CN111501100B - Preparation method and application of rubidium silicate nonlinear optical crystal - Google Patents

Preparation method and application of rubidium silicate nonlinear optical crystal Download PDF

Info

Publication number
CN111501100B
CN111501100B CN202010493030.6A CN202010493030A CN111501100B CN 111501100 B CN111501100 B CN 111501100B CN 202010493030 A CN202010493030 A CN 202010493030A CN 111501100 B CN111501100 B CN 111501100B
Authority
CN
China
Prior art keywords
crystal
crucible
melt
speed
nonlinear optical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010493030.6A
Other languages
Chinese (zh)
Other versions
CN111501100A (en
Inventor
潘世烈
黄述朝
杨云
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinjiang Technical Institute of Physics and Chemistry of CAS
Original Assignee
Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xinjiang Technical Institute of Physics and Chemistry of CAS filed Critical Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority to CN202010493030.6A priority Critical patent/CN111501100B/en
Publication of CN111501100A publication Critical patent/CN111501100A/en
Application granted granted Critical
Publication of CN111501100B publication Critical patent/CN111501100B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
    • 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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger 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
    • 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
    • C30B29/34—Silicates
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/3551—Crystals

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention relates to a preparation method and application of rubidium silicate nonlinear optical crystal, wherein the molecular formula of the crystal is Rb6Si10O23Molecular weight of 1161.65, belonging to orthorhombic system, space group ofAmm2, unit cell parameters are:a=8.049(6)Å,b=16.227(13)Å,c=9.385(7)Å,Z=2,V=1225.8(16)Å3. A crystal is grown by adopting a pulling method or a crucible moving method in a melt method to obtain a centimeter-level large-size rubidium silicate nonlinear optical crystal, and the crystal is used for preparing a frequency doubling generator of a nonlinear optical device. The crystal has the advantages of high growth speed, simple operation in the growth process, low cost, high hardness, stable physical and chemical properties, wide light-transmitting wave band and large size of the prepared crystal.

Description

Preparation method and application of rubidium silicate nonlinear optical crystal
Technical Field
The invention relates to a preparation method and application of rubidium silicate nonlinear optical crystal, wherein the chemical formula of the crystal is Rb6Si10O23。
Background
The laser light generated by stimulated emission generally has only one or a few wavelengths, while in practice, laser light of different wavelength bands is required in different fields of application, and thus tuning of the laser light is required. The nonlinear optical crystal can utilize the nonlinear optical effect of the crystal to carry out frequency conversion on laser. Any crystal has nonlinear optical effect, but the nonlinear optical effect caused by quadratic term is most significant in nonlinear high-order polarization terms, and the numerical value of each term is reduced by several orders of magnitude in turn as the times of the polarization terms are higher. Therefore, among nonlinear optical crystals, the second-order nonlinear optical crystal is the most promising tuning mode at present because of its high conversion efficiency, good beam quality, narrow output line width, easily available raw materials, and simplicity.
At present, KDP, beta-BaB is used in the long-wave ultraviolet to near-infrared short-wave band (320nm-1100nm)2O4(β-BBO)，LiB3O5(LBO)，KTiOPO4Investigation of second-order nonlinear optical crystal typified by (KTP) crystalThe method is complete and can basically meet the requirements. However, in the deep ultraviolet to medium-wave ultraviolet band, the existing nonlinear optical crystal materials such as beta-BBO, CsLiB6O10(CLBO),KBe2BO3F2(KBBF) and the like have great limitations, such as overlarge walk-off angle, easy moisture absorption, lamellar growth habit and the like, so that the development of a novel nonlinear optical crystal is urgently needed.
In the process from the discovery of a single crystal structure to the application of the nonlinear optical crystal, one of the most important steps is the growth of a large-size crystal, and the nonlinear optical crystal has application value only after growing up. This requires that the new materials be easy to prepare, have good physical and chemical properties, facilitate the growth of large crystals, and be inexpensive, so that large transparent nonlinear optical crystals can be obtained.
Disclosure of Invention
The invention aims to provide a preparation method and application of a rubidium silicate nonlinear optical crystal, wherein the chemical formula of the crystal is Rb6Si10O23Molecular weight is 1161.65, the crystal belongs to an orthorhombic system, space group is Amm2, unit cell parameters are:
Figure BDA0002521817560000011
Figure BDA0002521817560000012
another object of the present invention is to provide a method for preparing rubidium silicate nonlinear optical crystal by using melt method to grow crystal, and its operation is simple.
It is a further object of the present invention to provide the use of rubidium silicate nonlinear optical crystals.
The invention also aims to make up the blank spectral region of the laser wavelength emitted by various lasers, thereby providing the rubidium silicate nonlinear optical crystal.
The invention relates to a method for preparing rubidium silicate nonlinear optical crystal, the molecular formula of the crystal is Rb6Si10O23Molecular weight 1161.65, space group Amm2, unit cell parameters:
Figure BDA0002521817560000013
Figure BDA0002521817560000014
Z＝2，
Figure BDA0002521817560000015
the crystal is grown by a pulling method or a crucible moving method in a melt method, and the specific operation is carried out according to the following steps:
a. uniformly mixing an Rb-containing compound and a Si-containing compound according to the molar ratio of Rb to Si of 6:10, putting the mixture into a mortar, carefully grinding the mixture, then putting the mixture into an open corundum crucible with the diameter of 100mm multiplied by 100mm, compacting the mixture, putting the mixture into a muffle furnace, slowly heating the mixture to 700 ℃, keeping the temperature for 24 hours, taking out the crucible after cooling, taking out the sample to be loose, taking out the sample, uniformly grinding the sample again, putting the sample into the crucible, keeping the temperature for 48 hours in the muffle furnace at the temperature of 800 ℃, taking out the sample, putting the sample into the mortar, smashing and grinding the sample to obtain the Rb6Si10O23Polycrystalline powder, and subjecting the product to X-ray analysis to obtain X-ray spectrogram and Rb product6Si10O23The X-ray spectrogram of the single crystal after being ground into powder is consistent, wherein the rubidium-containing compound is Rb2O、Rb2CO3、RbNO3、Rb2C2O4·H2O、RbOH、RbC2H3O2RbF or RbCl; the silicon-containing compound is H2SiO3、SiO2、H4SiO4Or H2Si2O5；
b. B, reacting Rb obtained in step a6Si10O23The polycrystalline powder is heated in a crucible to be melted, the temperature is 950-6Si10O23Melting the materials;
c. rb obtained in step b6Si10O23Slowly cooling the melt to room temperature at the speed of 0.5-10 ℃/h, crystallizing to obtain seed crystals or obtaining small crystals as the seed crystals by using a platinum wire suspension method during cooling;
d. adopting a pulling method to grow crystals on the surface of the melt or in the melt: fixing the seed crystal in the step c on a seed crystal rod, contacting the seed crystal from the top with the surface of the melt in the step b, cooling at the rate of 0.1-10 ℃/day or directly, cooling to 880 plus 900 ℃, rotating the seed crystal rod or the rotating crucible at the rotating speed of 0-100rpm, pulling up the crystal at the speed of 0-15mm/h, increasing the pulling speed after the growth of the single crystal is stopped, separating the crystal from the liquid level of the melt, cooling to room temperature at the rate of 1-100 ℃/h, and then slowly taking out the crystal from the furnace chamber to obtain the rubidium silicate nonlinear optical crystal;
or growing the crystal in the melt by using a crucible moving method: placing the seed crystal prepared in the step c at the bottom of the crucible, and then placing the Rb prepared in the step a6Si10O23Putting polycrystalline powder into a crucible, sealing the platinum crucible, heating the growth furnace to 950-1000 ℃, keeping the temperature for 10-120 hours, adjusting the position of the crucible to slightly melt the seed crystal, then reducing the crucible at the speed of 0.1-10 mm/day, simultaneously keeping the growth temperature unchanged, and after the growth is finished, rapidly reducing the temperature to the room temperature at the speed of 5-20 ℃/h to obtain the Rb-Al-Si-Al alloy material6Si10O23A nonlinear optical crystal.
The rubidium silicate nonlinear optical crystal obtained by the method is used for preparing a frequency doubling generator.
The frequency doubling generator comprises a device for generating at least one beam of output radiation with a frequency different from that of the incident electromagnetic radiation after the incident electromagnetic radiation passes through at least one nonlinear optical crystal.
The rubidium silicate nonlinear optical crystal has the following characteristics in the preparation process:
providing a melt method for growing crystals, and adopting a pulling method or a crucible moving method:
firstly, heating rubidium silicate polycrystalline powder in a crucible to be molten, keeping the temperature at 950-; slowly cooling to room temperature at the speed of 0.5-10 ℃/h for spontaneous crystallization or obtaining small crystals as seed crystals by using a platinum wire suspension method, or processing the existing crystal blank to obtain the seed crystals;
in the meltAdopting a pulling method to grow crystals: comprises the steps of growing by using seed crystals, fixing the seed crystals on a seed crystal rod when using the seed crystals, contacting the seed crystals from the top with the surface of a compound melt prepared in a crucible, and cooling to 880-900 ℃ at a cooling rate of 0.1-10 ℃/day or directly; rotating the seed crystal and/or the crucible at the rotating speed of 0-100rpm, and pulling the crystal upwards at the speed of 0-15 mm/h; after the single crystal grows to the required size, increasing the pulling speed to ensure that the crystal is separated from the liquid level of the melt, reducing the temperature to room temperature at the speed of 1-100 ℃/h, and then preparing the prepared Rb6Si10O23The nonlinear optical crystal is slowly taken out of the hearth;
or growing the crystal in the melt by adopting a crucible moving method, moving the crucible or a heater (horizontally moving or vertically moving, and adopting or not using seed crystals) at the speed of 0.1-10mm/h, and solidifying the melt through a temperature gradient area to generate the single crystal; the process can also be realized by slowly cooling the crystallization furnace, and the heating mode can be resistance wire heating or silicon-carbon rod or silicon-molybdenum rod heating; the shape of the crucible can be cylindrical, the bottom of the crucible is provided with a conical sharp corner, boat shape or other shapes.
Rb can be synthesized by the existing synthesis method6Si10O23The polycrystalline raw material of (1) is preferably selected from a solid phase synthesis method, namely: uniformly mixing compound raw materials containing Rb and Si with the mol ratio of 6:10, heating for solid phase reaction to obtain the compound with the chemical formula of Rb6Si10O23The compound of (1).
In principle, compound melt growth methods can be used to prepare the Rb of the invention6Si10O23Crystals, using large-size crucibles, with correspondingly larger sizes of Rb6Si10O23And (4) crystals.
Preparation of Rb6Si10O23Chemical reaction formula of the compound:
(1)SiO2+Rb2CO3→Rb6Si10O23+CO2↑；
(2)H2SiO3+Rb2CO3→Rb6Si10O23+CO2↑+H2O↑；
(3)H4SiO4+Rb2CO3→Rb6Si10O23+CO2↑+H2O↑；
(4)H2Si2O5+Rb2CO3→Rb6Si10O23+CO2↑+H2O↑
(5)SiO2+Rb2O→Rb6Si10O23；
(6)H2SiO3+Rb2O→Rb6Si10O23+H2O↑；
(7)H4SiO4+Rb2O→Rb6Si10O23+H2O↑；
(8)H2Si2O5+Rb2O→Rb6Si10O23+H2O↑
(9)RbCl+SiO2+O2→Rb6Si10O23+Cl2↑
(10)RbF+SiO2+O2→Rb6Si10O23+F2↑
(11)H4SiO4+RbOH→Rb6Si10O23+H2O↑
(12)H2Si2O5+RbOH→Rb6Si10O23+H2O↑
(13)SiO2+RbOH→Rb6Si10O23+H2O↑
(14)H2Si2O5+RbNO3→Rb6Si10O23+NO2↑+H2O↑+O2↑
(15)SiO2+RbNO3→Rb6Si10O23+NO2↑+O2↑
(16)SiO2+RbCH3COO+O2→Rb6Si10O23+CO2↑
(17)Rb2C2O4·H2O+SiO2+O2→Rb6Si10O23+CO2↑+H2O↑
in the present invention, commercially available reagents and starting materials can be used for the Rb-and Si-containing compounds.
The frequency doubling generator of the nonlinear device manufactured by the rubidium silicate nonlinear optical crystal comprises at least one coherent light beam which penetrates through at least one incident fundamental wave light beam and has a frequency different from that of the incident light beam. A light beam 2 emitted by a laser 1 is incident into a rubidium silicate nonlinear optical crystal 3, and a generated emergent light beam 4 passes through a filter 5, so that a required laser beam is obtained; the nonlinear optical device is a frequency doubling generator and the like; the laser 1 is a neodymium-doped yttrium aluminum garnet (Nd: YAG) laser or other laser, and for a frequency doubling device using the Nd: YAG laser as a light source, the incident beam 2 is infrared light with a wavelength of 1064nm, which passes through Rb6Si10O23The single crystal generates a green double-frequency light with a wavelength of 532nm, the emergent light beam 4 contains an infrared light with a wavelength of 1064nm and a green light with a wavelength of 532nm, and the filter 5 functions to filter the infrared light component and only allow the green double-frequency light to pass through.
The invention provides a rubidium silicate nonlinear optical crystal prepared by a melt growth method and a nonlinear optical device manufactured by a rubidium silicate single crystal. The crystal of the invention is easy to grow and transparent without inclusion, and has the advantages of simple operation, fast growth speed, low cost, easy obtaining of larger crystal size and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of rubidium silicate powder of the present invention;
FIG. 2 is a diagram showing the structure of a rubidium silicate single crystal according to the present invention;
fig. 3 is a working schematic diagram of a nonlinear optical device manufactured by rubidium silicate crystal of the present invention, wherein 1 is a laser, 2 is a light beam, 3 is a crystal, 4 is an emergent light beam, and 5 is a filter.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
example 1
According to the chemical reaction formula: SiO 22+Rb2CO3→Rb6Si10O23+CO2↓ [ O ] synthetic compound Rb6Si10O23；
Mixing according to chemical reaction formula, placing into mortar, grinding carefully, placing into opening corundum crucible with diameter of 100mm × 100mm, compacting, placing into muffle furnace, slowly heating to 700 deg.C, holding at constant temperature for 24 hr, cooling, taking out crucible, loosening sample, taking out sample, grinding uniformly, placing into crucible, holding at 800 deg.C for 48 hr, taking out, placing into mortar, mashing and grinding to obtain Rb6Si10O23Polycrystalline powder, and subjecting the product to X-ray analysis to obtain X-ray spectrogram and Rb product6Si10O23The X-ray spectrograms of the single crystals after being ground into powder are consistent;
growing rubidium silicate (Rb) by pulling method6Si10O23) Crystal:
first synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of phi 100mm multiplied by 100mm, placing the crucible into a crystal growth furnace, heating the crucible to be molten, heating the crucible to 950 ℃, keeping the temperature for 100 hours, and then cooling the crucible to 890 ℃ to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 0.5 ℃/h, and crystallizing to obtain seed crystals;
growing crystals on the surface of the compound melt: fixing the obtained seed crystal on a seed crystal rod, discharging the seed crystal from the top, guiding the seed crystal fixed at the lower end of the seed crystal rod into a crucible from a small hole at the top of the furnace, and leading the seed crystal and Rb to be mixed6Si10O23The liquid level of the melt is contacted and directly fallsThe temperature is 885 ℃, the temperature is constant, the seed rod is rotated at the rotating speed of 50rpm, and the crystal is pulled upwards at the speed of 15 mm/h;
after the growth of the single crystal is stopped, increasing the pulling speed to separate the crystal from the liquid level of the melt, reducing the temperature to room temperature at the speed of 80 ℃/h, and then slowly taking out the crystal from the hearth to obtain the rubidium silicate nonlinear optical crystal with the size of 10mm multiplied by 30 mm.
Example 2
According to the reaction formula H2SiO3+Rb2CO3→Rb6Si10O23+CO2↑+H2O ↓syntheticcompound Rb6Si10O23The specific procedure was carried out as in example 1;
preparation of Rb by Czochralski method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of 70mm × 70mm, placing the crucible into a crystal growth furnace, heating to melt, heating to 1000 deg.C, holding for 48 hr, cooling to 900 deg.C to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 10 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
growing crystals on the surface of the compound melt: rb to be cut along an arbitrary axis6Si10O23Fixing seed crystals at the lower end of a seed crystal rod by using a platinum wire, guiding the seed crystals into a crucible from a small hole at the top of the furnace to enable the seed crystals to be in contact with the liquid level of a melt, directly cooling to 890 ℃, keeping the temperature, rotating the seed crystal rod at the speed of 20rpm, and upwards pulling the crystals at the speed of 0.1 mm/h;
after the growth of the single crystal is stopped, increasing the pulling speed to separate the crystal from the liquid level of the melt, reducing the temperature to room temperature at the speed of 40 ℃/h, and then slowly taking out the crystal from the hearth to obtain the rubidium silicate nonlinear optical crystal with the size of 30mm multiplied by 30 mm.
Example 3
According to the reaction formula H4SiO4+Rb2CO3→Rb6Si10O23+CO2↑+H2O ↓syntheticRb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by Czochralski method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of 60mm × 60mm, placing the crucible into a crystal growth furnace, heating to melt, heating to 1100 deg.C, holding for 1 hr, cooling to 910 deg.C to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 1 ℃/h, and crystallizing to obtain seed crystals;
growing crystals on the surface of the compound melt: rb to be cut along an arbitrary axis6Si10O23Fixing seed crystals at the lower end of a seed crystal rod by using a platinum wire, guiding the seed crystals into a crucible from a small hole at the top of the furnace, enabling the seed crystals to be in contact with the liquid level of a melt, reducing the temperature to 883 ℃ at the speed of 0.5 ℃/day, rotating the seed crystal rod at the speed of 100rpm, and lifting and pulling the crystals upwards at the speed of 5 mm/h;
after the crystal growth is finished, the crystal is lifted away from the liquid level of the melt, the temperature is reduced to room temperature at the speed of 30 ℃/h, and then the crystal is slowly taken out from the hearth, thus obtaining the rubidium silicate nonlinear optical crystal with the size of 20mm multiplied by 40 mm.
Example 4
According to the reaction formula H2Si2O5+Rb2CO3→Rb6Si10O23+CO2↑+H2O ↓syntheticRb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by Czochralski method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound in a platinum crucible with a diameter of 100mm × 100mm, and placing the crucible in a crystal generatorHeating in a long furnace to melt, heating to 1000 ℃, keeping the temperature for 24 hours, cooling to 920 ℃ to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 0.8 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
growing crystals in a compound melt: rb to be cut along an arbitrary axis6Si10O23Fixing seed crystal at the lower end of a seed crystal rod by a platinum wire, introducing the seed crystal into a crucible from a small hole at the top of the furnace, immersing the seed crystal into a melt, directly cooling to 885 ℃, keeping the temperature, and controlling the rotation speed of the seed crystal rod to be 0 (not rotating);
after the crystal growth is finished, the crystal is lifted away from the liquid level of the melt, the temperature is reduced to room temperature at the speed of 1 ℃/h, and then the crystal is slowly taken out from the hearth, thus obtaining the rubidium silicate nonlinear optical crystal with the size of 30mm multiplied by 20 mm.
Example 5
According to the reaction formula H2SiO3+Rb2O→Rb6Si10O23+H2O ↓syntheticRb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by Czochralski method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of 80mm × 80mm, heating to melt, heating to 980 deg.C, holding for 80 hr, cooling to 895 deg.C to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 5 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
growing crystals in a compound melt: rb to be cut along an arbitrary axis6Si10O23The seed crystal is fixed at the lower end of a seed rod by a platinum wire, and is guided into a crucible from a small hole at the top of the furnace and is immersed under the liquid level by 1Rapidly cooling to 900 ℃ at the speed of 0 ℃/day, rotating the crucible at the speed of 80rpm, keeping the temperature, and upwards pulling the crystal at the speed of 15 mm/h;
after the crystal growth is finished, the crystal is separated from the liquid level, the temperature is reduced to room temperature at the speed of 60 ℃/hour, and then the crystal is slowly taken out from the hearth, so that the transparent rubidium silicate nonlinear optical crystal with the size of 10mm multiplied by 45mm is obtained.
Example 6
According to the reaction formula H4SiO4+Rb2O→Rb6Si10O23+H2O ↓syntheticRb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by Czochralski method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of phi 100mm multiplied by 100mm, heating to melt, heating to 988 ℃, keeping the temperature for 10 hours, and then cooling to 893 ℃ to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 7 ℃/h, and crystallizing to obtain seed crystals;
growing crystals on the surface of the compound melt: rb to be cut along an arbitrary axis6Si10O23Fixing a crystal at the lower end of a seed rod by a platinum wire, guiding the seed crystal into a crucible from a small hole at the top of the furnace to be in contact with the liquid level, cooling to 891 ℃ at the speed of 8 ℃/day, and pulling the crystal upwards at the speed of 10mm/h without rotating the seed crystal;
after the crystal growth is finished, the crystal is separated from the liquid level, the temperature is reduced to the room temperature at the speed of 9 ℃/h, and then the crystal is slowly taken out from the hearth, thus obtaining the transparent rubidium silicate nonlinear optical crystal with the size of 25mm multiplied by 30 mm.
Example 7
According to the reaction formula H2Si2O5+Rb2O→Rb6Si10O23+H2O ↓syntheticRb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by Czochralski method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of phi 150mm multiplied by 150mm, heating to melt, heating to 1200 ℃, keeping the temperature for 60 hours, and then cooling to 898 ℃ to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 3 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
growing crystals on the surface of the compound melt: rb to be cut along an arbitrary axis6Si10O23Fixing seed crystals at the lower end of a seed crystal rod by using a platinum wire, guiding the seed crystals into a crucible from a small hole at the top of the furnace to enable the seed crystals to be in contact with the liquid level, rapidly cooling to 887 ℃ at a speed of 4 ℃/day, keeping the temperature constant, rotating the seed crystal rod at a rotating speed of 15rpm, and upwards pulling the crystals at a speed of 12 mm/h;
after the crystal growth is finished, the crystal is separated from the liquid level, the temperature is reduced to the room temperature at the speed of 100 ℃/h, and then the crystal is slowly taken out from the hearth, so that the transparent rubidium silicate nonlinear optical crystal with the size of 30mm multiplied by 40mm multiplied by 25mm can be obtained.
Example 8
According to the reaction formula SiO2+Rb2O→Rb6Si10O23Synthesis of Rb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by crucible moving method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of 80mm × 80mm, heating to melt, heating to 1150 deg.C, holding the temperature for 20 hr, and cooling to 900 deg.C to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23The melt is slowly cooled at the speed of 2 ℃/hCooling to room temperature, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
putting seed crystal at the bottom of a platinum crucible with a conical sharp corner, and synthesizing Rb6Si10O23Putting the polycrystalline powder into a crucible, putting the crucible into a vertical heating furnace, heating to 950 ℃, preserving heat for 10 hours, keeping the heating power constant, and then moving the crucible downwards at the speed of 1mm/d to enable the melt to be solidified and crystallized from bottom to top;
after the crystallization is finished, the temperature is reduced to the room temperature at the speed of 20 ℃/h, and the crucible is slowly taken out of the hearth, so that the rubidium silicate nonlinear optical crystal with the size of 10mm multiplied by 40mm can be obtained.
Example 9
According to the reaction formula Rb2C2O4·H2O+SiO2+O2→Rb6Si10O23+CO2↑+H2O ↓syntheticRb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by crucible moving method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of 60mm × 60mm, heating to melt, heating to 1000 deg.C, holding the temperature for 60 hr, cooling to 895 deg.C to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 5 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
putting seed crystal at the bottom of a platinum crucible with a conical sharp corner, and synthesizing Rb6Si10O23Putting the polycrystalline powder into a crucible, putting the crucible into a vertical heating furnace, heating to 1000 ℃, preserving heat for 20 hours and keeping the heating power constant, and then moving the crucible downwards at the speed of 3mm/d to enable the melt to be solidified and crystallized from bottom to top;
after the crystallization is finished, the temperature is reduced to the room temperature at the speed of 5 ℃/h, and the crucible is slowly taken out of the hearth, so that the rubidium silicate nonlinear optical crystal with the size of 15mm multiplied by 14mm multiplied by 30mm can be obtained.
Example 10
According to the reaction formula RbCl + SiO2+O2→Rb6Si10O23+Cl2↓ [ O ] synthetic Rb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by crucible moving method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of 40mm × 40mm, heating to melt, heating to 980 deg.C, holding for 30 hr, cooling to 890 deg.C to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 1.5 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
putting seed crystal at the bottom of a platinum crucible with a conical sharp corner, and synthesizing Rb6Si10O23Putting the polycrystalline powder into a crucible, putting the crucible into a vertical heating furnace, heating to 980 ℃, preserving heat for 120h and keeping the heating power constant, and then moving the crucible downwards at the speed of 8mm/d to enable the melt to be solidified and crystallized from bottom to top;
after the crystallization is finished, the temperature is reduced to the room temperature at the speed of 10 ℃/h, and the crucible is slowly taken out of the hearth, so that the rubidium silicate nonlinear optical crystal with the size of 18mm multiplied by 16mm multiplied by 23mm can be obtained.
Example 11
According to the reaction formula H4SiO4+RbOH→Rb6Si10O23+H2O ↓andRb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by crucible moving method6Si10O23Crystal
Synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of phi 50mm multiplied by 50mm, heating to melt, heating to 1050 ℃, keeping the temperature for 70 hours, and then cooling to 910 ℃ to obtain Rb6Si10O23Melting the materials;
will obtain Rb6Si10O23Slowly cooling the melt to room temperature at the speed of 7 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
putting seed crystal at the bottom of a platinum crucible with a conical sharp corner, and synthesizing Rb6Si10O23Putting the polycrystalline powder into a crucible, putting the crucible into a vertical heating furnace, heating to 960 ℃, preserving heat for 120h and keeping the heating power constant, and then moving the crucible downwards at the speed of 10mm/d to enable the melt to be solidified and crystallized from bottom to top;
after the crystallization is finished, the temperature is reduced to the room temperature at the speed of 12 ℃/h, and the crucible is slowly taken out of the hearth, so that the rubidium silicate nonlinear optical crystal with the size of 11mm multiplied by 14mm multiplied by 20mm can be obtained.
Example 12
According to the reaction formula H2Si2O5+RbNO3→Rb6Si10O23+NO2↑+H2O↑+O2↓ [ O ] synthetic Rb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by crucible moving method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of phi 30mm multiplied by 30mm, heating to melt, heating to 1080 ℃, keeping the temperature for 15 hours, and then cooling to 905 ℃ to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 0.5 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
putting seed crystal at the bottom of a platinum crucible with a conical sharp corner, and synthesizing Rb6Si10O23Putting the polycrystalline powder into a crucible, putting the crucible into a vertical heating furnace, heating to 970 ℃, preserving the temperature for 120h and keeping the heating power constant, and then moving the crucible downwards at the speed of 4mm/d to enable the melt to be solidified and crystallized from bottom to top;
after the crystallization is finished, the temperature is reduced to the room temperature at the speed of 14 ℃/h, and the crucible is slowly taken out of the hearth, so that the rubidium silicate nonlinear optical crystal with the size of 9mm multiplied by 10mm multiplied by 15mm can be obtained.
Example 13
According to the reaction formula SiO2+RbNO3→Rb6Si10O23+NO2↑+O2↓ [ O ] synthetic Rb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by crucible moving method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of 35mm × 35mm, heating to melt, heating to 985 deg.C, holding the temperature for 15 hr, and cooling to 912 deg.C to obtain Rb6Si10O23Melting the materials;
will give Rb6Si10O23Slowly cooling the melt to room temperature at the speed of 9 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
putting seed crystal at the bottom of a platinum crucible with a conical sharp corner, and synthesizing Rb6Si10O23Putting polycrystalline powder into a crucible, putting the crucible into a vertical heating furnace, heating to 965 ℃, preserving heat for 17 hours and keeping the heating power constant, and then moving the crucible downwards at the speed of 6mm/d to solidify and crystallize a melt from bottom to top;
after the crystallization is finished, the temperature is reduced to the room temperature at the speed of 16 ℃/h, and the crucible is slowly taken out of the hearth, thus obtaining the rubidium silicate nonlinear optical crystal with the size of 11mm multiplied by 12mm multiplied by 21 mm.
Example 14
According to the reaction formula RbF + SiO2+O2→Rb6Si10O23+F2↓ [ O ] synthetic Rb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by crucible moving method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of 40mm × 40mm, heating to melt, heating to 990 deg.C, holding for 3 hr, cooling to 905 deg.C to obtain Rb6Si10O23Melting the materials;
will give Rb6Si10O23Slowly cooling the melt to room temperature at the speed of 3.5 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
putting seed crystal at the bottom of a platinum crucible with a conical sharp corner, and synthesizing Rb6Si10O23Putting the polycrystalline powder into a crucible, putting the crucible into a vertical heating furnace, heating to 955 ℃, preserving the heat for 13h, keeping the heating power constant, and then moving the crucible downwards at the speed of 0.1mm/d to enable the melt to be solidified and crystallized from bottom to top;
after the crystallization is finished, the temperature is reduced to the room temperature at the speed of 9 ℃/h, and the crucible is slowly taken out of the hearth, so that the rubidium silicate nonlinear optical crystal with the size of 13mm multiplied by 5mm can be obtained.
Example 15
According to the reaction formula H2Si2O5+RbOH→Rb6Si10O23+H2O ↓syntheticRb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by crucible moving method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with an opening diameter of 30mm × 30mm, heating to melt, heating to 1020 deg.C, holding for 19 hr, cooling to 913 deg.C to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 7.5 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
putting seed crystal at the bottom of a platinum crucible with a conical sharp corner, and synthesizing Rb6Si10O23Putting the polycrystalline powder into a crucible, putting the crucible into a vertical heating furnace, heating to 967 ℃, preserving heat for 24 hours and keeping the heating power constant, and then moving the crucible downwards at the speed of 1.5mm/d to enable the melt to be solidified and crystallized from bottom to top;
after the crystallization is finished, the temperature is reduced to the room temperature at the speed of 19 ℃/h, and the crucible is slowly taken out of the hearth, so that the rubidium silicate nonlinear optical crystal with the size of 12mm multiplied by 13mm multiplied by 9mm can be obtained.
Example 16
According to the reaction formula SiO2+RbCH3COO+O2→Rb6Si10O23+CO2↓ [ O ] synthetic Rb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by crucible moving method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of 25mm × 25mm, heating to melt, heating to 1130 deg.C, holding for 48 hr, cooling to 915 deg.C to obtain Rb6Si10O23Melting the materials;
rb to be obtained6Si10O23Slowly cooling the melt to room temperature at the speed of 2 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
putting seed crystal at the bottom of a platinum crucible with a conical sharp corner, and synthesizing Rb6Si10O23Putting the polycrystalline powder into a crucible, putting the crucible into a vertical heating furnace, heating to 985 ℃, keeping the temperature for 96 hours and keeping the heating power constant, and then moving the crucible downwards at the speed of 1.5mm/d to enable the melt to be solidified and crystallized from bottom to top;
after the crystallization is finished, the temperature is reduced to the room temperature at the speed of 11 ℃/h, and the crucible is slowly taken out of the hearth, so that the rubidium silicate nonlinear optical crystal with the size of 10mm multiplied by 13mm multiplied by 19mm can be obtained.
Example 17
According to the reaction formula SiO2+RbOH→Rb6Si10O23+H2O ↓syntheticRb6Si10O23Compounds, the specific procedure was carried out according to example 1;
preparation of Rb by crucible moving method6Si10O23Crystal:
synthesized Rb6Si10O23Placing the compound into a platinum crucible with a diameter of phi 50mm × 50mm, heating to melt, heating to 1070 deg.C, holding the temperature for 90 hr, and cooling to 911 deg.C to obtain Rb6Si10O23Melting the materials;
will give Rb6Si10O23Slowly cooling the melt to room temperature at the speed of 6 ℃/h, and obtaining small crystals as seed crystals by using a platinum wire suspension method during cooling;
putting seed crystal at the bottom of a platinum crucible with a conical sharp corner, and synthesizing Rb6Si10O23Putting the polycrystalline powder into a crucible, putting the crucible into a vertical heating furnace, heating to 1000 ℃, keeping the temperature for 96 hours and keeping the heating power constant, and then moving the crucible downwards at the speed of 8.5mm/d to enable the melt to be solidified and crystallized from bottom to top;
after the crystallization is finished, the temperature is reduced to the room temperature at the speed of 15 ℃/h, and the crucible is slowly taken out of the hearth, so that the rubidium silicate nonlinear optical crystal with the size of 12mm multiplied by 13mm multiplied by 30mm can be obtained.
Example 18:
any one of Rb obtained in examples 1 to 17 was used6Si10O23A frequency doubling device with the size of 4mm multiplied by 8mm is processed by a nonlinear optical crystal according to the matching direction, the frequency doubling device is arranged at the position 3 according to the figure 3, a Q-switched Nd YAG laser is used as a light source at room temperature, the incident wavelength is 1064nm, an infrared beam 2 with the wavelength of 1064nm is emitted by the Q-switched Nd YAG laser 1 and enters Rb6Si10O23Single crystal 3, producing a wavelength of 532nmThe green frequency doubling light, the emergent light beam 4 contains infrared light with the wavelength of 1064nm and green light with the wavelength of 532nm, and the infrared light component is filtered by the filter 5 to obtain green laser with the wavelength of 532 nm.

Claims (2)

1. A method for preparing rubidium silicate nonlinear optical crystal is characterized in that the molecular formula of the crystal is Rb6Si10O23Molecular weight of 1161.65, space group ofAmm2, unit cell parameters are:a = 8.049(6) Å,b = 16.227(13) Å ,c = 9.385(7) Å,Z = 2, V =1225.8(16) Å3the crystal is grown by a pulling method or a crucible moving method in a melt method, and the specific operation is carried out according to the following steps:
a. uniformly mixing an Rb-containing compound and a Si-containing compound according to the molar ratio Rb: Si =6:10, putting the mixture into a mortar, carefully grinding the mixture, then putting the mixture into an open corundum crucible with the diameter of 100mm multiplied by 100mm, compacting the mixture, putting the crucible into a muffle furnace, slowly heating the mixture to 700 ℃, keeping the temperature for 24 hours, taking out the crucible after cooling, taking out the sample which is loose, taking out the sample, uniformly grinding the sample again, putting the sample into the crucible, keeping the temperature for 48 hours in the muffle furnace at 800 ℃, taking out the sample, putting the sample into the mortar, smashing and grinding the Rb-containing compound to obtain the Rb-containing corundum crucible6Si10O23Polycrystalline powder, and subjecting the product to X-ray analysis to obtain X-ray spectrogram and Rb product6Si10O23The X-ray spectrogram of the single crystal after being ground into powder is consistent, wherein the rubidium-containing compound is Rb2O、Rb2CO3、RbNO3、Rb2C2O4·H2O、RbOH、RbC2H3O2RbF or RbCl; the silicon-containing compound is H2SiO3、SiO2、H4SiO4Or H2Si2O5；
b. B, reacting Rb obtained in step a6Si10O23The polycrystalline powder is heated in a crucible to be melted, the temperature is 950-6Si10O23Melting the materials;
c. subjecting the product obtained in step bRb6Si10O23Slowly cooling the melt to room temperature at the speed of 0.5-10 ℃/h, crystallizing to obtain seed crystals or obtaining small crystals as the seed crystals by using a platinum wire suspension method during cooling;
d. adopting a pulling method to grow crystals on the surface of the melt or in the melt: fixing the seed crystal in the step c on a seed crystal rod, contacting the seed crystal from the top with the surface of the melt in the step b, cooling at the rate of 0.1-10 ℃/day or directly, cooling to 880 plus 900 ℃, rotating the seed crystal rod or the rotating crucible at the rotating speed of 0-100rpm, pulling up the crystal at the speed of 0-15mm/h, increasing the pulling speed after the growth of the single crystal is stopped, separating the crystal from the liquid level of the melt, cooling to room temperature at the rate of 1-100 ℃/h, and then slowly taking out the crystal from the furnace chamber to obtain the rubidium silicate nonlinear optical crystal;
or growing the crystal in the melt by using a crucible moving method: placing the seed crystal prepared in the step c at the bottom of the crucible, and then placing the Rb prepared in the step a6Si10O23Putting polycrystalline powder into a crucible, sealing the platinum crucible, heating the growth furnace to 950-1000 ℃, keeping the temperature for 10-120 hours, adjusting the position of the crucible to slightly melt the seed crystal, then reducing the crucible at the speed of 0.1-10 mm/day, simultaneously keeping the growth temperature unchanged, and after the growth is finished, rapidly reducing the temperature to the room temperature at the speed of 5-20 ℃/h to obtain the Rb-Al-Si-Al alloy material6Si10O23A nonlinear optical crystal.
2. Use of rubidium silicate nonlinear optical crystal obtained by the method according to claim 1 for the preparation of a frequency doubling generator.
CN202010493030.6A 2020-06-03 2020-06-03 Preparation method and application of rubidium silicate nonlinear optical crystal Active CN111501100B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010493030.6A CN111501100B (en) 2020-06-03 2020-06-03 Preparation method and application of rubidium silicate nonlinear optical crystal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010493030.6A CN111501100B (en) 2020-06-03 2020-06-03 Preparation method and application of rubidium silicate nonlinear optical crystal

Publications (2)

Publication Number Publication Date
CN111501100A CN111501100A (en) 2020-08-07
CN111501100B true CN111501100B (en) 2021-07-16

Family

ID=71873613

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010493030.6A Active CN111501100B (en) 2020-06-03 2020-06-03 Preparation method and application of rubidium silicate nonlinear optical crystal

Country Status (1)

Country Link
CN (1) CN111501100B (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0017516D0 (en) * 2000-07-17 2000-08-30 Isis Innovation Nonlinear optical materials
CN104018225B (en) * 2014-06-11 2017-01-18 山东大学 Neodymium-doped A3BGa3Si2O14 series crystal and preparation method and application thereof
CN107974711A (en) * 2016-10-25 2018-05-01 中国科学院新疆理化技术研究所 Zinc strontium silicate nonlinear optical crystal and its preparation method and application

Also Published As

Publication number Publication date
CN111501100A (en) 2020-08-07

Similar Documents

Publication Publication Date Title
CN110042467B (en) Compound lithium rubidium germanate and lithium rubidium germanate nonlinear optical crystal as well as preparation method and application thereof
CN106894085B (en) Compound fluoboric acid caesium and fluoboric acid caesium nonlinear optical crystal and preparation method and purposes
CN101876772B (en) Compound potassium lead borophosphate nonlinear optical crystal as well as preparation method and application thereof
CN102337586B (en) Compound barium borofluoride nonlinear optical crystal as well as preparation method and purposes thereof
CN101311370B (en) Large-sized bismuth zinc borate nonlinear optical crystal, preparation method and use
CN103628136B (en) Compound boron phosphoric acid rubidium is plumbous and boron phosphoric acid rubidium lead nonlinear optical crystal and preparation method and purposes
CN106868587B (en) Lithium rubidium barium aluminum boron oxygen fluorine and lithium rubidium barium aluminum boron oxygen fluorine nonlinear optical crystal, preparation method and application
CN107628629B (en) Compound cesium rubidium fluoroborate, nonlinear optical crystal of cesium rubidium fluoroborate, preparation method and application
CN110029397B (en) Compound lithium cesium germanate and lithium cesium germanate nonlinear optical crystal as well as preparation method and application thereof
CN113737282A (en) Compound zinc-rubidium germanate nonlinear optical crystal and preparation method and application thereof
CN110468445B (en) Cesium barium borate nonlinear optical crystal and preparation method and application thereof
CN114232093A (en) Compound zinc calcium borate, zinc calcium borate nonlinear optical crystal, preparation method and application
CN111501100B (en) Preparation method and application of rubidium silicate nonlinear optical crystal
CN106192005B (en) Compound lithium phosphate caesium nonlinear optical crystal and preparation method and purposes
CN103628135B (en) Compound phospho-molybdic acid rubidium and phospho-molybdic acid rubidium non-linear optic crystal and preparation method and purposes
CN110143610A (en) Compound lithium potassium titanium germanate and lithium potassium titanium germanate nonlinear optical crystal and preparation method and purposes
CN107217301B (en) Compound lithium fluoroborate potassium and lithium fluoroborate nonlinear optical crystal of potassium and preparation method and purposes
CN110408995B (en) Compound lead strontium silicate, lead strontium silicate nonlinear optical crystal, preparation method and application
CN109763169B (en) Potassium lutetium borate nonlinear optical crystal and its preparation method and use
CN103628139B (en) Compound phospho-molybdic acid caesium and phospho-molybdic acid caesium non-linear optic crystal and preparation method and purposes
CN106283193A (en) Bromine gallium barium borate sodium and bromine gallium barium borate sodium nonlinear optical crystal and preparation method and purposes
Li et al. Crystal growth of Na5 [B2P3O13]
CN106811800B (en) Lithium aluminosilicate nonlinear optical crystal and its preparation method and application
CN115198343B (en) Scandium rubidium lithium fluosilicate nonlinear optical crystal and preparation method and application thereof
CN1379125A (en) Non-linear optical crystal of magnesium zinc bromophosphate and its preparing process and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant