through spectrum and in infrared through spectrum display, this crystal all have in the wavelength region of 430 ~ 5350nm through, and its transmitance can reach more than 80% in uncoated situation; With the infrared laser entrance crystal that the wavelength that Nd:YAG laser apparatus produces is 1064nm, produce strong green glow.
A preparation method for wolframic acid tellurium caesium crystal, adopts flux method to carry out crystal growth, comprises the steps:
(1) by caesium source, TeO 2and WO 3stoichiometrically prepare burden, mix, compressing tablet, 400 ~ 450 DEG C of sintering 20 ~ 40h, after grinding, 500 ~ 600 DEG C of sintering 20 ~ 40h, obtain the wolframic acid tellurium caesium polycrystal powder of pure phase, the wolframic acid tellurium caesium polycrystal powder of pure phase is joined in fusing assistant system, obtains crystal growth material; Or by caesium source, TeO 2and WO 3according to stoichiometric ratio batching, directly join in fusing assistant system, mix, obtain crystal growth material;
Described caesium source is Cs 2cO 3, containing the cesium carbonate of crystal water or cesium hydroxide;
Described fusing assistant system is one of following:
(a) TeO 2-WO 3, wherein TeO 2with WO 3mol ratio (0.1 ~ 10): 1,
(b) Cs 2cO 3-TeO 2, wherein CsCO 3with TeO 2mol ratio (0.1 ~ 5): 1,
(c) Cs 2cO 3-WO 3, wherein CsCO 3with WO 3mol ratio (0.5 ~ 5): 1,
(d)TeO 2，
(e)WO 3,
(f)B 2O 3，
(g)PbO-B 2O 3，
Described caesium source, TeO 2, WO 3be 1:1:3:(0.1 ~ 10 with the mol ratio of compound total in fusing assistant);
(2) step (1) gained crystal growth material is loaded platinum crucible, be warming up to 750 DEG C and make it to melt completely, be uniformly mixed, cooling makes crystal spontaneous crystallization; Or
Step (1) gained crystal growth material is warming up to 750 DEG C make it to melt completely, is uniformly mixed, is cooled to liquation saturation point, under enter wolframic acid tellurium caesium seed crystal and rotate, cooling makes crystal growth;
The above crystal growth temperature interval is 650 ~ 600 DEG C, and rate of temperature fall is 0.01 ~ 5 DEG C/h.
Reaction formula in aforesaid method of the present invention is: Cs 2cO 3+ TeO 2+ 3WO 3→ Cs 2teW 3o 12+ CO 2↑
According to the present invention, preferably, the crystalline substance of wolframic acid tellurium caesium crystal growth turns parameter and is: rotating speed 5 ~ 50rd, accelerates 1 ~ 10s, runs 30 ~ 180s, interval 5 ~ 50s.
According to the present invention, the growth cycle of wolframic acid tellurium caesium crystal is 7 ~ 60 days.Preferably, the growth cycle of wolframic acid tellurium caesium crystal is 30 ~ 50 days.
According to the present invention, preferably, be cooled to 640 ~ 650 DEG C with the speed of 0.01 ~ 3 DEG C/h, growth cycle 30 days.
According to the present invention, gained wolframic acid tellurium caesium monocrystalline crystal length is not less than 10mm, thickness is not less than 5mm.
Needed for the flux growth method that the present invention adopts, experiment condition is simple; Growth cycle can obtain length for about 20 days more than 10mm, and thickness more than 5mm and the mutually single wolframic acid tellurium caesium monocrystalline of thing, can supply oriented machining, test related physical performance; In addition, the raw material that present method uses all can be buied in market, and low price.Use large size crucible can obtain the corresponding larger monocrystalline of size.
Adopt the wolframic acid tellurium caesium monocrystalline of the inventive method growth, the standard powdery diffractometry that its X-ray powder and Theoretical Calculation obtain is consistent, illustrates that the crystal of growth is the wolframic acid tellurium caesium of hexagonal system.
Wolframic acid tellurium caesium monocrystalline of the present invention is light yellow, very stable under room temperature, does not decompose, not deliquescence.Growth cycle can be adjusted as required, obtain the wolframic acid tellurium caesium monocrystalline of desired size, supply related industries demand.
Wolframic acid tellurium caesium crystal of the present invention is as the application of non-linear optic crystal, and for making laser frequency conversion device, described laser frequency conversion device is frequency doubling device and frequently device and difference frequency device; Also for making the associated op-tics such as photoparametric amplifier or optical parametric oscillator.
In addition, wolframic acid tellurium caesium crystal of the present invention also has following important use:
Wolframic acid tellurium caesium crystal is as the application of piezoquartz.
Wolframic acid tellurium caesium crystal is as the application of pyroelectric crystal.
Wolframic acid tellurium caesium crystal is as the application of ferroelectric crystal.
Wolframic acid tellurium caesium crystal is as the application of electro-optic crystal.
Wolframic acid tellurium caesium crystal is as the application of raman laser crystal.
Wolframic acid tellurium caesium crystal is as the application of laser host material.
Beneficial effect
1, compared with the synthetic technology of existing bibliographical information CTW polycrystalline, the present invention proposes adopt flux method growing high-quality CTW monocrystalline and successfully resolved its crystalline structure first in the world first, obtains the CTW monocrystalline that size is enough to meet application simultaneously;
2, utilize the large size single crystal grown to record the many critical natures of CTW crystal, comprise the character such as calorifics, optics, electricity, these all cannot realize with polycrystal powder;
3, the CTW monocrystalline that prepared by the present invention is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is wolframic acid tellurium caesium monocrystal X-ray diffractogram of the present invention and the calculated results;
A is wolframic acid tellurium caesium monocrystal X-ray diffractogram of the present invention, and b is the calculated results;
Fig. 2 is the structure sciagraph of the ab plane of wolframic acid tellurium caesium monocrystalline of the present invention, spacer P6 3, unit cell parameters z=2.
Fig. 3 is wolframic acid tellurium caesium monocrystalline prepared by embodiment 1;
Fig. 4 is wolframic acid tellurium caesium monocrystalline prepared by embodiment 2;
Fig. 5 is wolframic acid tellurium caesium monocrystalline prepared by embodiment 3;
Fig. 6 is wolframic acid tellurium caesium monocrystalline prepared by embodiment 4;
Fig. 7 is wolframic acid tellurium caesium monocrystalline prepared by embodiment 5;
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited thereto, and the ratio in fusing assistant system is mol ratio.
Embodiment 1
By raw material Cs 2cO 3, TeO 2and WO 3stoichiometrically prepare burden, mix, directly join fusing assistant system TeO 2-WO 3(TeO 2: WO 3mol ratio be 2:2.5) in, described Cs 2cO 3, TeO 2, WO 3the mol ratio total with compound in fusing assistant is 1:1:3:1, and loading volume is in the platinum crucible of Φ 50mm × 70mm, is warming up to 750 DEG C and makes melting sources and form homogeneous liquation; Be cooled to saturation point, now enter under preheated platinum wire, and lower the temperature with the rate of temperature fall of 1 DEG C/h, growth cycle 10 days, propose platinum wire and can obtain multiple light yellow tabular crystal (Fig. 3), more with platinum wire contact position stray crystal, this is because nucleation site is more herein, easy generation stray crystal, obviously improves away from platinum wire place crystal mass.Test its X-ray diffractogram, consistent with Theoretical Calculation (as shown in Figure 1), the structure of the ab plane of wolframic acid tellurium caesium monocrystalline as shown in Figure 2, what prove to obtain is the wolframic acid tellurium caesium crystal of hexagonal system, therefrom takes out the good small-crystalline of quality as seed crystal for growing the crystal of large-size.
Irradiate the wolframic acid tellurium caesium polycrystalline of porphyrize with the infrared laser that the wavelength that Nd:YAG produces is 1064nm, produce strong green glow, illustrate that it has very strong powder SHG effect.
Embodiment 2
By raw material Cs 2cO 3, TeO 2and WO 3stoichiometrically prepare burden, mix, directly join fusing assistant system TeO 2-WO 3(TeO 2: WO 3mol ratio be 2:2.5) in, described Cs 2cO 3, TeO 2, WO 3the mol ratio total with compound in fusing assistant is 1:1:3:3, and loading volume is in the platinum crucible of Φ 50mm × 70mm, is warming up to 750 DEG C and makes melting sources and form homogeneous liquation; Be cooled to saturation point, now entering in liquation under preheated seed crystal (taking from embodiment 1), and lower the temperature with the rate of temperature fall of 0.5 DEG C/h, growth cycle 20 days, light yellow bulk-shaped monocrystal (Fig. 4) can be obtained, test its X-ray diffractogram, consistent with Theoretical Calculation, what prove to obtain is the wolframic acid tellurium caesium crystal of hexagonal system.
Wolframic acid tellurium caesium monocrystalline oriented machining embodiment 2 obtained becomes the thin slice of desired size, test its ultraviolet-visible-near infrared through spectrum and in infrared through spectrum, result shows, it is 430 ~ 5350nm through wavelength region.
This crystal deposits 3 months in atmosphere, has no deliquescence Sum decomposition phenomenon, illustrates that crystal physical and chemical performance is stablized.
Embodiment 3
By raw material Cs 2cO 3, TeO 2and WO 3stoichiometrically prepare burden, mix, directly join fusing assistant system TeO 2-WO 3(TeO 2: WO 3mol ratio be 2:3) in, described Cs 2cO 3, TeO 2, WO 3the mol ratio total with compound in fusing assistant is 1:1:3:5, and loading volume is in the platinum crucible of Φ 50mm × 70mm, is warming up to 750 DEG C and makes melting sources and form homogeneous liquation; Be cooled to saturation point, now entered in liquation under preheated seed crystal, and lower the temperature with the rate of temperature fall of 0.3 DEG C/h, growth cycle 30 days, light yellow bulk-shaped monocrystal (Fig. 5) can be obtained, test its X-ray diffractogram, consistent with Theoretical Calculation, what prove to obtain is the wolframic acid tellurium caesium crystal of hexagonal system.
Embodiment 4
By raw material Cs 2cO 3, TeO 2and WO 3stoichiometrically prepare burden, mix, directly join fusing assistant system TeO 2-WO 3(TeO 2: WO 3mol ratio be 2:3) in, described Cs 2cO 3, TeO 2, WO 3the mol ratio total with compound in fusing assistant is 1:1:3:7, and loading volume is in the platinum crucible of Φ 50mm × 70mm, is warming up to 750 DEG C and makes melting sources and form homogeneous liquation; Be cooled to saturation point, now entered in liquation under preheated seed crystal, and lower the temperature with the rate of temperature fall of 0.3 DEG C/h, growth cycle 35 days, light yellow bulk-shaped monocrystal (Fig. 6) can be obtained, test its X-ray diffractogram, consistent with Theoretical Calculation, what prove to obtain is the wolframic acid tellurium caesium crystal of hexagonal system.
Embodiment 5
By Cs 2cO 3, TeO 2and WO 3stoichiometrically prepare burden, mix, compressing tablet, 400 DEG C of sintering 24h, take out and again grind, and 600 DEG C of sintering 48h, middle grinding 1 time, can obtain the CTW polycrystal powder of pure phase, the wolframic acid tellurium caesium polycrystalline of pure phase is joined fusing assistant system TeO 2-WO 3(TeO 2: WO 3mol ratio be 2:3) in, described Cs 2cO 3, TeO 2, WO 3the mol ratio total with compound in fusing assistant is 1:1:3:10, and the mol ratio that in wolframic acid tellurium caesium polycrystalline and fusing assistant, compound is total is 1:2, and loading volume is in the platinum crucible of Φ 50mm × 70mm, is warming up to 750 DEG C and makes melting sources and form homogeneous liquation; Be cooled to saturation point, now entered in liquation under preheated seed crystal, and lower the temperature with the rate of temperature fall of 0.3 DEG C/h, growth cycle 30 days, light yellow bulk-shaped monocrystal (Fig. 7) can be obtained, test its X-ray diffractogram, consistent with Theoretical Calculation, what prove to obtain is the wolframic acid tellurium caesium crystal of hexagonal system.
Embodiment 6
The wolframic acid tellurium caesium crystal obtained by embodiment 4, be processed into frequency-doubling crystal device by prior art, size 4mm × 4mm × 8mm, as laser frequency-doubling device.Irradiate wolframic acid tellurium caesium crystal with the infrared laser that the wavelength that Nd:YAG produces is 1064nm, can green glow be seen, illustrate that it has frequency-doubled effect.

Claims (8)

1. a wolframic acid tellurium caesium crystal, chemical formula is Cs 2teW 3o 12, belong to hexagonal system, spacer is P6 3, ultraviolet-visible-near infrared through spectrum and in infrared through spectrum display, this crystal all have in the wavelength region of 430 ~ 5350nm through, and its transmitance can reach more than 80% in uncoated situation; With the infrared laser entrance crystal that the wavelength that Nd:YAG laser apparatus produces is 1064nm, produce strong green glow.
2. the preparation method of wolframic acid tellurium caesium crystal described in claim 1, adopts flux method to carry out crystal growth, it is characterized in that, comprise the steps:
(1) by caesium source, TeO 2and WO 3stoichiometrically prepare burden, mix, compressing tablet, 400 ~ 450 DEG C of sintering 20 ~ 40h, after grinding, 500 ~ 600 DEG C of sintering 20 ~ 40h, obtain the wolframic acid tellurium caesium polycrystal powder of pure phase, the wolframic acid tellurium caesium polycrystal powder of pure phase is joined in fusing assistant system, obtains crystal growth material; Or by caesium source, TeO 2and WO 3according to stoichiometric ratio batching, directly join in fusing assistant system, mix, obtain crystal growth material;
Described caesium source is Cs 2cO 3, containing the cesium carbonate of crystal water or cesium hydroxide;
Described fusing assistant system is one of following:
(a) TeO 2-WO 3, wherein TeO 2with WO 3mol ratio (0.1 ~ 10): 1,
(b) Cs 2cO 3-TeO 2, wherein CsCO 3with TeO 2mol ratio (0.1 ~ 5): 1,
(c) Cs 2cO 3-WO 3, wherein CsCO 3with WO 3mol ratio (0.5 ~ 5): 1,
(d)TeO 2，
(e)WO 3,
(f)B 2O 3，
(g)PbO-B 2O 3，
Described caesium source, TeO 2, WO 3be 1:1:3:(0.1 ~ 10 with the mol ratio of compound total in fusing assistant);
(2) step (1) gained crystal growth material is loaded platinum crucible, be warming up to 750 DEG C and make it to melt completely, be uniformly mixed, cooling makes crystal spontaneous crystallization; Or
Step (1) gained crystal growth material is warming up to 750 DEG C make it to melt completely, is uniformly mixed, is cooled to liquation saturation point, under enter wolframic acid tellurium caesium seed crystal and rotate, cooling makes crystal growth;
The above crystal growth temperature interval is 650 ~ 600 DEG C, and rate of temperature fall is 0.01 ~ 5 DEG C/h.
3. preparation method as claimed in claim 2, it is characterized in that, the crystalline substance of wolframic acid tellurium caesium crystal growth turns parameter and is: rotating speed 5 ~ 50rd, accelerates 1 ~ 10s, runs 30 ~ 180s, interval 5 ~ 50s.
4. preparation method as claimed in claim 2, it is characterized in that, the growth cycle of wolframic acid tellurium caesium crystal is 7 ~ 60 days; Preferably, the growth cycle of wolframic acid tellurium caesium crystal is 30 ~ 50 days.
5. preparation method as claimed in claim 2, is characterized in that, be cooled to 640 ~ 650 DEG C with the speed of 0.01 ~ 3 DEG C/h, growth cycle 30 days.
6. preparation method as claimed in claim 2, it is characterized in that, gained wolframic acid tellurium caesium monocrystalline crystal length is not less than 10mm, thickness is not less than 5mm.
7. wolframic acid tellurium caesium crystal described in claim 1 is as the application of non-linear optic crystal, and for making laser frequency conversion device, described laser frequency conversion device is frequency doubling device and frequently device and difference frequency device; Also for making the associated op-tics such as photoparametric amplifier or optical parametric oscillator.
8. wolframic acid tellurium caesium crystal according to claim 2 is as the application of piezoquartz, pyroelectric crystal, ferroelectric crystal, electro-optic crystal, raman laser crystal or laser host material.
CN201510016098.4A 2015-01-13 2015-01-13 Cesium tungsten-tellurite crystal as well as flux growth method and application thereof Pending CN104562204A (en)

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CN112522786A (en) * 2020-11-10 2021-03-19 临沂大学 Self-excited Raman composite functional crystal bismuth tungsten molybdate and crystal growth method thereof
CN112522786B (en) * 2020-11-10 2022-02-01 临沂大学 Self-excited Raman composite functional crystal bismuth tungsten molybdate and crystal growth method thereof
CN115323495A (en) * 2021-05-11 2022-11-11 中国科学院理化技术研究所 Calcium tungsten tellurate compound Ca 3 Te 2 WO 10 Crystal, preparation method and application thereof

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Application publication date: 20150429